Upper layer film-forming composition and method for manufacturing phase separation pattern

Abstract

Provided is an upper layer film-forming composition which exhibits good solubility in hydrophobic solvents and can bring about vertical alignment of a block copolymer without dissolution, swelling or the like of a layer containing the block copolymer formed on a substrate. This upper layer film-forming composition is used for phase separation of a layer containing a block copolymer formed on a substrate, and contains: (A) a copolymer containing a unit structure derived from a maleimide structure (a) and a unit structure derived from a styrene structure; and (B) as a solvent, a non-aromatic hydrocarbon compound that is a liquid at normal temperature and pressure.

Description

Technical Field

[0001] The present invention relates to an upper layer film forming composition and a method for manufacturing a phase separation pattern.

Background Art

[0002] In a technique of subjecting a substrate formed with a block copolymer layer on a substrate such as a semiconductor substrate to phase separation, removing a part of the block copolymer, and then subjecting the substrate to etching, a technique of providing an upper layer film on the block copolymer layer and performing thermal annealing or the like to control to a desired lithography pattern is well known (Patent Document 1). However, conventional upper layer films dissolve rapidly in hydrophilic solvents such as water, methanol, and isopropyl alcohol, but do not show high solubility in hydrophobic solvents. As a means showing high solubility in such hydrophobic solvents, a method using an ether-based solvent such as diisoamyl ether is known (Patent Document 2). On the other hand, in recent years, further densification of lithography patterns has been required, and even for hydrophobic solvents, there has been a concern that an ether-based solvent such as diisoamyl ether may dissolve a block copolymer that meets such requirements.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] Therefore, there is a long-awaited development of an upper layer film forming composition that can cause a vertical alignment of a block copolymer without dissolving or swelling a layer containing the block copolymer formed on a substrate, and provides an upper layer film showing good solubility in a hydrophobic solvent.

Means for Solving the Problem

[0005] The present invention includes the following. [1] An upper layer film forming composition used for phase-separating a layer containing a block copolymer formed on a substrate, (A) A copolymer containing a unit structure derived from a maleimide structure and a unit structure derived from a styrene structure, (B) As a solvent, a non-aromatic hydrocarbon compound that is liquid at normal temperature and pressure and an upper layer film forming composition containing the same. [2] The upper layer film forming composition according to [1], wherein the solvent is a non-aromatic hydrocarbon compound having 4 to 26 carbon atoms. [3] The upper layer film forming composition according to [1] or [2], wherein the solvent is an acyclic hydrocarbon compound or a cyclic hydrocarbon compound. [4] The upper layer film forming composition according to [3], wherein the acyclic hydrocarbon compound is a saturated straight-chain, unsaturated straight-chain, saturated branched-chain, or unsaturated branched-chain hydrocarbon compound. [5] The upper layer film forming composition according to [3], wherein the cyclic hydrocarbon compound is a monocyclic compound having a substituent, or a bicyclic or condensed ring compound that may have a substituent. [6] The upper layer film forming composition according to [3], wherein the cyclic hydrocarbon compound is a cyclic hydrocarbon compound having 6 to 19 carbon atoms. [7] The unit structure derived from the maleimide structure is represented by the formula (1):

Chemical formula

Chemical formula

[10] The unit structure derived from the (meth)acrylic group is represented by formula (3):

Chemical formula

[11] Formula (4):

Chemical formula

Chemical formula

[10] , comprising a copolymer (A) obtained by copolymerizing a monomer mixture containing a compound represented by .

[12] (1) A step of forming a block copolymer layer on a substrate, (2) A step of forming an upper layer film using the composition according to any one of [1] to

[11] on the block copolymer layer, and (3) A step of phase-separating the block copolymer layer formed on the substrate, A method for forming a phase separation pattern of a block copolymer, comprising the above steps.

[13] (1) A step of forming a block copolymer layer on a substrate, (2) A step of forming an upper layer film using the composition according to any one of [1] to

[11] on the block copolymer layer, (3) A step of phase-separating the block copolymer layer formed on the substrate, and (4) A step of etching the phase-separated block copolymer layer, A pattern manufacturing method, comprising the above steps.

[14] (1) A step of forming a block copolymer layer on a substrate, (2) A step of forming an upper layer film using the composition according to any one of [1] to

[11] on the block copolymer layer, (3) A step of phase-separating the block copolymer layer formed on the substrate, and (4) A step of etching the phase-separated block copolymer layer, (5) A step of etching the substrate, A method for manufacturing a semiconductor device, comprising the above steps. [Advantages of the Invention]

[0006] The upper layer film produced using the upper layer film forming composition of the present invention exhibits good solubility in a hydrophobic solvent that does not dissolve the block copolymer and can cause a vertical alignment of the block copolymer.

Brief Description of Drawings

[0007]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0008] [1. Upper layer film forming composition] The upper layer film forming composition according to the present invention is an upper layer film forming composition used for phase-separating a layer containing a block copolymer formed on a substrate, (A) A copolymer containing a unit structure derived from a maleimide structure and a unit structure derived from a styrene structure, and (B) As a solvent, a non-aromatic hydrocarbon compound that is liquid at normal temperature and pressure and is an upper layer film forming composition. This composition can be used as an upper layer film forming composition that is formed on a block copolymer thin film, controls the orientation of the above block copolymer by heating, and then is removed. Even for a block copolymer layer that cannot be oriented by heating alone, orientation becomes possible by using the upper layer film formed by this composition.

