Compositions and polymers

Abstract

The present invention provides a composition and polymer capable of forming polymer brushes that exhibit good substrate selectivity and have good brush density and heat resistance. [Solution] A composition used for selective modification of a substrate having a surface including two or more regions of different materials, comprising a polymer (A) and a solvent (S), wherein polymer (A) has constituent units derived from styrene and / or constituent units derived from styrene derivatives, and polymer (A) has a group represented by the following formula (1) at the end of its main chain. -R 1 -OP(=O)(OR 2 )2(1)

Description

[Technical Field]

[0001] The present invention relates to compositions and polymers used for selective modification of a substrate having a surface that includes two or more regions of different materials. [Background technology]

[0002] With the further miniaturization of semiconductor devices, there is a demand for technologies that can form finer patterns than 30 nm. However, conventional lithography methods are becoming technically difficult to use due to optical factors and other limitations.

[0003] Therefore, techniques are being developed to form even finer patterns by utilizing the phase separation structure formed by the self-assembly of block copolymers, in which mutually incompatible blocks are bonded together. For example, Patent Document 1 proposes a 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 adhesion group, which is used to phase separate a layer containing a block copolymer and to modify the substrate surface.

[0004] Furthermore, methods for selectively modifying substrates having two or more fine regions on their surface with different materials are being investigated. This selective modification method requires materials that can modify surface regions simply and with high selectivity, and various materials are being considered. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2018-159061 [Overview of the project] [Problems that the invention aims to solve]

[0006] In the above selective modification method, polymer brushes using polymers having adsorptive end groups have been developed. However, a primer capable of forming a polymer brush that exhibits good substrate selectivity and has a good brush density is not yet known.

[0007] In addition, after the above selective modification, high-temperature treatment such as annealing treatment during self-organization of the block copolymer may be performed, and a primer capable of forming a polymer brush having good heat resistance is also required.

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

Means for Solving the Problems

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

[0010] A first aspect is a composition used for selective modification of a substrate having a surface including two or more regions made of different materials, containing a polymer (A) and a solvent (S), The polymer (A) has a structural unit derived from styrene and / or a structural unit derived from a styrene derivative, The polymer (A) has the following formula (1): -R 1 -O-P(=O)(OR 2 )2(1) (In formula (1), R 1 is a divalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R 2 is a monovalent hydrocarbon group.) and is a composition having a group represented by the formula at the end of the main chain.

[0011] The second aspect has a structural unit derived from styrene and / or a structural unit derived from a styrene derivative, the following formula (1): -R 1 -O-P(=O)(OR 2 )2(1) (In formula (1), R 1 is a divalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R 2 is a monovalent hydrocarbon group.) and is a polymer having a group represented by the formula at the end of the main chain.

Advantages of the Invention

[0012] According to the present invention, it is possible to provide a composition and a polymer that exhibit good substrate selectivity and can form a polymer brush having good brush density and heat resistance.

Modes for Carrying Out the Invention

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

[0014] <<Composition>> The composition is used for the selective modification of 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 structural unit derived from styrene and / or a structural unit derived from a styrene derivative. The polymer (A) has a group represented by the following formula (1) at the end of the main chain. -R 1 -O-P(=O)(OR 2 )2(1) (In formula (1), R 1 is a divalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R 2 is a monovalent hydrocarbon group.)

[0015] The surface of the substrate preferably includes a region containing metal (hereinafter also referred to as "region (I)"), and more preferably includes region (I) and a region consisting substantially only of nonmetals (hereinafter also referred to as "region (II)").

[0016] The metal is not particularly limited as long as it is a metallic element. Note that silicon is a nonmetal and does not qualify as a 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 are preferred.

[0017] Examples of metal content in region (I) include elemental metals, alloys, conductive nitrides, metal oxides, and silicides.

[0018] Examples of elemental metals include 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 silicides include iron silicide and molybdenum silicide.

[0019] Among these, elemental metals, alloys, conductive nitrides, or silicides are preferred, elemental metals or conductive nitrides are more preferred, and elemental copper, elemental cobalt, elemental tungsten, elemental tantalum, or tantalum nitride are even more preferred.

