Method for producing a composition, a reactive film, a lower film, a structure including a phase separation structure, and a polymer

Abstract

The present invention provides a composition capable of forming a heat-resistant guide pattern in a simple manner, a method for producing a structure including a reactive film, an underlayer film, and a phase-separated structure, and a polymer. [Solution] A composition containing polymer (A), wherein polymer (A) has a structural unit (A1) in which a hydrogen atom in a carboxyl group or hydroxyl group is substituted by an acid-dissociable group, and a structural unit (A2) derived from styrene and / or a styrene derivative, and the acid-dissociable group is not a tertiary carbon atom-containing aliphatic group or an acetal protecting group.

Description

Technical Field

[0001] The present invention relates to a composition, a reactive film, an underlayer film, a method for manufacturing a structure including a phase-separated structure, and a polymer.

Background Art

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

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

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

[0005] In the chemical epitaxy process, as a guide pattern, for example, a pattern of a neutralized film having an affinity with any block constituting the block copolymer, a crosslinked polystyrene film having an affinity with a part of the blocks constituting the block copolymer, and a pattern in which the neutralized film is repeated are used.

Prior Art Documents

Patent Documents

[0006] [Patent Document 1] Japanese Patent Publication No. 2008-36491 [Overview of the project] [Problems that the invention aims to solve]

[0007] Photolithography is typically used to form the guide patterns described above. However, photolithography requires complicated operations such as forming a photosensitive resin film, exposure, development, etching, and removal of the resist film. Furthermore, exposure with extreme ultraviolet (EUV) light is required to form finer guide patterns. However, EUV exposure presents a problem in that etching is difficult because the photosensitive resin film (resist film) needs to be thin.

[0008] Furthermore, high-temperature heat treatment is performed when separating the layers containing block copolymers. For this reason, the guide pattern material must also have heat resistance, meaning that the chemical state of the guide pattern does not change during heat treatment.

[0009] The present invention has been made in view of the above circumstances, and aims to provide a composition that can form a guide pattern with excellent heat resistance in a simple manner, a method for producing a structure including a reactive film, an underlayer film, and a phase separation structure, and a polymer. [Means for solving the problem]

[0010] To solve the above problems, the inventors conducted extensive research and found that the above problems can be solved by using a polymer (A) having a structural unit (A1) in which a hydrogen atom in a carboxyl group or hydroxyl group is substituted with a predetermined acid-dissociable group, and a structural unit (A2) derived from styrene and / or a styrene derivative, thereby completing the present invention. Specifically, the present invention provides the following.

[0011] The first embodiment is a composition containing polymer (A), The polymer (A) comprises a structural unit (A1) in which a hydrogen atom in a carboxyl group or hydroxyl group is substituted by an acid-dissociable group, and a structural unit (A2) derived from styrene and / or a styrene derivative. The aforementioned acid-dissociable group is not a tertiary carbon-carbon-containing aliphatic group, nor an acetal protecting group, The aforementioned tertiary carbon-containing aliphatic group is a group that contains a tertiary carbon atom and can bond to the carboxyl group or a residue from which a hydrogen atom has been removed via a bond attached to the tertiary carbon atom. The acetal protecting group is a composition in which a group can form an acetal structure by bonding with a residue from which a hydrogen atom has been removed from the carboxyl group or the hydroxyl group.

[0012] A second embodiment is a reactive film containing polymer (A) whose hydrophilicity changes upon the action of an acid, The polymer (A) comprises a structural unit (A1) in which a hydrogen atom in a carboxyl group or hydroxyl group is substituted by an acid-dissociable group, and a structural unit (A2) derived from styrene and / or a styrene derivative. The aforementioned acid-dissociable group is not a tertiary carbon-carbon-containing aliphatic group, nor an acetal protecting group, The aforementioned tertiary carbon-containing aliphatic group is a group that contains a tertiary carbon atom and can bond to the carboxyl group or a residue from which a hydrogen atom has been removed via a bond attached to the tertiary carbon atom. The acetal protecting group is a reactive film that can form an acetal structure by bonding with a residue from which a hydrogen atom has been removed from the carboxyl group or the hydroxyl group.

[0013] A third aspect is a lower layer film used as a template for phase separation of block copolymers, The aforementioned lower layer film is formed by regioselectively applying an acid to the reactive film of the second embodiment. It is an underlayer film comprising two or more regions with differing hydrophilicity.

[0014] A fourth aspect involves forming a reactive film according to the second aspect on a substrate, A photosensitive composition containing a photoacid generator is applied to the reactive film to form a photosensitive film. The photosensitive film is exposed to light in a position-selective manner, and the reactive film is treated with an acid in a position-selective manner to form a lower layer film. Removing the aforementioned photosensitive film, Forming an upper layer film containing a block copolymer on the aforementioned lower layer film, A method for producing a structure having a phase-separated structure, comprising the steps of: phase-separating the block copolymer in the upper layer film.

[0015] A fifth aspect comprises a structural unit (A1) having a structure in which a hydrogen atom in a carboxyl group or hydroxyl group is substituted by an acid-dissociable group, and a structural unit (A2) derived from styrene and / or a styrene derivative. The aforementioned acid-dissociable group is not a tertiary carbon-carbon-containing aliphatic group, nor an acetal protecting group, The aforementioned tertiary carbon-containing aliphatic group is a group that contains a tertiary carbon atom and can bond to the carboxyl group or a residue from which a hydrogen atom has been removed via a bond attached to the tertiary carbon atom. The acetal protecting group is a polymer that can form an acetal structure by bonding with a residue from which a hydrogen atom has been removed from the carboxyl group or the hydroxyl group. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a composition that can form a heat-resistant guide pattern in a simple manner, a method for producing a reactive film, a base film, a structure including a phase separation structure, and a polymer. [Brief explanation of the drawing]

[0017] [Figure 1] This is a schematic process diagram illustrating one embodiment of a method for manufacturing a structure including a phase-separated structure. [Modes for carrying out the invention]

[0018] The embodiments of the present invention will be described in detail below, but the present invention is not limited to the embodiments described below and can be implemented with appropriate modifications within the scope of the object of the present invention.

