Composition and polymer

Abstract

To provide a composition which exhibits good substrate selectivity and can form a polymer brush having good brush density and heat resistance, and to provide a polymer.SOLUTION: A composition used for selective modification of a base material having a surface including two or more regions having different materials from each other, the composition comprising a polymer (A) and a solvent (S), wherein the polymer (A) has a block (A1) and a block (A2), and the block (A1) has a constitutional unit derived from at least one selected from the group consisting of styrene, a styrene derivative, and (α - substituted) acrylic ester; The block (A2) has two or more groups represented by Formula (1), and the group represented by Formula (1) is bonded to a carbon atom. -X-P (= O) (OR1) 2. (1) In the formula (1), X is a single bond or oxygen, and R1 is an alkyl group. ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition and a polymer used for selectively modifying a substrate having a surface including two or more regions made of different materials. [Background technology]

[0002] As semiconductor devices continue to shrink, there is a demand for technology to form finer patterns of less than 30 nm. However, with conventional lithography methods, it is becoming technically difficult to form finer patterns due to optical factors and other factors.

[0003] Therefore, development of a technology for forming even finer patterns is being conducted by utilizing a phase-separated structure formed by the self-assembly of a block copolymer in which mutually incompatible blocks are bonded together. For example, Patent Document 1 proposes a primer that is used to phase-separate a layer containing a block copolymer and modify the surface of a substrate, the primer containing a polymer compound in which a first polymer block and a second polymer block are bonded via a linking group containing a substrate-adhesive group.

[0004] In addition, methods for selectively modifying a substrate having two or more microscopic regions on its surface made of different materials have been investigated. This selective modification method requires a material that can modify the surface region easily and highly selectively, and various materials have been investigated. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2018-159061 Summary of the Invention [Problem to be solved by the invention]

[0006] In the selective modification method, polymer brushes using polymers with adsorptive end groups have been developed, but no primers that can form polymer brushes with good substrate selectivity and high brush density have been identified.

[0007] Furthermore, after the selective modification, high-temperature treatment such as annealing may be performed when self-assembling block copolymers, and therefore a primer capable of forming polymer brushes with good heat resistance is also required.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition and a polymer that can form polymer brushes that exhibit good substrate selectivity and have good brush density and heat resistance. [Means for solving the problem]

[0009] In order to solve the above problems, the present inventors have conducted extensive research and found that the above problems can be solved by using a composition containing a specific polymer (A), and have thus completed the present invention. Specifically, the present invention provides the following.

[0010] A first aspect of the present invention is a composition used for selectively modifying a substrate having a surface including two or more regions made of different materials, the composition comprising: A polymer (A) and a solvent (S), The polymer (A) has a block (A1) and a block (A2), the block (A1) has a structural unit derived from at least one selected from the group consisting of styrene, a styrene derivative, and an (α-substituted) acrylic acid ester, The block (A2) is represented by the following formula (1): -XP(=O)(OR 1 )2···(1) (In formula (1), X is a single bond or an oxygen atom, and R 1 is an alkyl group. and having two or more groups represented by The group represented by the formula (1) is a composition bonded to a carbon atom.

[0011] A second aspect of the present invention is a polymer having a block (A1) and a block (A2), the block (A1) has a structural unit derived from at least one selected from the group consisting of styrene, a styrene derivative, and an (α-substituted) acrylic acid ester, The block (A2) is represented by the following formula (1): -XP(=O)(OR 1 )2···(1) (In formula (1), X is a single bond or an oxygen atom, and R 1 is an alkyl group. and having two or more groups represented by The group represented by the formula (1) is a polymer bonded to a carbon atom. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a composition and a polymer that can form polymer brushes that exhibit good substrate selectivity and have good brush density and heat resistance. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments and can be practiced with appropriate modifications within the scope of the object of the present invention.