[0009] [(A) Copolymer] [(a) A copolymer containing a unit structure derived from a maleimide structure and a unit structure derived from a styrene structure]

[0010] As used herein, the "maleimide structure" and the "styrene structure" each refer to a chemical structure having maleimide and styrene as the backbone, respectively. The "derived unit structure" refers to a repeating unit forming the main chain of a copolymer, which is derived from a compound having the maleimide structure or the styrene structure while maintaining its backbone.

[0011] Preferably, the unit structure derived from the maleimide structure is represented by the formula (1):

Chemical formula

[0012] Preferably, the unit structure derived from the styrene structure is represented by the formula (2):

Chemical formula

[0013] The molar ratio of the unit structures represented by formula (1) and formula (2) to the entire copolymer (A) is, with respect to the entire copolymer (A), Structural unit of formula (1): 30 to 70 mol% Structural unit of formula (2): 20 to 50 mol% which is preferably the case.

[0014] [(b) Unit structure derived from (meth)acrylic group] Furthermore, in addition to the units represented by formula (1) and formula (2), the copolymer (A) may contain a unit structure derived from a (meth)acrylic group. In the present invention, the (meth)acrylic group means both an acrylic group and a methacrylic group. The (meth)acrylate compound means both an acrylate compound and a methacrylate compound. For example, (meth)acrylic acid means acrylic acid and methacrylic acid.

[0015] Preferably, the unit structure derived from the (meth)acrylic group is represented by formula (3):

Chemical formula

[0016] The molar ratio of the unit structure of formula (3) to the entire copolymer (A) is 0.1 to 50 mol%, more preferably 0.1 to 30 mol%, still more preferably 0.1 to 20 mol%, and most preferably 0.1 to 10 mol% based on the entire copolymer (A).

[0017] In the above formulas (1), (2), and (3), examples of the linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a 1,1-diethyl-n-propyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a 2-ethyl-cyclopropyl group, an n-hexyl group, a 1-methyl-n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, a 1-ethyl-2-methyl-n-propyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group, a 2-methyl-cyclopentyl group, a 3-methyl-cyclopentyl group, a 1-ethyl-cyclobutyl group, a 2-ethyl-cyclobutyl group, a 3-ethyl-cyclobutyl group, a 1,2-dimethyl-cyclobutyl group, a 1,3-dimethyl-cyclobutyl group, a 2,2-dimethyl-cyclobutyl group, a 2,3-dimethyl-cyclobutyl group, a 2,4-dimethyl-cyclobutyl group, a 3,3-dimethyl-cyclobutyl group, a 1-n-propyl-cyclopropyl group, a 2-n-propyl-cyclopropyl group, a 1-i-propyl-cyclopropyl group, a 2-i-propyl-cyclopropyl group, a 1,2,2-trimethyl-cyclopropyl group, a 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, n-heptyl group, 1-methyl-n-heptyl group, n-octyl group, 1-methyl-n-octyl group, n-nonyl group, 1-methyl-n-nonyl group, n-decanyl group, 2-oxohexahydro-2H-3,5-methanocyclopenta[b]furan-6-yl group, 1-adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 2-isopropyl-2-adamantyl group, 3-hydroxy-1-adamantyl group and isobornyl group etc. may be mentioned.,

[0018] In the above formulas (1), (2) and (3), examples of the aryl group having 6 to 10 carbon atoms include phenyl group, benzyl group, naphthyl group etc.,

[0019] In the above formulas (1), (2) and (3), examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, cyclopropoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, cyclobutoxy group, 1-methyl-cyclopropoxy group, 2-methyl-cyclopropoxy group, n-pentoxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, 1,1-diethyl-n-propoxy group, cyclopentoxy group, 1-methyl-cyclobutoxy group, 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group, 1-ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group etc.,

[0020] Examples of the halogen atom include F, Cl, Br and I.,

[0021] The distribution of the unit structures represented by formulas (1), (2), and (3) in the copolymer (A) is not particularly limited. That is, in the copolymer (A), the unit structures represented by formulas (1) and (2) may be alternately copolymerized or randomly copolymerized. Further, when the unit structure represented by formula (3) coexists, the unit structures represented by formulas (1), (2), and (3) in the copolymer (A) may each form a block or may be randomly bonded.

[0022] The number of repetitions of the unit structures represented by formulas (1), (2), and (3) in the copolymer (A) is within the range of the mol% of each of the above-mentioned unit structures, and can be appropriately selected within the range where the weight-average molecular weight Mw of the copolymer (A) is usually 5,000 to 500,000, preferably 5,000 to 100,000, more preferably 5,000 to 50,000.

[0023] [Method for producing copolymer (A)] The method for producing the copolymer (A) used in the present invention is a compound represented by formula (4): [Chemical formula] (In formula (4), R 1 represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom), and a compound represented by formula (5): [Chemical formula] (In formula (5), R 2 to R 4 , R 7 and R 8 each independently represent a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. The method includes a step of copolymerizing a monomer mixture containing a compound represented by. R 7 and R 8 are preferably hydrogen atoms.