[0019] <<Composition>> The composition of the first embodiment contains a polymer (A). Polymer (A) has a constituent unit (A1) having a structure in which a hydrogen atom in a carboxyl group or hydroxyl group is substituted by an acid-dissociable group, and a constituent unit (A2) derived from styrene and / or a styrene derivative. The acid-dissociable group is not a tertiary carbon atom-containing aliphatic group or an acetal protecting group. A tertiary carbon atom-containing aliphatic group is a group that contains a tertiary carbon atom and can bond to the carboxyl group or the residue from which a hydrogen atom has been removed from the hydroxyl group via a bond bonded to the tertiary carbon atom. An acetal protecting group is a group that can form an acetal structure by bonding to the carboxyl group or the residue from which a hydrogen atom has been removed from the hydroxyl group.

[0020] When a photosensitive film containing a photoacid generator is formed on a reactive film formed from the composition of the first embodiment, and the photosensitive film is exposed to light in a positional manner, the acid generated from the photoacid generator in the exposed region acts on the adjacent region of the reactive film. Specifically, the acid dissociable groups in the constituent units (A1) of the polymer (A) are hydrolyzed by the action of the acid, and highly polar carboxyl groups and hydroxyl groups are exposed. As a result, an underlying film can be formed that has a highly hydrophilic region (a region adjacent to the exposed part of the photosensitive film) and a less hydrophilic region (a region adjacent to the unexposed part of the photosensitive film), and a guide pattern can be formed by a simple method without performing complicated operations such as etching.

[0021] In addition, when the acid-dissociable group is an aliphatic group containing a tertiary carbon atom such as a tert-butyl group or an acetal protecting group, the acid-dissociable group may dissociate even in the non-exposed area due to heat treatment at a high temperature, and the chemical state of the guide pattern may change. On the other hand, since the acid-dissociable group in the structural unit (A1) of the polymer (A) is not such a functional group, it is difficult to dissociate even by heat treatment at a high temperature and has excellent heat resistance.

[0022] <Polymer (A)> [Structural unit (A1)] The structural unit (A1) includes a structure in which a hydrogen atom in a carboxy group or a hydroxy group is substituted by an acid-dissociable group. The acid-dissociable group is not an aliphatic group containing a tertiary carbon atom and an acetal protecting group. The aliphatic group containing a tertiary carbon atom contains a tertiary carbon atom and is a group that can be bonded to a residue obtained by removing a hydrogen atom from the carboxy group or the hydroxy group through a bond bonded to the tertiary carbon atom. The acetal protecting group is a group that can form an acetal structure by bonding to a residue obtained by removing a hydrogen atom from the carboxy group or the hydroxy group.

[0023] From the viewpoint of heat resistance, the structural unit (A1) preferably includes a structure in which a hydrogen atom in a hydroxy group is substituted by an acid-dissociable group.

[0024] As the acid-dissociable group, a group represented by the following formula (a1-1a) or the following formula (a1-2a) is preferable. -CR 12 R 13 R 14 (a-1a) -SiR 22 R 23 R 24 (a1-2a)

[0025] In the formula (a1-1a), R 12 ~R 14 are each independently an aromatic group which may have a substituent. In the formula (a1-2a), R 22 ~R 24 are each independently a hydrocarbon group which may have a substituent.

[0026] R 12 ~R 14 The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but it is preferably an aromatic hydrocarbon group. An aromatic hydrocarbon group consists solely of an aromatic hydrocarbon ring, or a group in which two or more aromatic hydrocarbon rings are linked by a single bond. The aromatic hydrocarbon ring may be a monoring or a fused ring formed by the fusion of two or more rings. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 20, and more preferably 6 to 12. Examples of aromatic hydrocarbon groups include the phenyl group, naphthyl group, anthryl group, phenanthryl group, and biphenyl group. Among these, the phenyl group is preferred.

[0027] R 12 ~R 14 Examples of substituents that the aromatic group may have include alkyl groups and alkoxy groups. Among these, alkyl groups are preferred. The number of carbon atoms in the alkyl group as a substituent is preferably 1 to 10, and more preferably 1 to 5. The alkyl group may be linear or branched. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. The number of carbon atoms in the alkoxy group as a substituent is preferably 1 to 10, and more preferably 1 to 5. The alkyl group in the alkoxy group may be linear or branched. Examples of alkyl groups in the alkoxy group include those listed as alkyl groups as substituents.

[0028] R 22 ~R 24 The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but it is preferable that it be an aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 10, and more preferably 1 to 5. Alkyl groups are preferred as aliphatic hydrocarbon groups. Alkyl groups may be linear or branched. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. An aromatic hydrocarbon group consists solely of an aromatic hydrocarbon ring, or a group in which two or more aromatic hydrocarbon rings are linked by a single bond. The aromatic hydrocarbon ring may be a monoring or a fused ring formed by the fusion of two or more rings. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 20, and more preferably 6 to 12. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, phenanthryl, and biphenyl groups.

[0029] R 22 ~R 24 Examples of substituents that the hydrocarbon group may have include alkyl groups and alkoxy groups.

[0030] The constituent unit (A1) is preferably a constituent unit represented by the following formula (a1-1) or formula (a1-2). [ka]

[0031] In formula (a1-1), R 11 L is a hydrogen atom or a methyl group. 11 X is a single bond or a divalent linking group. 11 R is a single bond or a carbonyl group. 12 ~R 14 These are, independently, aromatic groups that may have substituents.

[0032] In formula (a1-2), R 21 L is a hydrogen atom or a methyl group. 21 X is a single bond or a divalent linking group. 21 R is a single bond or a carbonyl group.22 ~R 24 These are, independently, hydrocarbon groups that may have substituents.

[0033] L 11 The divalent linking group is not particularly limited as long as it is a group that links the main chain of polymer (A) with a structure in which a hydrogen atom in a carboxyl group or hydroxyl group is substituted by an acid-dissociable group. 11 The number of carbon atoms in the divalent linking group is preferably 1 to 10, and more preferably 1 to 5.