[0014] ≪Composition≫ The composition is used for selectively modifying a substrate having a surface including two or more regions made of different materials, and contains a polymer (A) and a solvent (S). The polymer (A) has a block (A1) and a block (A2). The block (A1) has a structural unit derived from at least one selected from the group consisting of styrene, a styrene derivative, and an (α-substituted) acrylic acid ester. The block (A2) has two or more groups represented by the following formula (1). The group represented by formula (1) is bonded to a carbon atom. -XP(=O)(OR 1 )2···(1) (In formula (1), X is a single bond or an oxygen atom, and R 1 is an alkyl group.

[0015] The surface of the substrate preferably includes a region containing a metal (hereinafter also referred to as "region (I)"), and more preferably includes region (I) and a region consisting essentially of non-metallic materials (hereinafter also referred to as "region (II)").

[0016] The metal is not particularly limited as long as it is a metal element. Silicon is a nonmetal and does not fall under the category of metal. Examples of metals include copper, iron, zinc, cobalt, aluminum, tin, tungsten, zirconium, titanium, tantalum, germanium, molybdenum, ruthenium, gold, silver, platinum, palladium, and nickel. Among these, copper, cobalt, tungsten, or tantalum is preferred.

[0017] Examples of the form in which the metal is contained in the region (I) include an elemental metal, an alloy, a conductive nitride, a metal oxide, and a silicide.

[0018] Examples of the elemental metal include elemental metals such as copper, iron, cobalt, tungsten, and tantalum. Examples of alloys include nickel-copper alloys, cobalt-nickel alloys, and gold-silver alloys. Examples of conductive nitrides include tantalum nitride, titanium nitride, iron nitride, and aluminum nitride. Examples of metal oxides include tantalum oxide, aluminum oxide, iron oxide, and copper oxide. Examples of silicide include iron silicide and molybdenum silicide.

[0019] Among these, a metal element, an alloy, a conductive nitride, or a silicide is preferred, a metal element or a conductive nitride is more preferred, and copper element, cobalt element, tungsten element, tantalum element, or tantalum nitride is even more preferred.

[0020] Examples of the form in which the nonmetal is contained in region (II) include a nonmetal element, a nonmetal oxide, a nonmetal nitride, and a nonmetal oxide nitride.

[0021] Examples of the non-metal element include elements such as silicon and carbon. Examples of non-metal oxides include silicon oxide. Examples of non-metallic nitrides include SiN x , and Si3N4, etc. Examples of non-metal oxide nitrides include SiON.

[0022] Among these, non-metal oxides or non-metal nitrides are preferred, and non-metal oxides are more preferred.

[0023] The shape of the region (I) and / or region (II) on the surface of the substrate is not particularly limited, and examples thereof include a planar shape, a dotted shape, a striped shape, etc. The size of the region (I) and region (II) is not particularly limited, and the region can be of any desired size. The shape of the substrate is not particularly limited, and may be any desired shape such as a plate (substrate) or a sphere.

[0024] <Polymer (A)> The polymer (A) has a block (A1) and a block (A2).

[0025] (Block (A1)) The block (A1) has a structural unit derived from at least one selected from the group consisting of styrene, styrene derivatives, and (α-substituted) acrylic esters.

[0026] Examples of styrene derivatives include compounds in which the hydrogen atom bonded to the carbon atom at the α-position of styrene is substituted with a substituent such as an alkyl group having from 1 to 10 carbon atoms, and compounds in which the hydrogen atom of the phenyl group of styrene is substituted with a substituent such as an alkyl group having from 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a hydroxy group, a nitro group, a halogen atom, or an acetoxy group. 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, and 4-chloromethylstyrene.

[0027] The (α-substituted) acrylic ester is an acrylic ester or an acrylic acid derivative in which the hydrogen atom bonded to the carbon atom at the α-position of the acrylic ester is substituted with a substituent. Examples of the substituent in the (α-substituted) acrylic acid ester include an alkyl group having from 1 to 5 carbon atoms and a halogenated alkyl group having from 1 to 5 carbon atoms. Among these, an alkyl group having from 1 to 5 carbon atoms is preferred, and a methyl group is more preferred.