[0024] The monomer mixture may optionally contain a compound of formula (6):

Chemical formula

[0025] The "linear, branched or cyclic alkyl group having 1 to 15 carbon atoms", "aryl group having 6 to 10 carbon atoms", "alkoxy group having 1 to 5 carbon atoms", and "halogen atom" are as described above.

[0026] The above monomer mixture contains the compounds represented by formula (4) and formula (5) in a proportion of Compound represented by formula (4): 30 to 70 mol% Compound represented by formula (5): 20 to 50 mol% preferably.

[0027] When containing the compound represented by formula (6), the above monomer mixture contains the compound represented by formula (4) in a proportion of Compound represented by formula (4): 30 to 70 mol% Compound represented by formula (5): 20 to 50 mol% Compound represented by formula (6): 0.1 to 40 mol% preferably.

[0028] Specific examples of the compound represented by formula (4) include the following.

Chemical formula

[0029] Specific examples of the compound represented by formula (5) include the following.

Chem.

Chem.

[0030] Specific examples of the compound represented by formula (6) include the following.

Chem.

Chem.

Chem.

[0031] The copolymer (A) can be obtained by a known polymerization method. Examples of the known polymerization method include radical polymerization, anionic polymerization, cationic polymerization, etc. Various known techniques such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization can be used.

[0032] As the polymerization initiator used during polymerization, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(2-methylpropionamidine) dihydrochloride, etc. are used.

[0033] As the solvent used during polymerization, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxysuccinate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, etc. can be used. These can be used alone or in combination.

[0034] The reaction conditions are to carry out a stirring reaction at 50°C to 200°C for 1 hour to 48 hours to obtain the copolymer (A) used in the present invention.

[0035] The solution containing the copolymer (A) thus obtained can be used as it is for the preparation of the upper layer film-forming composition. Also, the copolymer (A) can be precipitated and isolated in a poor solvent such as methanol, ethanol, isopropanol, water, or a mixed solvent thereof, and then recovered and used.

[0036] After isolating the copolymer (A), it may be redissolved directly in a liquid non-aromatic hydrocarbon compound at normal temperature and pressure as described below for use, or it may be dried before use. When drying, the drying conditions are desirably 30 to 100°C for 6 to 48 hours in an oven or the like. After recovering the copolymer (A), it is redissolved in a liquid non-aromatic hydrocarbon compound at normal temperature and pressure as described below to prepare the composition of the present invention and can be used as an upper layer film-forming composition.

[0037] The weight average molecular weight of the copolymer (A) used in the present invention measured by gel permeation chromatography (GPC) varies depending on the coating solvent used, solution viscosity, etc., but is usually 5,000 to 500,000 in terms of polystyrene conversion, preferably 5,000 to 100,000, more preferably 5,000 to 50,000.

[0038] [(B) Solvent] The solvent used in the composition of the present invention is a non-aromatic hydrocarbon compound that is liquid at normal temperature and pressure. More specifically, the non-aromatic hydrocarbon compound (hereinafter sometimes referred to as "non-aromatic hydrocarbon solvent") that is liquid at normal temperature and pressure and used as a solvent in the composition of the present application is as follows. Preferably, the non-aromatic hydrocarbon compound that is liquid at normal temperature and pressure is a non-aromatic hydrocarbon compound having 4 to 26 carbon atoms. Preferably, the non-aromatic hydrocarbon compound that is liquid at normal temperature and pressure is an acyclic hydrocarbon compound or a cyclic hydrocarbon compound. Preferably, the acyclic hydrocarbon compound is a saturated straight-chain hydrocarbon compound (SLC), an unsaturated straight-chain hydrocarbon compound (ULC), a saturated branched-chain hydrocarbon compound (SBC), or an unsaturated branched-chain hydrocarbon compound (UBC). Preferably, the cyclic hydrocarbon compound is a monocyclic compound with a substituent (S1R), a bicyclic compound with a substituent (S2R), a condensed-ring compound with a substituent (SFR), a bicyclic compound without a substituent (U2R), or a condensed-ring compound without a substituent (UFR).

[0039] The substituent is not particularly limited, but is preferably a straight-chain, branched or cyclic alkyl, alkenyl or alkynyl group having 1 to 12 carbon atoms, or a halogen atom.

[0040] Examples of the linear, branched or cyclic alkyl, alkenyl or alkynyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, 1,1-diethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples include 3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, n-heptyl group, 1-methyl-n-heptyl group, n-octyl group, 1-methyl-n-octyl group, n-nonyl group, 1-methyl-n-nonyl group, n-decanyl group, vinyl group, ethynyl group, allyl group, isopropenyl group, propylidene group, and isopropylidene group, etc.

[0041] Examples of the halogen atom include F, Cl, Br, and I.

[0042] Preferably, the cyclic hydrocarbon compound is a cyclic hydrocarbon compound having 6 to 19 carbon atoms. In this case, the number of carbon atoms includes the number of carbon atoms of the substituent.

[0043] Specific examples of the saturated straight-chain hydrocarbon compound (SLC) include alkanes having 4 to 14 carbon atoms typified by n-octane, n-nonane, n-decane, etc.