[0034] L 11 As a divalent linking group, *-L 12 -R 15 -** is a preferred base. 12 R is a divalent linking group containing heteroatoms (such as oxygen, nitrogen, and sulfur atoms). 15 * is a divalent aliphatic hydrocarbon group. * is a bond with a carbon atom in the main chain. ** is X 11 This is a combination of the two. L 12 Examples of divalent linking groups include those represented as -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-. In the above formulas, R is independently either a hydrogen atom or a substituent. Examples of substituents include alkyl groups and acyl groups. Unless otherwise specified in this specification, the orientation of the divalent group bond is not particularly limited. Among these linking groups, the group represented as -C(=O)-O- is preferred.

[0035] R 15The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 10, and more preferably 1 to 5. An alkylene group is preferred as the divalent aliphatic hydrocarbon group. The alkylene group may be linear or branched. Examples of alkylene groups include methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5-diyl.

[0036] X 11 From the viewpoint of heat resistance, it is preferable that the bond be a single bond.

[0037] R in equation (a1-1) 12 ~R 14 These are similar to the groups in equation (a1-1a).

[0038] L 21 The divalent linking group as L 11 It is similar to a divalent linking group.

[0039] X 21 From the viewpoint of heat resistance, it is preferable that the bond be a single bond.

[0040] R in equation (a1-2) 22 ~R 24 These are similar to the groups in equation (a1-2a).

[0041] The ratio of moles of constituent unit (A1) to the total number of moles of all constituent units constituting polymer (A) is preferably 1 mol% to 40 mol%, more preferably 3 mol% to 30 mol%, and even more preferably 5 mol% to 25 mol%. The desired effect is more likely to be obtained when the ratio is within the above numerical range.

[0042] [Constituent Unit (A2)] The constituent unit (A2) is derived from styrene and / or styrene derivatives.

[0043] Examples of styrene derivatives include compounds in which the hydrogen atom bonded to the α-carbon atom of styrene is substituted with substituents such as alkyl groups having 1 to 10 carbon atoms; compounds in which the hydrogen atoms of the phenyl group of styrene are substituted with substituents such as alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, hydroxyl groups, nitro groups, halogen atoms, and acetoxy groups; and compounds in which two or more hydrogen atoms on the phenyl group of styrene are substituted and the substituents are bonded to each other to form a ring. Specific examples of styrene derivatives include α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-tert-butylstyrene, 4-n-octylstyrene, 2,4,6-trimethylstyrene, 4-methoxystyrene, 4-tert-butoxystyrene, 4-hydroxystyrene, 4-nitrostyrene, 3-nitrostyrene, 4-chlorostyrene, 4-fluorostyrene, 4-acetoxystyrene, 4-chloromethylstyrene, and 4-vinylbenzocyclobutene.

[0044] The constituent unit (A2) is preferably the constituent unit (A2-1) represented by the following formula (a2-1), and / or the constituent unit (A2-2) represented by the following formula (a2-2). [ka]

[0045] In formula (a2-1) and formula (a2-2), R a21 , and R a22 Each of these is an alkyl group having 1 to 5 carbon atoms. n1 is an integer between 0 and 5. n2 is an integer between 0 and 3. a Each of these is independently either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0046] R a21 , R a22 , and R a The alkyl group may be linear or branched. n1 is preferably an integer between 0 and 3, more preferably 0 or 1, and even more preferably 0. n2 is preferably 0 or 1, and more preferably 0.

[0047] When reinforcing the reactive film and the underlying film is desired, it is preferable that the constituent unit (A2) includes the constituent unit (A2-2). The crosslinkable benzocyclobutene structure in the constituent unit (A2-2) can crosslink polymers together, thereby improving the reinforcing properties.

[0048] The ratio of moles of constituent unit (A2) to the total number of moles of constituent units constituting polymer (A) is preferably 50 mol% to 95 mol%, more preferably 60 mol% to 95 mol%, and even more preferably 70 mol% to 95 mol%. The desired effect is more likely to be obtained when the ratio is within the above numerical range.

[0049] The ratio of moles of constituent unit (A2-1) to the total number of moles of constituent units constituting polymer (A) is preferably 50 mol% to 95 mol%, more preferably 60 mol% to 90 mol%, and even more preferably 70 mol% to 90 mol%. The desired effect is more likely to be obtained when the ratio is within the above numerical range.

[0050] The ratio of moles of constituent unit (A2-2) to the total number of moles of constituent units constituting polymer (A) is preferably 1 mol% to 20 mol%, and more preferably 3 mol% to 10 mol%. Within this numerical range, reinforcement and desired effects are more likely to be obtained.

[0051] [Component Unit (A3)] The polymer (A) may further have a constituent unit (A3) having a substrate-adsorbing group. The substrate-adsorbing group is a functional group that can form a bond with the substrate. The bond with the substrate may be, for example, a covalent bond, a coordination bond, or a hydrogen bond. Examples of substrate-adsorbing groups include hydroxyl groups, thiol groups, primary amino groups, and secondary amino groups.

[0052] The preferred constituent unit (A3) is the constituent unit (A3-1) represented by the following formula (a3-1). [ka]

[0053] In formula (a3-1), L 31 R is a single bond or a divalent linking group. 31 X is a divalent hydrocarbon group. X is a hydroxyl group, a thiol group, -NH2, or -NHR 32 That is. R 32 R is an alkyl group. a3 This is a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms.

[0054] L 31 A divalent linking group is preferred. 31 As a divalent linking group, a divalent linking group containing heteroatoms such as an oxygen atom, a nitrogen atom, or a sulfur atom is preferred. 31 Examples of divalent linking groups include those represented as -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-. In the above formulas, R is independently either a hydrogen atom or a substituent. Examples of substituents include alkyl groups and acyl groups. Among these linking groups, the group represented as -C(=O)-O- is preferred.

[0055] R 31 The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. An alkylene group is preferred as the divalent aliphatic hydrocarbon group. The alkylene group may be linear or branched, but linear is preferred. Examples of alkylene groups include methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5-diyl. A hydroxyl group is preferred as X. R a3 The number of carbon atoms in the alkyl group is preferably 1 or more and 5 or less. a3 Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. Among these, the methyl group is preferred.