[0028] Suitable examples of the (α-substituted) acrylic acid ester include (α-substituted) alkyl acrylates, (α-substituted) cycloalkyl acrylates, (α-substituted) hydroxyalkyl acrylates, (α-substituted) aryl acrylates, (α-substituted) aralkyl acrylates, (α-substituted) epoxyalkyl acrylates, and (α-substituted) epoxycycloalkyl acrylates. Among these (α-substituted) acrylic acid esters, (α-substituted) alkyl acrylate esters are preferred. In the (α-substituted) alkyl acrylate esters, the alkyl group constituting the alkyl ester preferably has 1 or more and 10 or less carbon atoms, more preferably 1 or more and 5 or less carbon atoms. Specific examples of the (α-substituted) acrylic acid ester include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, octyl acrylate, nonyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, benzyl acrylate, anthracene acrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethane acrylate, and 3-trimethoxysilylpropyl acrylate; and methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, nonyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, benzyl methacrylate, anthracene methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethane methacrylate, and 3-trimethoxysilylpropyl methacrylate.

[0029] Of the above, the (α-substituted) acrylic acid ester is preferably an alkyl acrylate or an alkyl methacrylate, more preferably methyl acrylate, ethyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, or tert-butyl methacrylate, and even more preferably methyl methacrylate.

[0030] The block (A1) preferably has a structural unit derived from styrene or methyl methacrylate.

[0031] The ratio of the number of moles of all structural units constituting block (A1) to the number of moles of all structural units constituting polymer (A) is preferably 40 mol% or more, more preferably 50 mol% or more, even more preferably 60 mol% or more, particularly preferably 70 mol% or more, and most preferably 80 mol% or more. This ratio is preferably 99 mol% or less, more preferably 95 mol% or less. Within this numerical range, good brush density is likely to be obtained.

[0032] (Block A2) The block (A2) has two or more groups represented by the following formula (1): The group represented by formula (1) is bonded to a carbon atom. -XP(=O)(OR 1 )2···(1) (In formula (1), X is a single bond or an oxygen atom, and R 1 is an alkyl group. 1 may be the same or different.)

[0033] From the viewpoint of heat resistance, X is preferably an oxygen atom.

[0034] R 1 The number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and even more preferably 1 or more and 3 or less. R 1 The alkyl group may be linear or branched, but is preferably linear. Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Examples of branched alkyl groups include isopropyl, sec-butyl, isobutyl, tert-butyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, and tert-pentyl.

[0035] The block (A2) may or may not be an oligomer or polymer composed of a plurality of structural units, but is preferably an oligomer or polymer.

[0036] It is preferable that block (A2) has two or more structural units having a group represented by formula (1). Note that the number of structural units does not refer to the number of types of structural units, but rather to the number of structural units having a group represented by formula (1) present in block (A2). The two or more structural units having a group represented by formula (1) may consist of only the same type of structural unit, or may consist of two or more types of structural units. In the structural unit having a group represented by formula (1), the number of groups represented by formula (1) is not particularly limited, but may be, for example, 1 or 2, or 1.

[0037] The block (A2) preferably has two or more structural units derived from a compound having a group represented by formula (1) and an ethylenically unsaturated group. The ethylenically unsaturated group is a group containing an ethylenically unsaturated double bond. The ethylenically unsaturated group is not particularly limited, but examples thereof include alkenyl groups such as vinyl, 1-propenyl, 2-n-propenyl (allyl), 1-n-butenyl, 2-n-butenyl, and 3-n-butenyl; (meth)acryloyl group-containing groups such as (meth)acryloyl, (meth)acryloyloxy, and (meth)acryloylamino; and the like. Among these, (meth)acryloyl group-containing groups are preferred, and (meth)acryloyloxy groups are preferred.