[0044] Specific examples of the unsaturated straight-chain hydrocarbon compound (ULC) include the following compounds having 4 to 14 carbon atoms. [Chemical formula]

[0045] Specific examples of the saturated branched-chain hydrocarbon compound (SBC) include the following compounds having 5 to 26 carbon atoms. [Chemical formula]

[0046] Specific examples of the saturated straight-chain hydrocarbon compound (SLC) include the following compounds having 6 to 16 carbon atoms. [Chemical formula]

[0047] Specific examples of the unsaturated branched-chain hydrocarbon compound (UBC) include the following compounds.

Chemical formula

[0048] Specific examples of the monocyclic compound (S1R) having a substituent include the following compounds having 6 to 19 carbon atoms.

Chemical formula

[0049] Specific examples of the bicyclic compound (U2R) having no substituent include the following compounds.

Chemical formula

[0050] Specific examples of the condensed-ring compound (UFR) having no substituent include the following compounds.

Chemical formula

[0051] Among these, preferred solvents include saturated straight-chain hydrocarbon compounds having 8 to 10 carbon atoms and monocyclic compounds having 7 to 10 carbon atoms and having a substituent, which are excellent in the balance between the solubility of the copolymer (A) and the insolubility of the block copolymer of the present application. Particularly preferred solvents are saturated straight-chain hydrocarbon compounds having 8 carbon atoms, saturated straight-chain hydrocarbon compounds having 10 carbon atoms, and cyclohexane having a substituent (for example, 1-methyl-4-isopropylcyclohexane). These solvents can be used alone or as a mixture.

[0052] Also, for convenience in synthesizing the copolymer (A) used in the present invention, the following organic solvents may be mixed with the non-aromatic hydrocarbon solvent. Such solvents are, for example, those listed in the section on the method for producing the copolymer (A) described above. Solvents other than the non-aromatic hydrocarbon solvent may be present in a proportion of 0.01 to 13% by mass relative to the non-aromatic hydrocarbon solvent.

[0053] [Additive] The upper layer film-forming composition according to the present invention may further contain additives such as surfactants and rheology modifiers.

[0054] In addition to the above, further rheology modifiers, surfactants, etc. can be added to the upper layer film-forming composition of the present invention as needed. The rheology modifier is mainly added for the purpose of improving the fluidity of the composition of the present invention. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, butyl isodecyl phthalate; adipic acid derivatives such as dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate, octyl decyl adipate; maleic acid derivatives such as dinormal butyl maleate, diethyl maleate, dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, tetrahydrofurfuryl oleate; or stearic acid derivatives such as normal butyl stearate, glyceryl stearate. These rheology modifiers are usually blended in a proportion of less than 30% by mass based on 100% by mass of the whole composition of the present invention.

[0055] In the upper layer film-forming composition of the present invention, in order to prevent the occurrence of pinholes, striations, etc. and further improve the coatability with respect to surface unevenness, a surfactant can be blended. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; nonionic surfactants; fluorine-based surfactants such as F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and Fujent series (manufactured by Neos Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The blending amount of these surfactants is usually 0.2% by mass or less, preferably 0.1% by mass or less, per 100% by mass of the entire upper layer film-forming composition of the present invention. These surfactants may be added alone or in combination of two or more kinds.

[0056] The content of the copolymer (A) in the solid content of the composition is preferably 20% by mass or more, for example, 20 to 100% by mass, or 30 to 100% by mass. The solid content of the composition of the present invention is preferably 0.1 to 50% by mass, more preferably 0.3 to 30% by mass. Here, the solid content is obtained by removing the solvent component from the upper layer film-forming composition.

[0057] The upper layer film-forming composition of the present invention can be produced by mixing the copolymer (A), a non-aromatic hydrocarbon compound that is liquid at normal temperature and pressure as a solvent, and, if necessary, the above additives according to the composition, for example, by stirring and mixing at room temperature to 40°C.

[0058] 2. Method for forming phase separation pattern of block copolymer The upper layer film-forming composition according to the present invention is used for phase-separating a layer containing a block copolymer formed on a substrate.

[0059] The method for forming a phase separation pattern of a block copolymer according to the present invention (1) A step of forming a block copolymer layer on a substrate, (2) A step of forming an upper layer film using the above upper layer film-forming composition on the block copolymer layer, and (3) A step of phase-separating the block copolymer layer formed on the substrate, is included.

[0060] (1) Step of forming a block copolymer layer on a substrate A block copolymer is a polymer (block) in which a plurality of chemically different and covalently bonded polymers are bonded. Regarding block copolymers, many applications have been proposed based on their performance of forming nanometer-scale patterns. For example, the self-assembled pattern of a block copolymer can be used as a nano-lithography mask or a template for further synthesis of inorganic or organic structures. This can be achieved by utilizing the difference in etching rates between the respective blocks.

[0061] The block copolymer used in the present invention includes an organic polymer chain (A) containing an organic monomer (a) as a unit structure, and a polymer chain (B) containing a monomer (b) different from the organic monomer (a) as a unit structure and bonded to the organic polymer chain (A).

[0062] The self-assembled film-forming composition can have a solid content of 0.1 to 10% by mass, or 0.1 to 5% by mass, or 0.1 to 3% by mass. The solid content is the remaining ratio after removing the solvent from the film-forming composition.