[0056] When polymer (A) has constituent units (A3), the ratio of moles of constituent units (A3) to the total number of moles of constituent units constituting polymer (A) is preferably 1 mol% to 20 mol%, and more preferably 3 mol% to 10 mol%. The desired effect is more likely to be obtained when the ratio is within the above numerical range.

[0057] <Organic solvent (S)> The composition of the first embodiment preferably contains an organic solvent (S). The organic solvent (S) can be any organic solvent that can dissolve each component used to form a homogeneous solution. Any organic solvent can be selected from organic solvents that have been conventionally known as solvents for compositions mainly composed of resins.

[0058] Examples of organic solvents include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; monoacetates of polyhydric alcohols such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; and polyhydric alcohols such as monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or compounds having ether bonds such as monophenyl ether of the aforementioned polyhydric alcohols or monoacetates of the aforementioned polyhydric alcohols. Derivatives [of which propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane, monoacetates of polyhydric alcohols such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate, and esters other than the aforementioned derivatives of 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 solvents 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.

[0059] The content of the organic solvent in the composition of the first embodiment is not particularly limited. The organic solvent is appropriately set according to the film thickness to be applied, so that the concentration of the composition of the first embodiment is at a concentration that can be applied. Generally, the organic solvent is used such that the solid content concentration of the composition of the first embodiment 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.

[0060] <Other ingredients> The composition of the first embodiment may further optionally contain miscible additives, such as additional resins to improve the performance of the underlying film, surfactants to improve coatability, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, sensitizers, base enhancers, and basic compounds.

[0061] <<polymer>> The polymer of the fifth embodiment has a structural unit (A1) in which a hydrogen atom in a carboxyl group or hydroxyl group is substituted by an acid-dissociable group, and a structural unit (A2) derived from styrene and / or a styrene derivative. The acid-dissociable group is not a tertiary carbon atom-containing aliphatic group or an acetal protecting group. The tertiary carbon atom-containing aliphatic group is a group that contains a tertiary carbon atom and can bond to the carboxyl group or the residue from which a hydrogen atom has been removed from the hydroxyl group via a bond bonded to the tertiary carbon atom. The acetal protecting group is a group that can form an acetal structure by bonding to the carboxyl group or the residue from which a hydrogen atom has been removed from the hydroxyl group.

[0062] The polymer of the fifth embodiment is the same as polymer (A) contained in the composition of the first embodiment.

[0063] <<Method for manufacturing a structure having a phase-separated structure>> A method for manufacturing a structure having a phase-separated structure according to a fourth embodiment includes: forming a reactive film on a substrate (step (i)); applying a photosensitive composition containing a photoacid generator on the reactive film to form a photosensitive film (step (ii)); regioselectively exposing the photosensitive film to light to regioselectively react with acid on the reactive film to form a lower layer film (step (iii)); removing the photosensitive film (step (iv)); forming an upper layer film containing a block copolymer on the lower layer film (step (v)); and causing phase separation of the block copolymer in the upper layer film (step (vi)).

[0064] <Process (i)> In step (i), a reactive film 2 is formed on the substrate 1 (see Figure 1(i)). The reactive film contains polymer (A), and its hydrophilicity changes upon the action of acid. Polymer (A) is the same as polymer (A) contained in the composition of the first embodiment.

[0065] The reactive film can be formed, for example, by applying the composition of the first embodiment onto a substrate by a conventionally known method such as spin coating to form a coating film, and then drying it. The drying method for the coating film is sufficient to volatilize the organic solvent contained in the composition of the first embodiment, for example, by baking. In this case, the baking temperature is preferably between 80°C and 350°C. The baking time is preferably between 30 seconds and 600 seconds, and more preferably between 60 seconds and 600 seconds. The thickness of the reactive film after drying of the coating is preferably between 1 nm and 150 nm, and more preferably between 1 nm and 100 nm.

[0066] The type of substrate is not particularly limited, as long as the composition of the first embodiment 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 inorganic oxides such as SiO2; substrates made of inorganic nitrides such as SiN; substrates made of inorganic 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 substrate are not particularly limited. The substrate does not necessarily need to have a smooth surface, and various shapes of substrates can be selected as appropriate. Examples include substrates with curved surfaces, flat plates with uneven surfaces, and substrates in the shape of thin flakes.

[0067] The surface of the substrate 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 substrate 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, it is preferable that the organic film forming material is capable of forming an etchable, particularly dry-etchable, organic film, so that the pattern can be transferred to the organic film by etching the organic film using a patterned mask made of a block copolymer formed by processing the upper layer film, thereby forming a patterned organic film. 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.

[0068] The substrate may be surface-treated beforehand. By treating the substrate surface, the coatability of the composition of the first embodiment may be improved, or the polymer (A) may be more easily fixed to the substrate. Conventional known surface treatment methods can be used, such as oxygen plasma treatment, ozone oxidation treatment, acid-alkali treatment, and chemical modification treatment.

[0069] <Process (ii)> In step (ii), a photosensitive composition containing a photoacid generator is applied to the reactive film 2 to form a photosensitive film 3 (see Figure 1(ii)).

[0070] For example, a photosensitive film can be formed by applying a photosensitive composition onto a reactive film using a conventionally known method such as spin coating, forming a coating film, and then drying it. The drying method for the coating film is not particularly limited. The drying temperature is preferably between 80°C and 350°C. The drying time is preferably between 30 seconds and 600 seconds, and more preferably between 60 seconds and 600 seconds. The thickness of the photosensitive film after drying of the coating is preferably between 1 nm and 150 nm, and more preferably between 1 nm and 100 nm.

[0071] The photoacid generator included in the photosensitive composition is not particularly limited, and conventionally known photoacid generators can be used. Specifically, examples include iodonium salts and sulfonium salts (onium salt-based acid generators), oximesulfonate-based acid generators, halogen-containing triazine compounds, diazomethane-based acid generators, nitrobenzyl sulfonate-based acid generators (nitrobenzyl derivatives), iminosulfonate-based acid generators, and disulfone-based acid generators.

[0072] The photosensitive composition may contain a resin as a base component. The resin is not particularly limited as long as it is easily removed in a later step (iv). Examples of such resins include polymers of monomers having unsaturated double bonds, including hydroxystyrenes (polyhydroxystyrene resins).