[0038] The block (A2) preferably has two or more structural units derived from an (α-substituted) acrylic acid ester having a group represented by formula (1). The substituent in the (α-substituted) acrylic acid ester is the same as the substituent in the (α-substituted) acrylic acid ester in the block (A1).

[0039] As a structural unit derived from an (α-substituted) acrylic acid ester having a group represented by formula (1), a structural unit represented by the following formula (2) is preferred. [ka] (In formula (2), R 21is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and R 22 represents an alkylene group which may have a substituent, and A represents a group represented by formula (1).

[0040] R 21 Examples of the alkyl group having 1 to 5 carbon atoms as the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, and a tert-pentyl group. A halogenated alkyl group having from 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of an alkyl group having from 1 to 5 carbon atoms have been substituted with halogen atoms. Fluorine atoms are particularly preferred as the halogen atoms. R 21 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group.

[0041] R 22 The alkylene group as the alkylene group preferably has 1 or more and 10 or less carbon atoms, and more preferably has 1 or more and 8 or less carbon atoms. R 22 The alkylene group as may be linear or branched, but is preferably linear. Examples of the linear alkylene group include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], and a hexamethylene group [-(CH2)6-]. Examples of branched alkylene groups include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0042] R 22 Examples of the substituent that the alkylene group may have include a halogen atom and a halogenated alkyl group having 1 to 5 carbon atoms and substituted with a halogen atom.

[0043] Specific examples of structural units derived from (α-substituted) acrylic acid esters having a group represented by formula (1) are shown below. [ka]

[0044] The ratio of the number of moles of all structural units constituting block (A2) to the number of moles of all structural units constituting polymer (A) is preferably greater than 0 mol%, more preferably 1 mol% or more, and even more preferably 5 mol% or more. Furthermore, this ratio is preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably 40 mol% or less, particularly preferably 30 mol% or less, and most preferably 20 mol% or less. Within the above numerical range, good brush density is likely to be obtained.

[0045] The polymer (A) may have blocks other than the block (A1) and the block (A2), but preferably has no other blocks. When the polymer (A) has other blocks, it is preferable that the block (A2) is not sandwiched between blocks other than the block (A2) (it is located at either end of the main chain of the polymer (A)).

[0046] The sum of the ratio of the number of moles of all structural units constituting the block (A1) and the number of moles of all structural units constituting the block (A2) to the number of moles of all structural units constituting the polymer (A) is preferably 70 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and may be 100 mol%.

[0047] The number average molecular weight (Mn) of the polymer (A) is preferably 30,000 or less, more preferably 20,000 or less, even more preferably 10,000 or less, and particularly preferably 8,000 or less. Furthermore, the Mn is preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 3,000 or more. Within the above numerical range, good brush density is easily obtained. In this specification, the "number average molecular weight" (Mn) is the number average molecular weight calculated in terms of standard polystyrene by size exclusion chromatography (SEC) measurement.

[0048] The method for producing the polymer (A) is not particularly limited. For example, when the block (A2) is an oligomer or a polymer, it can be produced by polymerizing a monomer of the structural unit constituting the block (A1) and a monomer of the structural unit constituting the block (A2) by a conventionally known polymerization method.

[0049] <Solvent (S)> The composition contains a solvent (S). The solvent (S) may be an organic solvent. The organic solvent may be any organic solvent capable of dissolving each component to be used and forming a homogeneous solution. Any organic solvent selected from organic solvents conventionally known as solvents for compositions containing a resin as a main component may be used.

[0050] 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, and dipropylene glycol monoacetate; and compounds of polyhydric alcohols having an ether bond such as monoalkyl ethers, monomethyl ethers, monoethyl ethers, monopropyl ethers, and monobutyl ethers of the polyhydric alcohols or monoacetates of the polyhydric alcohols, or monophenyl ethers. Derivatives [among these, 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 derivatives of the aforementioned polyhydric alcohols; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene. The organic solvent components may be used alone or in a mixture of two or more. Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, or ethyl lactate (EL) is preferred.