[0020] Examples of nonmetallic forms in region (II) include elemental nonmetals, nonmetallic oxides, nonmetallic nitrides, and nonmetallic oxide nitrides.

[0021] Examples of nonmetallic elements include silicon and carbon. Examples of nonmetallic oxides include silicon dioxide. Examples of nonmetallic nitrides include SiN x Examples include Si3N4, etc. Examples of nonmetallic oxide nitrides include silicon oxide (SiON).

[0022] Among these, nonmetallic oxides or nonmetallic nitrides are preferred, and nonmetallic oxides are more preferred.

[0023] The shape of region (I) and / or region (II) on the surface of the substrate is not particularly limited, and examples include planar, dotted, and striped shapes in plan view. The size of region (I) and region (II) is not particularly limited and can be any desired size. The shape of the substrate is not particularly limited and can be any desired shape, such as a plate (substrate) or a sphere. A substrate is preferred as the substrate. The substrate may have a curved surface and may have irregularities on its surface. A flat substrate with a smooth surface is preferred as the substrate.

[0024] <Polymer (A)> Polymer (A) has a group represented by the following formula (1) at the end of its main chain. -R 1 -OP(=O)(OR 2 )2(1) (In formula (1), R 1 R is a divalent hydrocarbon group having 1 to 10 carbon atoms, which may have substituents. 2 (This is a monovalent hydrocarbon group.)

[0025] [Base represented by formula (1)] Polymer (A) preferably has the group represented by formula (1) at only one end of the main chain, as this makes it easier to obtain the desired effect. In polymer (A), the number of groups represented by formula (1) is preferably 1 or more and 3 or less, more preferably 1 or 2, and even more preferably 1.

[0026] R 1 The number of carbon atoms in the divalent hydrocarbon group is preferably 1 to 8, and more preferably 2 to 5, from the viewpoint of brush density. 1 As for the hydrocarbon group, an aliphatic hydrocarbon group is preferred, and an alkylene group is more preferred. The alkylene group may be linear or branched, but linear is preferred from the viewpoint of brush density. Examples of alkylene groups include methylene group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, etc. Among these, ethane-1,2-diyl group or propane-1,3-diyl group is preferred, and ethane-1,2-diyl group is more preferred.

[0027] R 1 Examples of substituents that the divalent hydrocarbon group may have include carbonyl groups and ester groups. In this specification, the carbonyl group and ester group as substituents are groups that substitute any methylene group (-CH2-) constituting the above hydrocarbon group. 1 The divalent hydrocarbon group, as such, is preferably without substituents from the viewpoint of brush density.

[0028] R 2 The monovalent hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group consisting of a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, but from the viewpoint of brush density, an aliphatic hydrocarbon group is preferred. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 or 3. Alkyl groups are preferred as aliphatic hydrocarbon groups. Alkyl groups may be linear or branched, but branched groups are preferred from the viewpoint of brush density. 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] [Constituent Units] Polymer (A) has constituent units derived from styrene and / or constituent units (A1) derived from styrene derivatives.

[0030] 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, and compounds in which the hydrogen atom of the phenyl group of styrene is 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. 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.

[0031] The constituent unit (A1) is preferably the constituent unit represented by the following formula (a1-1). [ka] (In formula (a1-1), R a1 R is an alkyl group having 1 to 5 carbon atoms, n is an integer between 0 and 5, and a2 (This is a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms.)

[0032] R a1 , and R a2 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.

[0033] n is preferably 0 or greater and 3 or less, more preferably 0 or 1, and even more preferably 0.

[0034] Polymer (A) may have structural units other than structural unit (A1), but it is preferable that it does not have structural units containing the group represented by formula (1).

[0035] The ratio of moles of constituent unit (A1) to the total number of moles of constituent units constituting polymer (A) is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, particularly preferably 95 mol% or more, and may also be 100 mol%.