[0073] The photosensitive composition may contain an organic solvent. Examples of organic solvents include those that can be used in the composition of the first embodiment.

[0074] <Step (iii)> In step (iii), the photosensitive film 3 is exposed to light in a regioselective manner, and the reactive film is reacted with acid in a regioselective manner to form an underlying film 2' having two regions 2'a and 2'b with different polarities (see (iii) in Figure 1).

[0075] Methods for selectively exposing a photosensitive film include, for example, exposure via a mask. Exposure is performed by irradiating with radiation such as ultraviolet light, ArF excimer laser, KrF excimer laser, F2 excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beam, X-ray, and soft X-ray. Even under low exposure conditions, the polarity of the film surface can be changed by exposure, so the exposure dose is 10 mJ / cm². 2 More than 300mJ / cm 2 It is preferable that the following is the case: 20 mJ / cm² 2 More than 200mJ / cm 2 More preferably, the following is true: 30 mJ / cm² 2 More than 150mJ / cm 2The following is even more preferable:

[0076] In the reactive film region adjacent to the exposed area of ​​the photosensitive film, the acid-dissociable groups are hydrolyzed by the action of the acid, revealing highly polar carboxyl and hydroxyl groups, and the region becomes highly hydrophilic. On the other hand, the reactive film region adjacent to the unexposed area of ​​the photosensitive film is not affected by the acid, and therefore maintains its hydrophobicity. As a result, the underlying film obtained by regioselectively applying acid to the reactive film has two or more regions with differing hydrophilicity, and can be used as a template for phase separation of block copolymers.

[0077] <Process (iv)> In step (iv), the photosensitive film 3 is removed (see Figure 1(iv)). The method for removing the photosensitive film 3 is not particularly limited, and one example is rinsing the photosensitive film with the organic solvent used in the photosensitive composition.

[0078] <Process (v)> In step (v), an upper layer 4 containing a block copolymer is formed on the lower layer 2' (see Figure 1(v)). The block copolymer is not particularly limited, and conventionally known block copolymers such as polystyrene-polymethyl methacrylate (PS-PMMA) block copolymer can be used, which are obtained by bonding a block having a structural unit containing an aromatic group with a block having a structural unit derived from an (α-substituted) acrylic acid ester. The method for forming the upper layer on the lower layer is not particularly limited, and examples include applying a resin composition for forming a phase-separated structure containing a block copolymer or an organic solvent onto the lower layer by a conventionally known method such as spin coating to form a coating film, and then drying it.

[0079] <Process (vi)> In step (vi), the block copolymer is phase-separated in the upper film 4 (see (vi) in Figure 1). The substrate after step (v) is heated and annealed, causing the upper layer film 4 to be phase-separated into phase 4'a and phase 4'b, thereby forming a phase-separated structure 4'.

[0080] <Optional process> A method for manufacturing a structure having a phase-separated structure may include steps other than steps (i) to (vi) (optional steps). Such optional steps include a step of selectively removing a phase from the upper film that consists of at least one type of block from among the blocks constituting the block copolymer (hereinafter referred to as "step (vii)").

[0081] Regarding process (vii) In step (vii), a phase consisting of at least one type of block from the blocks constituting the block copolymer is selectively removed from the upper layer film formed on the lower layer film. This forms a fine pattern (polymer nanostructure).

[0082] Methods for selectively removing the block-based phase include treating the upper film with oxygen plasma or hydrogen plasma.

[0083] As described above, the inventors provide the following (1) to (9). (1) A composition containing polymer (A), The polymer (A) comprises a structural unit (A1) in which a hydrogen atom in a carboxyl group or hydroxyl group is substituted by an acid-dissociable group, and a structural unit (A2) derived from styrene and / or a styrene derivative. The aforementioned acid-dissociable group is not a tertiary carbon-carbon-containing aliphatic group, nor an acetal protecting group, The aforementioned tertiary carbon-containing aliphatic group is a group that contains a tertiary carbon atom and can bond to the carboxyl group or a residue from which a hydrogen atom has been removed via a bond attached to the tertiary carbon atom. The composition wherein the acetal protecting group is a group that can form an acetal structure by bonding with the carboxyl group or the residue from which a hydrogen atom has been removed from the hydroxyl group. (2) The constituent unit (A1) is the composition described in (1), which is represented by the following formula (a1-1) or formula (a1-2). [ka] (In formula (a1-1), R 11 is a hydrogen atom or a methyl group, L 11 is a single bond or a divalent linking group, X 11 R is a single bond or a carbonyl group. 12 ~R 14 These are, independently, aromatic groups which may have substituents, In formula (a1-2), R 21 is a hydrogen atom or a methyl group, L 21 is a single bond or a divalent linking group, X 21 R is a single bond or a carbonyl group. 22 ~R 24 These are each independently hydrocarbon groups that may have substituents. (3) The constituent unit (A1) is represented by the formula (a1-1), R 12 ~R 14 The composition according to (2), wherein each is independently a phenyl group which may have substituents. (4) The constituent unit (A1) is represented by the formula (a1-2), R 22 ~R 24 The composition according to (2), wherein each is independently an alkyl group. (5) With respect to the total number of moles of all constituent units that make up the polymer (A), The ratio of moles of the aforementioned constituent unit (A1) is between 1 mol% and 40 mol%, The composition according to any one of (1) to (4), wherein the ratio of moles of the constituent unit (A2) is 50 mol% or more and 95 mol% or less. (6) A reactive film containing polymer (A) whose hydrophilicity changes upon the action of an acid, The polymer (A) comprises a structural unit (A1) in which a hydrogen atom in a carboxyl group or hydroxyl group is substituted by an acid-dissociable group, and a structural unit (A2) derived from styrene and / or a styrene derivative. The aforementioned acid-dissociable group is not a tertiary carbon-carbon-containing aliphatic group, nor an acetal protecting group, The aforementioned tertiary carbon-containing aliphatic group is a group that contains a tertiary carbon atom and can bond to the carboxyl group or a residue from which a hydrogen atom has been removed via a bond attached to the tertiary carbon atom. A reactive film in which the acetal protecting group is a group that can form an acetal structure by bonding with the carboxyl group or the hydroxyl group from which a hydrogen atom has been removed. (7) A lower layer film used as a template for phase separation of block copolymers, The aforementioned lower layer film is formed by regioselectively applying an acid to the reactive film described in (6), An underlying film comprising two or more regions with differing hydrophilic properties. (8) Forming the reactive film described in (6) on the substrate, A photosensitive composition containing a photoacid generator is applied to the reactive film to form a photosensitive film. The photosensitive film is exposed to light in a position-selective manner, and the reactive film is treated with an acid in a position-selective manner to form a lower layer film. Removing the aforementioned photosensitive film, Forming an upper layer film containing a block copolymer on the aforementioned lower layer film, A method for producing a structure having a phase-separated structure, comprising phase-separating the block copolymer in the upper layer film. (9) A structural unit (A1) having a structure in which a hydrogen atom in a carboxyl group or hydroxyl group is substituted with an acid-dissociable group, and a structural unit (A2) derived from styrene and / or a styrene derivative, The aforementioned acid-dissociable group is not a tertiary carbon-carbon-containing aliphatic group, nor an acetal protecting group, The aforementioned tertiary carbon-containing aliphatic group is a group that contains a tertiary carbon atom and can bond to the carboxyl group or a residue from which a hydrogen atom has been removed via a bond attached to the tertiary carbon atom. The polymer is characterized in that the acetal protecting group is a group that can form an acetal structure by bonding with a residue from which a hydrogen atom has been removed from the carboxyl group or the hydroxyl group. [Examples]