[0051] The content of the solvent contained in the composition is not particularly limited. The solvent is appropriately selected depending on the coating film thickness so that the concentration of the composition is a concentration that can be applied. The solvent is generally used so that the solid content concentration of the composition is in the range of 0.2% by mass to 70% by mass, preferably 0.2% by mass to 50% by mass.

[0052] <Other ingredients> If desired, the composition may further contain compatible additives, such as additional resins for improving the performance of the underlayer film, surfactants for improving coatability, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, sensitizers, base amplifiers, and basic compounds.

[0053] <Polymer> The polymer has a block (A1) and a block (A2). The block (A1) has a structural unit derived from at least one selected from the group consisting of styrene, a styrene derivative, and an (α-substituted) acrylic acid ester. The block (A2) has two or more groups represented by the following formula (1). The group represented by formula (1) is bonded to a carbon atom. -XP(=O)(OR 1 )2···(1) (In formula (1), X is a single bond or an oxygen atom, and R 1 is an alkyl group.

[0054] The details and preferred embodiments of the polymer are the same as those of the polymer (A) in the above-mentioned "Composition."

[0055] As described above, the present inventors provide the following [1] to [7]. [1] A composition used for selectively modifying a substrate having a surface including two or more regions made of different materials, A polymer (A) and a solvent (S), The polymer (A) has a block (A1) and a block (A2), the block (A1) has a structural unit derived from at least one selected from the group consisting of styrene, a styrene derivative, and an (α-substituted) acrylic acid ester, The block (A2) is represented by the following formula (1): -XP(=O)(OR 1 )2···(1) (In formula (1), X is a single bond or an oxygen atom, and R 1 is an alkyl group. and having two or more groups represented by A composition, wherein the group represented by formula (1) is bonded to a carbon atom. [2] The block (A2) has two or more structural units derived from an (α-substituted) acrylic acid ester having a group represented by the formula (1), The composition according to [1], wherein the ratio of the number of moles of all structural units constituting the block (A2) to the number of moles of all structural units constituting the polymer (A) is more than 0 mol% and 50 mol% or less. [3] The composition according to [2], wherein the ratio of the number of moles of all structural units constituting the block (A2) to the number of moles of all structural units constituting the polymer (A) is more than 0 mol% and 20 mol% or less. [4] The composition according to any one of [1] to [3], wherein the number average molecular weight of the polymer (A) is 2,000 or more and 10,000 or less. [5] The composition according to any one of [1] to [4], wherein the block (A1) has a structural unit derived from styrene or methyl methacrylate. [6] A polymer having a block (A1) and a block (A2), the block (A1) has a structural unit derived from at least one selected from the group consisting of styrene, a styrene derivative, and an (α-substituted) acrylic acid ester, The block (A2) is represented by the following formula (1): -XP(=O)(OR 1 )2···(1) (In formula (1), X is a single bond or an oxygen atom, and R 1 is an alkyl group. and having two or more groups represented by A polymer in which the group represented by formula (1) is bonded to a carbon atom. [7] The block (A2) has two or more structural units derived from an (α-substituted) acrylic acid ester having a group represented by the formula (1), The polymer according to [6], wherein the ratio of the number of moles of all structural units constituting the block (A2) to the number of moles of all structural units constituting the polymer (A) is more than 0 mol % and 50 mol % or less. [Example]