[0063] The proportion of the block copolymer in the solid content can be 30 to 100% by mass, or 50 to 100% by mass, or 50 to 90% by mass, or 50 to 80% by mass.

[0064] The number of types of blocks present in the block copolymer can be 2 or 3 or more. And the number of blocks present in the block copolymer can be 2 or 3 or more.

[0065] By changing the polymer chain (B), for example, it is possible to use an adjacent polymer chain (C) containing a monomer (c) as a unit structure.

[0066] Examples of the block polymer include combinations such as AB, ABAB, ABA, and ABC.

[0067] As one method for synthesizing a block copolymer, it can be obtained by living radical polymerization or living cationic polymerization in which the polymerization process consists only of an initiation reaction and a growth reaction and does not involve a side reaction that deactivates the growth terminus. The growth terminus can maintain a growth active reaction during the polymerization reaction. By preventing chain transfer, a polymer (A) with a uniform length can be obtained. By using the growth terminus of this polymer (A) and adding a different monomer (b), polymerization can proceed under this monomer (b) to form a block copolymer (AB).

[0068] For example, when there are two types of blocks, A and B, the molar ratio of polymer chain (A) to polymer chain (B) can be 1:9 to 9:1, preferably 3:7 to 7:3.

[0069] The volume ratio of the block copolymer of the present application is, for example, 30:70 to 70:30.

[0070] The homopolymer A or B is a polymerizable compound having at least one radically polymerizable reactive group (vinyl group or vinyl group-containing organic group).

[0071] The weight-average molecular weight Mw of the block copolymer used in the present invention is 1,000 to 100,000, preferably 5,000 to 100,000, more preferably 5,000 to 50,000, and most preferably 5,000 to 30,000. If it is less than 1,000, the coatability on the base substrate may be poor, and if it is 100,000 or more, the solubility in the solvent may be poor.

[0072] The polydispersity (Mw / Mn) of the block copolymer of the present application is preferably 1.00 to 1.50, and particularly preferably 1.00 to 1.20.

[0073] Specific examples of the block copolymer include, for example, combinations of an aromatic polymer chain and an acrylic resin polymer chain. More specifically, combinations of a poly(vinylpyridine) derivative polymer and a polyacrylate ester derivative polymer such as poly(4-vinylpyridine) and polymethyl methacrylate, combinations of a polyacrylic acid derivative polymer and a polystyrene derivative polymer, or combinations of a poly(hydroxystyrene) derivative polymer and a polyacrylate ester derivative polymer can be mentioned.

[0074] Also, when a silicon-containing polymer chain such as polysilanes such as polydihexylsilane, polysiloxanes such as polydimethylsiloxane, silylated polystyrene derivatives such as poly(trimethylsilylstyrene) and poly(pentamethyldisilylstyrene) is combined with a non-silicon-containing polymer chain, for example, the difference in dry etching rate can be increased, which is preferable. In particular, as the silylated polystyrene derivative, poly(4-trimethylsilylstyrene) and poly(4-pentamethyldisilylstyrene) having a substituent at the 4-position are preferable. Among these, a combination of a silylated polystyrene derivative and a polystyrene derivative polymer, a combination of two different polystyrene derivative polymers, or a combination of a silylated polystyrene derivative polymer and polylactide is preferable. Among these, a combination of a silylated polystyrene derivative having a substituent at the 4-position and a polystyrene derivative polymer having a substituent at the 4-position, a combination of two different polystyrene derivative polymers having a substituent at the 4-position, or a combination of a silylated polystyrene derivative polymer having a substituent at the 4-position and polylactide is preferable.

[0075] More preferable specific examples of the block copolymer include a combination of poly(trimethylsilylstyrene) and polymethoxystyrene, a combination of polystyrene and poly(tert-butylstyrene), a combination of polystyrene and poly(trimethylsilylstyrene), and a combination of poly(trimethylsilylstyrene) and poly(D,L-lactide).

[0076] More preferable specific examples of the block copolymer include a combination of poly(4-trimethylsilylstyrene) and poly(4-methoxystyrene), a combination of polystyrene and poly(4-tert-butylstyrene), a combination of polystyrene and poly(4-trimethylsilylstyrene), and a combination of poly(4-trimethylsilylstyrene) and poly(D,L-lactide).

[0077] The above-mentioned substrate is selected from the group consisting of silicon, silicon oxide, glass, surface-modified glass, plastic, ceramic, transparent substrate, flexible substrate, and substrates used in roll-to-roll processing (or combinations thereof). Preferably, it is a silicon wafer, quartz, glass, or plastic, and more preferably a silicon wafer.

[0078] If necessary, a lower layer film for surface energy neutralization may be provided on the above-mentioned substrate. The lower layer film is applied to have a predetermined film thickness by conventional means such as spin coating on the substrate, and then heated, immersed, etc. if necessary.

[0079] The block copolymer is applied to have a predetermined film thickness by conventional means such as spin coating on the substrate or the lower layer film.