[0036] [Structure represented by formula (2-1) or formula (2-2)] From the standpoint of easily obtaining the desired effect, it is preferable that polymer (A) has a structure (constituent unit and terminal structure) represented by the following formula (2-1) or formula (2-2). [ka] (In equations (2-1) and (2-2), R 1 , R 2 , R a1, R a2 , and n are the same as these bases in equations (1) and (a1-1).

[0037] The number-average molecular weight (Mn) of polymer (A) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and even more preferably 2,000 to 15,000. A good brush density is easily obtained when the number-average molecular weight is within the above range. In this specification, "number-average molecular weight" (Mn) is the number-average molecular weight on a standard polystyrene basis determined by size exclusion chromatography (SEC) measurement.

[0038] The method for producing polymer (A) is not particularly limited, and conventionally known polymerization methods can be used. For example, by polymerizing monomers using a specific initiator and / or termination agent, -R can be added to the end of the main chain. 1 To synthesize a polymer having a group represented by -OH, and to add XP(=O)(OR 2 A polymer (A) can be obtained by a method that includes reacting with a compound represented by )2 (end modifier). 1 , and R 2 These are similar to the groups in formula (1), where X is a halogen atom such as a chlorine atom.

[0039] <Solvent (S)> The composition contains a solvent (S). Examples of solvents (S) include organic solvents. Any organic solvent that can dissolve each component used and form a homogeneous solution is acceptable. Conventionally, any organic solvent selected from organic solvents known to be used as solvents for resin-based compositions can be used.

[0040] 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 solvent components may be used individually or as a mixture of two or more solvents. Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, or ethyl lactate (EL) are preferred.

[0041] The solvent content in the composition is not particularly limited. The solvent is appropriately set according to the coating thickness so that the concentration of the composition is at a coating-compatible concentration. Generally, the solvent is used such 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.

[0042] <Other ingredients> The composition 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.

[0043] <<polymer>> The polymer has structural units derived from styrene and / or styrene derivatives. The polymer has a group represented by the following formula (1) at the end of its main chain. -R 1 -OP(=O)(OR 2 )2(1) (In formula (1), R 1 R is a divalent hydrocarbon group having 1 to 10 carbon atoms, which may have substituents. 2 (This is a monovalent hydrocarbon group.)

[0044] The details and preferred embodiments of the polymer are the same as those of polymer (A) in the above-described composition.

[0045] As described above, the present inventors provide the following [1] to [6]. [1] A composition used for selective modification of a substrate having a surface that includes two or more regions of different materials, It contains a polymer (A) and a solvent (S), The polymer (A) has constituent units derived from styrene and / or constituent units derived from styrene derivatives, The polymer (A) is given by the following formula (1): -R 1 -OP(=O)(OR2 )2(1) (In formula (1), R 1 R is a divalent hydrocarbon group having 1 to 10 carbon atoms, which may have substituents. 2 (This is a monovalent hydrocarbon group.) A composition having a group represented by at the end of its main chain. [2] The R 1 The composition according to [1], wherein the linear alkylene group has 1 to 10 carbon atoms. [3] The R 2 The composition according to [1] or [2], wherein the alkyl group is an alkyl group. [4] The polymer (A) is a composition according to any one of [1] to [3], wherein the polymer (A) does not have a constituent unit containing the group represented by formula (1). [5] The composition according to any one of [1] to [4], wherein the number average molecular weight of the polymer (A) is 1,000 or more and 20,000 or less. [6] Having constituent units derived from styrene and / or constituent units derived from styrene derivatives, Formula (1): -R 1 -OP(=O)(OR 2 )2(1) (In formula (1), R 1 R is a divalent hydrocarbon group having 1 to 10 carbon atoms, which may have substituents. 2 (This is a monovalent hydrocarbon group.) A polymer having a group represented by at the end of its main chain. [Examples]

[0046] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0047] The polymers used in the examples and comparative examples are described below.