[0084] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0085] <polymer> The polymers used in the examples and comparative examples are described below.

[0086] [Precursors of UL-1 and synthesis of UL-1] All reactions were carried out under a nitrogen atmosphere. 38.3 g of styrene, 3.03 g of vinylbenzocyclobutene, 12.1 g of hydroxyethyl methacrylate, and 0.269 g of 2,2'-azimonos(isobutyrate)dimethyl (V-601) were dissolved in 73.5 g of propylene glycol monomethyl ether acetate (PGMEA). The solution was added dropwise over 2 hours to a 200 mL three-necked flask containing 26 g of PGMEA (ambient temperature: 87 °C). After the addition was complete, the reaction solution was heated and stirred for 3 hours. After the reaction solution was cooled to room temperature, it was added to 1490 g of methanol for reprecipitation and purification. The obtained solid was added to 250 g of methanol and washed. It was dried under reduced pressure at 40 °C to obtain a white solid as a precursor of UL-1.

[0087] 8.15 g of UL-1 precursor, 7.47 g of trityl chloride (TrCl), 2.97 g of triethylamine (TEA), and 0.184 g of 4-dimethylaminopyridine (DMAP) were dissolved in 49.8 g of dichloromethane (DCM), and the solution was stirred at room temperature for 6 hours. The reaction solution was added to 600 g of methanol and reprecipitated. The resulting solid was dissolved in 60 g of dichloromethane, and the solution was added to 600 g of methanol and reprecipitated. The same procedure was repeated once more for purification. The resulting solid was dried under reduced pressure to obtain a white solid as UL-1. [ka]

[0088] [Synthesis of UL-2] UL-2 was synthesized in the same manner as UL-1, except that the ratio of monomers such as styrene was changed.

[0089] [Synthesis of UL-3 and UL-4] UL-3 and UL-4 were synthesized in the same manner as UL-1 and UL-2, except that trityl chloride was replaced with 4-methyltrityl chloride. [ka]

[0090] [Synthesis of UL-5 and UL-6] UL-5 and UL-6 were synthesized in the same manner as UL-1 and UL-2, except that trityl chloride was replaced with 4-tert-butyltrityl chloride. [ka]

[0091] [Synthesis of UL-7 and UL-8] UL-7 and UL-8 were synthesized in the same manner as UL-1 and UL-2, except that trityl chloride was replaced with 4,4'-dimethoxytrityl chloride. [ka]

[0092] [Synthesis of UL-9 and UL-10] UL-9 and UL-10 were synthesized in the same manner as UL-1 and UL-2, except that trityl chloride was replaced with tert-butyldimethylchlorosilane. [ka]

[0093] [Monomers of UL-11, and synthesis of UL-11] All reactions were carried out under a nitrogen atmosphere. 15.0 g of hydroxyethyl methacrylate, 30.5 g of trityl chloride (TrCl), 17.5 g of triethylamine (TEA), and 1.41 g of 4-dimethylaminopyridine (DMAP) were dissolved in 204 g of dichloromethane (DCM), and the solution was stirred at room temperature for 16 hours. 400 g of hexane was added to the reaction solution, and liquid-liquid extraction with 200 g of water was performed three times. The organic layer was dried under reduced pressure to obtain the monomer UL-11. [ka]

[0094] 38.3 g of styrene, 3.00 g of hydroxyethyl methacrylate, 18.0 g of UL-11 monomer, and 0.269 g of 2,2'-azimonos(isobutyrate)dimethyl (V-601) were dissolved in 73.5 g of propylene glycol monomethyl ether acetate (PGMEA). The solution was added dropwise over 2 hours to a 200 mL three-necked flask containing 26 g of PGMEA (at ambient temperature: 87 °C). After the addition was complete, the reaction solution was heated and stirred for 3 hours. After the reaction solution was cooled to room temperature, it was added to 1490 g of methanol for reprecipitation and purification. The obtained solid was added to 250 g of methanol and washed. It was dried under reduced pressure at 40 °C to obtain a white solid as UL-11. [ka]

[0095] [Synthesis of UL-12] UL-12 was synthesized in the same manner as UL-11, except that the ratio of monomers such as styrene was changed.