[0080] (2) A step of forming an upper layer film using an upper layer film-forming composition on the block copolymer layer The upper layer film-forming composition is as described above. The thus-prepared upper layer film-forming composition is applied on the block copolymer layer by conventional means such as spin coating, and an upper layer film is formed. The film thickness of the formed upper layer film is not particularly limited, but generally it is 3 nm to 100 nm, preferably 10 - 70 nm, and particularly preferably 20 - 60 nm. If it is less than 3 nm, a desired uniform phase separation pattern of the block copolymer cannot be formed. If it is more than 100 nm, it takes too much time during etching processing, which is not preferable. The upper layer film-forming composition according to the present invention is dissolved in a solvent or a solvent mixture that does not damage, dissolve, or substantially swell the block copolymer, which is extremely advantageous.

[0081] (3) A step of phase-separating the block copolymer layer formed on the substrate The phase separation of the block copolymer layer can be carried out by a process that results in the rearrangement of the block copolymer material in the presence of the upper layer film, for example, ultrasonic treatment, solvent treatment, thermal annealing, etc. In many applications, it is desirable to achieve the phase separation of the block copolymer layer simply by heating or so-called thermal annealing. Thermal annealing can be carried out in the atmosphere or in an inert gas under normal pressure, reduced pressure or pressurized conditions.

[0082] The phase separation of the block copolymer layer forms block copolymer domains oriented substantially perpendicular to the substrate or the lower layer film surface. The form of the domains is, for example, lamellar, spherical, cylindrical, etc. The domain spacing is, for example, 50 nm or less, 40 nm or less, 30 nm or less, or 20 nm or less. According to the method of the present invention, it is possible to form a structure having a desired size, shape, orientation and periodicity.

[0083] The upper layer film can be peeled off after the phase separation of the block copolymer layer. The peeling can be carried out using a solvent or a mixture of solvents (peeling solvent) that does not damage, dissolve or substantially swell the block copolymer. The peeled upper layer film composition can also be isolated and reused. The isolation can be carried out by conventional means such as precipitation, distillation, etc.

[0084] The pattern manufacturing method according to the present invention (1) A step of forming a block copolymer layer on a substrate, (2) A step of forming an upper layer film on the block copolymer layer using the upper layer film forming composition, (3) A step of phase-separating the block copolymer layer formed on the substrate, and (4) A step of etching the phase-separated block copolymer layer, is included.

[0085] The block copolymer layer phase-separated by the above-described method can be further subjected to an etching process. Usually, before etching, a part of the phase-separated block copolymer is removed. The etching can be performed by known means. This method can be used for the production of semiconductor substrates.

[0086] That is, the method for manufacturing a semiconductor device according to the present invention is (1) a step of forming a block copolymer layer on a substrate, (2) a step of forming an upper layer film on the block copolymer layer using the above upper layer film forming composition, (3) a step of phase-separating the block copolymer layer formed on the substrate, (4) a step of etching the phase-separated block copolymer layer, and (5) a step of etching the substrate, and includes.

[0087] For etching, for example, gases such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane (CHF3), difluoromethane (CH2F2), carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, trichloroborane and dichloroborane, or a combination of the above gases can be used.

[0088] By utilizing the pattern of the phase-separated block copolymer layer formed using the upper layer film forming composition according to the present invention, a desired shape can be imparted to the substrate to be processed by etching, and a suitable semiconductor device can be fabricated.

Examples

[0089] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0090] [Example 1] (Preparation of Self-Assembled Membrane-Forming Composition 1 Composed of Block Copolymer 1) Dissolve 0.5 g of a poly(4-methoxystyrene) / poly(4-trimethylsilylstyrene) copolymer (weight-average molecular weight Mw = 30200, polydispersity = 1.12, volume ratio 50:50), which is a block copolymer, in 24.5 g of propylene glycol monomethyl ether acetate to obtain a 2 mass% solution. After that, filter it using a polyethylene microfilter with a pore size of 0.02 μm to prepare a solution of Self-Assembled Membrane-Forming Composition 1 composed of Block Copolymer 1.

[0091] (Preparation of Self-Assembled Membrane-Forming Composition 2 Composed of Block Copolymer 2) Dissolve 0.5 g of a poly(4-methoxystyrene) / poly(4-trimethylsilylstyrene) copolymer (weight-average molecular weight Mw = 17600, polydispersity = 1.11, volume ratio 50:50), which is a block copolymer, in 24.5 g of propylene glycol monomethyl ether acetate to obtain a 2 mass% solution. After that, filter it using a polyethylene microfilter with a pore size of 0.02 μm to prepare a solution of Self-Assembled Membrane-Forming Composition 2 composed of Block Copolymer 2.

[0092] (Solvent Resistance Evaluation of Self-Assembled Membrane Composed of Block Copolymer) Apply the self-assembled membrane-forming composition composed of Block Copolymer 1 or 2 with a spin coater and heat it on a hot plate at 100 °C for 1 minute to obtain a self-assembled membrane with a film thickness of 40 nm. Immerse the obtained coated film in n-octane for 1 minute, spin-dry it, and then measure the film thickness of the film heated at 100 °C for 30 seconds to confirm the change in film thickness.

[0093] [Examples 2 - 3] The solvent resistance of the block copolymer layer was confirmed in the same manner as in Example 1, except that n-decane or p-menthane was used instead of n-octane.

[0094] [Comparative Examples 1 - 5] The solvent resistance of the block copolymer layer was confirmed in the same manner as in Example 1, except that diisopentyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl acetate, and 2-heptanone were used instead of n-octane.