[0056] The present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[0057] The polymers used in the examples and comparative examples will be described below. A-1 to A-5: Polymers represented by the following formulas. In the formulas, x and y in the lower right of the parentheses represent the ratio (mol %) of the number of moles of each structural unit to the number of moles of all structural units. A-1 has a number average molecular weight (Mn) of 5,000, x is 50 mol %, and y is 50 mol %. A-2 has an Mn of 5,000, x is 80 mol %, and y is 20 mol %. A-3 has an Mn of 5,000, x is 90 mol %, and y is 10 mol %. A-4 has an Mn of 10,000, x is 90 mol %, and y is 10 mol %. A-5 has an Mn of 15,000, x is 90 mol %, and y is 10 mol %. [ka]

[0058] A-6 to A-10: Polymers represented by the following formulas. In the formulas, x and y at the bottom right of the parentheses represent the ratio (mol %) of the number of moles of each structural unit to the number of moles of all structural units. Mn of A-6 is 5,000, x is 50 mol %, and y is 50 mol %. Mn of A-7 is 5,000, x is 80 mol %, and y is 20 mol %. Mn of A-8 is 5,000, x is 90 mol %, and y is 10 mol %. Mn of A-9 is 10,000, x is 90 mol %, and y is 10 mol %. Mn of A-10 is 15,000, x is 90 mol %, and y is 10 mol %. [ka]

[0059] A-11: A polymer represented by the following formula. In the formula, x and y at the bottom right of the parentheses represent the ratio (mol %) of the number of moles of each structural unit to the number of moles of all structural units. Mn of A-11 is 5,000, x is 90 mol %, and y is 10 mol %. [ka]

[0060] A-12: A polymer represented by the following formula. In the formula, x and y at the bottom right of the parentheses represent the ratio (mol %) of the number of moles of each structural unit to the number of moles of all structural units. Mn of A-12 is 5,000, x is 90 mol %, and y is 10 mol %. [ka]

[0061] A-13: A polymer represented by the following formula. In the formula, x and y at the bottom right of the parentheses represent the ratio (mol %) of the number of moles of each structural unit to the number of moles of all structural units. Mn of A-13 is 5,000, x is 90 mol %, and y is 10 mol %. [ka]

[0062] A-14 and A-15: Polymers represented by the following formulae. Mn of A-14 is 10,000. Mn of A-15 is 4,700. [ka]

[0063] A-16: A polymer represented by the following formula. In the formula, x and y at the bottom right of the parentheses represent the ratio (mol %) of the number of moles of each structural unit to the number of moles of all structural units. Mn of A-16 is 5,000, x is 90 mol %, and y is 10 mol %. [ka]

[0064] <Preparation of Composition> The compositions of each example were prepared by mixing the polymer type listed in Table 1 with propylene glycol monomethyl ether acetate (PGMEA) to a concentration of 1.0% by weight.

[0065] <Evaluation of the composition> (Substrate surface treatment) A tungsten (W) substrate was immersed in 0.2 mass % hydrofluoric acid, rinsed with pure water, and then dried under a nitrogen flow. The silicon oxide (SiO2) substrate was surface treated with isopropanol.

[0066] (film formation) Each composition was applied to a surface-treated tungsten substrate by spin coating at 1500 rpm. The coated substrate was then baked in an air atmosphere on a hot plate at 200°C for 5 minutes. The substrate was then rinsed with PGMEA to remove unreacted polymer. The substrate was then baked at 100°C for 1 minute to remove the solvent, forming a film on the tungsten substrate. Similarly, a film was also formed on a silicon oxide substrate.

[0067] (Contact angle evaluation) Using a DropMaster 700 (Kyowa Interface Science Co., Ltd.), a droplet of pure water (2.0 μL) was dropped onto the surface of the substrate on which the film had been formed, and the contact angle of the substrate was measured once per second, a total of 10 times. Measurements were taken at three different points on the substrate, and the average of a total of 30 measurements was used as the water contact angle. As a reference example, the contact angle of the substrate before the film was formed was also measured in the same way. The results are shown in Table 1.

[0068] (Evaluation of film thickness) The thickness of the formed film was measured using a spectroscopic ellipsometer (M-2000 manufactured by JA Woollam Co., Ltd.) The results are shown in Table 1.