[0096] [Synthesis of UL-13 and UL-14] UL-13 and UL-14 were synthesized in the same manner as UL-11 and UL-12, except that trityl chloride was replaced with 4-methyltrityl chloride. [ka]

[0097] [Synthesis of UL-15 and UL-16] UL-15 and UL-16 were synthesized in the same manner as UL-11 and UL-12, except that trityl chloride was replaced with 4-tert-butyltrityl chloride. [ka]

[0098] [Synthesis of UL-17 and UL-18] UL-17 and UL-18 were synthesized in the same manner as UL-11 and UL-12, except that trityl chloride was replaced with 4,4'-dimethoxytrityl chloride. [ka]

[0099] [Synthesis of UL-19 and UL-20] UL-19 and UL-20 were synthesized in the same manner as UL-11 and UL-12, except that trityl chloride was replaced with tert-butyldimethylchlorosilane. [ka]

[0100] [Precursors of UL-21 and synthesis of UL-21] All reactions were carried out under a nitrogen atmosphere. 38.3 g of styrene, 3.03 g of vinylbenzocyclobutene, 4.00 g of methacrylic acid, and 0.269 g of 2,2'-azimonos(isobutyrate)dimethyl (V-601) were dissolved in 73.5 g of propylene glycol monomethyl ether acetate (PGMEA). The solution was added dropwise over 2 hours to a 200 mL three-necked flask containing 26 g of PGMEA (ambient temperature: 87 °C). After the addition was complete, the reaction solution was heated and stirred for 3 hours. After the reaction solution was cooled to room temperature, it was added to 1490 g of methanol for reprecipitation and purification. The resulting solid was added to 250 g of methanol and washed. It was dried under reduced pressure at 40 °C to obtain a white solid as a precursor of UL-21.

[0101] 8.15 g of UL-21 precursor, 7.47 g of trityl chloride (TrCl), 2.97 g of triethylamine (TEA), and 0.184 g of 4-dimethylaminopyridine (DMAP) were dissolved in 49.8 g of dichloromethane (DCM), and the solution was stirred at room temperature for 6 hours. The reaction solution was added to 600 g of methanol and reprecipitated. The resulting solid was dissolved in 60 g of dichloromethane, and the solution was added to 600 g of methanol and reprecipitated. The same procedure was repeated once more for purification. The resulting solid was dried under reduced pressure to obtain a white solid as UL-21. [ka]

[0102] [Synthesis of UL-22] UL-22 was synthesized in the same manner as UL-21, except that the ratio of monomers such as styrene was changed.

[0103] [Monomers of UL-23, and synthesis of UL-23] All reactions were carried out under a nitrogen atmosphere. 9.92 g of methacrylic acid, 30.5 g of trityl chloride (TrCl), 17.5 g of triethylamine (TEA), and 1.41 g of 4-dimethylaminopyridine (DMAP) were dissolved in 204 g of dichloromethane (DCM), and the solution was stirred at room temperature for 16 hours. 400 g of hexane was added to the reaction solution, and liquid-liquid extraction with 200 g of water was performed three times. The organic layer was dried under reduced pressure to obtain the UL-23 monomer. [ka]

[0104] 38.3 g of styrene, 3.00 g of hydroxyethyl methacrylate, 15.0 g of UL-23 monomer, and 0.269 g of 2,2'-azimonos(isobutyrate)dimethyl (V-601) were dissolved in 73.5 g of propylene glycol monomethyl ether acetate (PGMEA). The solution was added dropwise over 2 hours to a 200 mL three-necked flask containing 26 g of PGMEA (at ambient temperature: 87 °C). After the addition was complete, the reaction solution was heated and stirred for 3 hours. After the reaction solution was cooled to room temperature, it was added to 1490 g of methanol for reprecipitation and purification. The obtained solid was added to 250 g of methanol and washed. It was dried under reduced pressure at 40 °C to obtain a white solid as UL-23. [ka]

[0105] [Synthesis of UL-24] UL-24 was synthesized in the same manner as UL-23, except that the ratio of monomers such as styrene was changed.

[0106] UL-25: A random copolymer represented by the following formula (x:y:z = 77:2:21 (mol%)). [ka]

[0107] <Preparation of composition> The polymers listed in Table 1 or Table 2 were mixed with propylene glycol monomethyl ether acetate (PGMEA) to prepare the compositions for each example (solid content concentration: 1.3% by mass).

[0108] <Heat resistance evaluation> In Examples 1-10, 21, and 22, the composition of each example was applied to a silicon substrate by spin coating (1500 rpm) to a film thickness of 6 nm, and then baked at 110°C in an air atmosphere. Furthermore, the substrate was baked on a hot plate at 250°C or 310°C for 5 minutes in a nitrogen atmosphere to form a reactive film. In Examples 11-20, 23, 24, and Comparative Example 1, the composition of each example was applied to a silicon substrate by spin coating (1500 rpm) to a film thickness of 30 nm, and baked at 200°C in an air atmosphere. The substrate was then rinsed with PGMEA to remove unreacted polymers. Furthermore, the substrate was baked on a hot plate at 250°C or 310°C for 5 minutes in a nitrogen atmosphere to form a reactive film.

[0109] Using DropMaster700 (manufactured by Kyowa Interface Science Co., Ltd.), a 2.0 μL drop of pure water was placed on the surface of reactive films formed by baking at various temperatures, and the contact angle was measured once per second for a total of 10 times. Measurements were taken at three different points on the reactive film, and the average value of 30 measurements is shown in Table 1 as the "water contact angle". If the difference between the water contact angle of the reactive film formed by baking at 250°C and the water contact angle of the reactive film formed by baking at 310°C was 10° or more, it was evaluated as "B", and if it was less than 10°, it was evaluated as "A", and the results are shown in Table 1 as "heat resistance".

[0110] [Table 1]

[0111] As shown in Table 1, in the example using polymer (A) having a constituent unit (A1) containing a predetermined acid-dissociable group, the water contact angle remained almost unchanged even after high-temperature heat treatment. In contrast, in the comparative example using polymer having a constituent unit containing an acid-dissociable group which is a tertiary carbon atom-containing aliphatic group, the water contact angle changed significantly after high-temperature heat treatment. These results indicate that polymer (A) having a constituent unit (A1) containing a predetermined acid-dissociable group exhibits excellent heat resistance.