[0095] (Confirmation of Solvent Resistance of Block Copolymer Layer) The results of the solvent resistance confirmed in Examples 1 to 3 and Comparative Examples 1 to 5 are shown in Table 1.

[0096]

Table 1

[0097] The weight average molecular weight (Mw) of the polymer (A) shown in the following synthesis example is the measurement result by the Gel Permeation Chromatography (GPC) method. For the measurement, a GPC apparatus manufactured by Tosoh Corporation was used, and the measurement conditions are as follows. Measuring device: HLC-8020GPC [trade name] (manufactured by Tosoh Corporation) GPC column: TSKgel G2000HXL; 2 pieces, G3000HXL: 1 piece, G4000HXL; 1 piece [trade name] (all manufactured by Tosoh Corporation) Column temperature: 40 °C Solvent: Tetrahydrofuran (THF) Flow rate: 1.0 ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0098] [Synthesis Example 1] Synthesis of Polymer 1 3.20 g of N-cyclohexylmaleimide, 2.00 g of 4-tert-butylstyrene, 0.76 g of tert-butyl methacrylate, and 0.18 g of 2,2'-azobisisobutyronitrile were dissolved in 24.0 g of propylene glycol monomethyl ether acetate. After that, this solution was heated and stirred at 140 °C for about 2 hours. This reaction solution was dropped into methanol, and the precipitate was collected by suction filtration. Then, it was dried under reduced pressure at 60 °C to recover Polymer 1. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 13,100.

[0099] [Synthesis Example 2] Synthesis of Polymer 2 3.14 g of N-cyclohexylmaleimide, 2.24 g of 4-tert-butylstyrene, 0.45 g of isopropyl methacrylate, and 0.18 g of 2,2'-azobisisobutyronitrile were dissolved in 24.0 g of propylene glycol monomethyl ether acetate. After that, this solution was heated and stirred at 140 °C for about 2 hours. This reaction solution was dropped into methanol, and the precipitate was collected by suction filtration. Then, it was dried under reduced pressure at 60 °C to recover Polymer 2. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 12,800.

[0100] [Synthesis Example 3] Synthesis of Polymer 3 3.06 g of N-cyclohexylmaleimide, 2.19 g of 4-tert-butylstyrene, 0.58 g of cyclohexyl methacrylate, and 0.18 g of 2,2'-azobisisobutyronitrile were dissolved in 24.0 g of propylene glycol monomethyl ether acetate. After that, this solution was heated and stirred at 140 °C for about 2 hours. This reaction solution was dropped into methanol, and the precipitate was collected by suction filtration. Then, it was dried under reduced pressure at 60 °C to recover Polymer 3. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 11,700.

[0101] [Synthesis Example 4] Synthesis of Polymer 4 2.80 g of N-cyclohexylmaleimide, 1.50 g of 4-tert-butylstyrene, 1.64 g of isopropyladamantyl methacrylate, and 0.06 g of 2,2'-azobisisobutyronitrile were dissolved in 24.0 g of propylene glycol monomethyl ether acetate. Then, this solution was heated and stirred at 140 °C for about 2 hours. This reaction solution was dropped into methanol, and the precipitate was collected by suction filtration. After that, it was dried under reduced pressure at 60 °C to recover Polymer 4. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 34,600.

[0102] [Synthesis Example 5] Synthesis of Polymer 5 2.78 g of N-cyclohexylmaleimide, 1.24 g of 4-tert-butylstyrene, 1.93 g of ethyladamantyl methacrylate, and 0.05 g of 2,2'-azobisisobutyronitrile were dissolved in 24.0 g of propylene glycol monomethyl ether acetate. Then, this solution was heated and stirred at 140 °C for about 2 hours. This reaction solution was dropped into methanol, and the precipitate was collected by suction filtration. After that, it was dried under reduced pressure at 60 °C to recover Polymer 5. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 21,100.

[0103] [Example 4] (Preparation of Upper Layer Film Composition 1) 0.25 g of the resin obtained in Synthesis Example 1 was dissolved in 9.75 g of p-menthane, which gave good results in Examples 1 to 3, to form a 2.5 mass% solution. Then, it was filtered using a polyethylene microfilter with a pore size of 0.2 μm to prepare a solution of the upper layer film-forming composition 1 of the self-assembled film.

[0104] (Preparation of Lower Layer Film-forming Composition 1) 0.1 g of poly(styrene-co-4-tert-butylstyrene) having a hydroxyl group at the terminal was dissolved in 19.9 g of propylene glycol monomethyl ether acetate to form a 0.5 mass% solution. Then, it was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a solution of the lower layer film-forming composition of the self-assembled film composed of a block copolymer.

[0105] (Self-organization evaluation of block copolymer) The lower layer film-forming composition 1 of the self-organized film obtained above was applied onto a silicon wafer, heated on a hot plate at 240 °C for 1 minute, and then immersed in propylene glycol monomethyl ether acetate for 1 minute to obtain a lower layer film (A layer). On top of this, the self-organized film-forming composition 2 composed of block copolymer 2 was applied by a spin coater, heated on a hot plate at 100 °C for 1 minute to form a self-organized film (B layer) with a film thickness of 40 nm. On top of this, the upper layer film-forming composition 1 was applied by a spinner, and then heated on a hot plate at 200 °C for 10 minutes to induce the microphase separation structure of the block copolymer. The arrangement of each layer is shown in Fig. 1.