[0069] (Brush density evaluation) Based on the film thickness on the tungsten substrate, the brush density of the film (polymer brush) formed on the tungsten substrate was calculated using the following formula. The results are shown in Table 1. The density of A-1 was 1.09 g / cm 3 , the density of A-2 is 1.07 g / cm 3 , the density of A-3 to A-5 is 1.06 g / cm 3 , the density of A-6 to A-13 is 1.17 g / cm 3 , the density of A-14 to A-15 is 1.05 g / cm 3 , the density of A-16 is 1.17g / cm 3 It was calculated as: σ=d×L×NA×10 -21 / Mn [σ: brush density (number of chains / nm 2 ), d: polymer density (g / cm 3 ), L: film thickness (nm), NA: Avogadro's number, Mn: number average molecular weight of polymer (g / number of chains)]

[0070] (Evaluation of heat resistance) The tungsten substrate on which the film was formed was baked in an air atmosphere on a hot plate at 280°C for 5 minutes, then rinsed with PGMEA and further baked at 100°C for 1 minute. After these treatments, the film thickness of the substrate was measured and the brush density was calculated. The results were evaluated as "B" when there was a change of 5% or more compared to the brush density of the substrate before treatment, and "A" when there was no change of 5% or more. The results are shown in Table 1.

[0071] [Table 1]

[0072] As shown in Table 1, in Examples 1 to 13 using predetermined polymers, it was confirmed that selectivity to metal surfaces was good from the change in water contact angle compared to the Reference Example. Furthermore, it was confirmed that the film formed was thicker and had a higher brush density than in Comparative Examples 1 to 3. Furthermore, it was confirmed that the heat resistance was good.

Claims

1. A composition used for selectively modifying a substrate having a surface including two or more regions made of different materials, comprising: Contains a polymer (A) and a solvent (S), The polymer (A) has a block (A1) and a block (A2), the block (A1) has a structural unit derived from at least one selected from the group consisting of styrene, a styrene derivative, and an (α-substituted) acrylic acid ester, The block (A2) is represented by the following formula (1): -X-P(=O)(OR １ ) ２ ・・・(1) (In formula (1), X is a single bond or an oxygen atom, and R １ is an alkyl group. and having two or more groups represented by A composition, wherein the group represented by formula (1) is bonded to a carbon atom.

2. the block (A2) has two or more structural units derived from an (α-substituted) acrylic acid ester having a group represented by formula (1), 2. The composition according to claim 1, wherein the ratio of the number of moles of all structural units constituting the block (A2) to the number of moles of all structural units constituting the polymer (A) is more than 0 mol% and 50 mol% or less.

3. The composition according to claim 2, wherein the ratio of the number of moles of all structural units constituting the block (A2) to the number of moles of all structural units constituting the polymer (A) is more than 0 mol% and 20 mol% or less.

4. The composition according to claim 1 or 2, wherein the number average molecular weight of the polymer (A) is 2,000 or more and 10,000 or less.

5. The composition according to claim 1 or 2, wherein the block (A1) has a structural unit derived from styrene or methyl methacrylate.

6. A polymer having a block (A1) and a block (A2), the block (A1) has a structural unit derived from at least one selected from the group consisting of styrene, a styrene derivative, and an (α-substituted) acrylic acid ester, The block (A2) is represented by the following formula (1): -X-P(=O)(OR １ ) ２ ・・・(1) (In formula (1), X is a single bond or an oxygen atom, and R １ is an alkyl group. and having two or more groups represented by A polymer in which the group represented by formula (1) is bonded to a carbon atom.

7. the block (A2) has two or more structural units derived from an (α-substituted) acrylic acid ester having a group represented by formula (1), The polymer according to claim 6, wherein the ratio of the number of moles of all structural units constituting the block (A2) to the number of moles of all structural units constituting the polymer (A) is more than 0 mol% and 50 mol% or less.

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