[0112] <Exposure Evaluation> In Examples 1-10, 21, and 22, the composition of each example was applied to a silicon substrate by spin coating (1500 rpm) to a film thickness of 6 nm, and then baked at 110°C in an air atmosphere. Furthermore, the substrate was baked on a hot plate at 250°C for 5 minutes in a nitrogen atmosphere to form a reactive film. In Examples 11-20, 23, 24, and Comparative Example 1, the composition of each example was applied to a silicon substrate by spin coating (1500 rpm) to a film thickness of 30 nm, and baked at 200°C in an air atmosphere. The substrate was then rinsed with PGMEA to remove unreacted polymers. Furthermore, the substrate was baked on a hot plate at 250°C for 5 minutes in a nitrogen atmosphere to form a reactive film.

[0113] A photoacid generator represented by the following formula and a 20% by mass PGMEA solution of polyhydroxystyrene were applied to a reactive film by spin coating (1500 rpm) to a thickness of 30 nm, and then baked at 110°C in an air atmosphere to form a photosensitive film. [ka]

[0114] The photosensitive film was irradiated with a KrF excimer laser (wavelength: 248 nm) at an exposure dose of 25 mJ using a KrF exposure apparatus. The substrate was then post-baked at 110°C for 1 minute, and the photosensitive film was removed by rinsing with a mixed solvent of propylene glycol monomethyl ether and PGMEA (8:2 mass ratio). The rinsed substrate was then baked at 100°C for 1 minute.

[0115] Using a DropMaster 700 (manufactured by Kyowa Interface Science Co., Ltd.), a 2.0 μL drop of pure water was applied to the reactive film before the formation of the photosensitive film, or to the underlying film after the photosensitive film was removed. The contact angle was measured once per second for a total of 10 times. Measurements were taken at three different points on the reactive film or underlying film, and the average value of 30 measurements is shown in Table 2 as the "water contact angle".

[0116] [Table 2]

[0117] As shown in Table 2, in the example using polymer (A) having a constituent unit (A1) containing a predetermined acid-dissociable group, the water contact angle changed significantly when the photosensitive film formed on the reactive film was exposed to light. From these results, it can be seen that a chemical guide pattern can be formed by a simple method without complicated procedures.

Claims

1. A composition containing polymer (A), The polymer (A) comprises a structural unit (A1) in which a hydrogen atom in a carboxyl group or hydroxyl group is substituted by an acid-dissociable group, and a structural unit (A2) derived from styrene and / or a styrene derivative. The aforementioned acid-dissociable group is not a tertiary carbon-carbon-containing aliphatic group, nor an acetal protecting group, The aforementioned tertiary carbon-containing aliphatic group is a group that contains a tertiary carbon atom and can bond to the carboxyl group or a residue from which a hydrogen atom has been removed via a bond attached to the tertiary carbon atom. The composition wherein the acetal protecting group is a group that can form an acetal structure by bonding with the carboxyl group or the residue from which a hydrogen atom has been removed from the hydroxyl group.

2. The composition according to claim 1, wherein the constituent unit (A1) is represented by the following formula (a1-1) or formula (a1-2). 【Chemistry 1】 (In formula (a1-1), R １１ L is a hydrogen atom or a methyl group. １１ is a single bond or a divalent linking group, X １１ R is a single bond or a carbonyl group. １２ ~R １４ These are, independently, aromatic groups which may have substituents, In formula (a1-2), R ２１ is a hydrogen atom or a methyl group, and L ２１ is a single bond or a divalent linking group, and X ２１ is a single bond or a carbonyl group, and R ２２ to R ２４ are each independently a hydrocarbon group which may have a substituent.

3. The aforementioned constituent unit (A1) is represented by the above formula (a1-1), R １２ ~R １４ The composition according to claim 2, wherein each of them is independently a phenyl group which may have substituents.

4. The aforementioned constituent unit (A1) is represented by the above formula (a1-2), R ２２ ~R ２４ The composition according to claim 2, wherein each of them is independently an alkyl group.

5. With respect to the total number of moles of all constituent units that make up the polymer (A), The ratio of moles of the aforementioned constituent unit (A1) is 1 mol% or more and 40 mol% or less. The composition according to claim 1, wherein the ratio of moles of the constituent unit (A2) is 50 mol% or more and 95 mol% or less.

6. A reactive film containing polymer (A) whose hydrophilicity changes upon the action of an acid, The polymer (A) comprises a structural unit (A1) in which a hydrogen atom in a carboxyl group or hydroxyl group is substituted by an acid-dissociable group, and a structural unit (A2) derived from styrene and / or a styrene derivative. The aforementioned acid-dissociable group is not a tertiary carbon-carbon-containing aliphatic group, nor an acetal protecting group, The aforementioned tertiary carbon-containing aliphatic group is a group that contains a tertiary carbon atom and can bond to the carboxyl group or a residue from which a hydrogen atom has been removed via a bond attached to the tertiary carbon atom. A reactive film in which the acetal protecting group is a group that can form an acetal structure by bonding with the carboxyl group or the hydroxyl group from which a hydrogen atom has been removed.

7. A lower layer film used as a template for phase separation of block copolymers, The aforementioned lower layer film is formed by regioselectively applying an acid to the reactive film described in claim 6. An underlayer film comprising two or more regions with differing hydrophilicity.

8. Forming the reactive film described in claim 6 on the substrate, A photosensitive composition containing a photoacid generator is applied to the reactive film to form a photosensitive film. The photosensitive film is exposed to light in a position-selective manner, and the reactive film is treated with an acid in a position-selective manner to form a lower layer film. Removing the aforementioned photosensitive film, Forming an upper layer film containing a block copolymer on the aforementioned lower layer film, A method for producing a structure having a phase-separated structure, comprising phase-separating the block copolymer in the upper layer film.

9. The structure comprises a constituent unit (A1) having a structure in which a hydrogen atom in a carboxyl group or hydroxyl group is substituted by an acid-dissociable group, and a constituent unit (A2) derived from styrene and / or a styrene derivative. The aforementioned acid-dissociable group is not a tertiary carbon-carbon-containing aliphatic group, nor an acetal protecting group, The aforementioned tertiary carbon-containing aliphatic group is a group that contains a tertiary carbon atom and can bond to the carboxyl group or a residue from which a hydrogen atom has been removed via a bond attached to the tertiary carbon atom. The polymer is characterized in that the acetal protecting group is a group that can form an acetal structure by bonding with a residue from which a hydrogen atom has been removed from the carboxyl group or the hydroxyl group.

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