[0106] (Observation of microphase separation structure) The silicon wafer with the induced microphase separation structure was etched for 25 seconds using O2 gas as the etching gas with an etching apparatus (Lam 2300 Versys Kiyo45) manufactured by Lam Research Corporation to remove the upper layer film and preferentially etch the polymethoxystyrene region, and then the shape was observed with an electron microscope (S-4800) (Fig. 2).

[0107] [Examples 5 to 8] Samples were prepared and the microphase separation structure of the block copolymer was formed in the same manner as in Example 4, except that polymers 2 to 5 were used instead of polymer 1.

[0108] [Comparative Examples 6 to 10] Samples were prepared and the microphase separation structure of the block copolymer was formed in the same manner as in Example 4, except that diisopentyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl acetate, and 2-heptanone, which gave poor results in Comparative Examples 1 to 5, were used instead of p-menthane, which is the solvent of the upper layer film-forming composition.

[0109] (Confirmation of block copolymer sequence) The solubility of the upper layer films prepared in Examples 4 to 8 and Comparative Examples 6 to 10 and the alignment of the block copolymers were confirmed. The results are shown in Table 2 and FIG. 2.

[0110] [Table 2]

[0111] As shown in Table 2, the top coat prepared using the upper layer film forming composition of the present invention can be applied without dissolving the block copolymer, and can cause a vertical alignment of the block copolymer.

Industrial Applicability

[0112] An upper layer film forming composition that can cause a vertical alignment of a block copolymer without dissolving or swelling a layer containing the block copolymer formed on a substrate and provides an upper layer film having good solubility in a hydrophobic solvent is extremely useful industrially.

Claims

1. An upper layer film forming composition used for phase-separating a layer containing a block copolymer formed on a substrate, (A) (a) A copolymer containing a unit structure derived from a maleimide structure and a unit structure derived from a styrene structure, and (B) a non-aromatic hydrocarbon compound that is liquid at normal temperature and pressure as a solvent The upper layer film forming composition containing these.

2. The upper layer film forming composition according to claim 1, wherein the solvent is a non-aromatic hydrocarbon compound having 4 to 26 carbon atoms.

3. The upper layer film forming composition according to claim 1 or 2, wherein the solvent is an acyclic hydrocarbon compound or a cyclic hydrocarbon compound.

4. The upper layer film forming composition according to claim 3, wherein the acyclic hydrocarbon compound is a saturated straight-chain, unsaturated straight-chain, saturated branched-chain, or unsaturated branched-chain hydrocarbon compound.

5. The upper layer film forming composition according to claim 3, wherein the cyclic hydrocarbon compound is a monocyclic compound having a substituent, or a bicyclic or condensed ring compound that may have a substituent.

6. The upper layer film forming composition according to claim 3, wherein the cyclic hydrocarbon compound is a cyclic hydrocarbon compound having 6 to 19 carbon atoms.

7. The unit structure derived from the maleimide structure is represented by the formula (1): 【Chemical 1】 (In formula (1), R １ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom). The composition according to any one of claims 1 to 6.

8. The unit structure derived from the styrene structure is represented by the formula (2): [Chemical Formula 2] (In formula (2), R ２ to R ４ , R 7 and R 8 each independently represents a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom.) The composition according to any one of claims 1 to 7.

9. The copolymer (A) further contains (b) a unit structure derived from a (meth)acrylic group, The composition according to any one of claims 1 to 8.

10. The unit structure derived from the (meth)acrylic group is represented by the formula (3): 【Chemical Formula 3】 (In formula (3), R ５ and R ６ each independently represents a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom.) The composition according to claim 9.

11. The formula (4): 【Chemical Formula 4】 (In formula (4), R １ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom). A composition according to any one of claims 1 to 10, comprising a copolymer (A) obtained by copolymerizing a monomer mixture containing a compound represented by and a compound represented by the formula (5): 【Chemical Formula 5】 (In formula (5), R ２ to R ４ , R ７ and R ８ each independently represents a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom.)

12. (1) A step of forming a block copolymer layer on a substrate, (2) A step of forming an upper layer film using the composition according to any one of claims 1 to 11 on the block copolymer layer, and (3) A step of phase-separating the block copolymer layer formed on the substrate, A method for forming a phase separation pattern of a block copolymer, including these steps.

13. (1) A step of forming a block copolymer layer on a substrate, ​ (2) A step of forming an upper layer film using the composition according to any one of claims 1 to 11 on the block copolymer layer; (3) A step of phase-separating the block copolymer layer formed on the substrate; and (4) A step of etching the phase-separated block copolymer layer, A pattern manufacturing method comprising the above steps.

14. (1) A step of forming a block copolymer layer on a substrate; (2) A step of forming an upper layer film using the composition according to any one of claims 1 to 11 on the block copolymer layer; (3) A step of phase-separating the block copolymer layer formed on the substrate; and (4) A step of etching the phase-separated block copolymer layer, (5) A step of etching the substrate, A manufacturing method of a semiconductor device comprising the above steps.

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