[0048] <polymer> A-1 to A-3: Polymers represented by the following formulas (number average molecular weight (Mn) of A-1: ​​3,000, Mn of A-2: 5,000, Mn of A-3: 10,000). [ka]

[0049] A-4: A polymer represented by the following formula (Mn: 5,000). [ka]

[0050] A-5: A polymer represented by the following formula (Mn: 5,000). [ka]

[0051] A-6: A polymer represented by the following formula (Mn: 5,000). [ka]

[0052] A-7: A polymer represented by the following formula (Mn: 5,000). [ka]

[0053] A-8: A polymer represented by the following formula (Mn: 5,000). [ka]

[0054] A-9: A polymer represented by the following formula (Mn: 5,000). [ka]

[0055] A-10: A polymer represented by the following formula (Mn: 5,000). [ka]

[0056] B-1 and B-2: Polymers represented by the following formulas (Mn of B-1: 10,000, Mn of B-2: 4,700). [ka]

[0057] B-3: A polymer represented by the following formula (Mn: 7,900). [ka]

[0058] B-4: A polymer represented by the following formula (Mn: 5,000). [ka]

[0059] <Synthesis of Polymer Precursor 1> All anionic polymerization was carried out under an argon atmosphere. 200 mL of tetrahydrofuran (THF) was transferred to a 300 mL Schlenk tube and cooled to -78°C in a Coolnics bath. sec-butyllithium (sec-BuLi) (1.19 M hexane / cyclohexane solution) was added to the Schlenk tube until the solution turned yellow. The Schlenk tube was removed from the Coolnics bath and warmed to room temperature until the solution became colorless. The Schlenk tube was cooled again to -78°C in a Coolnics bath and sec-BuLi (4.17 mL, 4.96 mmol) was added as an initiator. Styrene (27.4 mL, 0.238 mol) was added to the Schlenk tube and stirred for 30 minutes. A bright orange solution was obtained. Distilled (2-bromoethoxy)tert-butyldimethylsilane (5.46 mL, 24.6 mmol) was added to the Schlenk tube as a termination agent to terminate the polymerization. The Schlenk tube was withdrawn from the Coolnics bath, and the solution was added to methanol for reprecipitation. After filtering the solid precipitate, it was dried under reduced pressure at 40°C to obtain a white powder. Next, the white powder and THF (10 wt% solution) were placed in a 300 mL glass tube, and tetrabutylammonium fluoride (TBAF) (12 molar equivalents / polymer end group) was added. The mixture was stirred overnight at room temperature to synthesize polymer precursor 1. The polymer precursor 1 solution was added to methanol for reprecipitation. After filtering the solid precipitate, it was dried under reduced pressure at 40°C to obtain a white powder of polymer precursor 1. The Mn and dispersion (PDI = Mw / Mn) of polymer precursor 1, as measured by size exclusion chromatography (SEC), were 5,000 and 1.04, respectively. 1 H NMR(400MHz,CDCl3,δ,ppm):1.23-1.69(br,backbone,-CH2-CH-,PS,br,-CH2-CH2-OH),1.74-2.02(br,backbone, -CH2-CH-,PS),3.24-3.45(br,-CH2-CH2-OH),6.39-6.85(m,o-aromatic,PS),6.91-7.42(m,m-,p-aromatic,PS).

[0060] <Synthesis of Polymer Precursors 2 and 3> Polymer precursors 2 and 3 were synthesized in the same manner as polymer precursor 1. The Mn and PDI values ​​of polymer precursor 2 were 3,000 and 1.05, respectively, and the Mn and PDI values ​​of polymer precursor 3 were 10,000 and 1.04, respectively.

[0061] <Synthesis of Polymer Precursors 4-7> Polymer precursors 4 to 7 were synthesized in the same manner as polymer precursor 1, except that (3-bromopropoxy)tert-butyldimethylsilane (for polymer precursor 4), (8-bromooctoxy)tert-butyldimethylsilane (for polymer precursor 5), tert-butyldimethylsilyl 2-bromoacetate (for polymer precursor 6), or 2-[(tert-butyldimethylsilyl)oxy]propyl bromide (for polymer precursor 7) were used as the stopping agent instead of (2-bromoethoxy)tert-butyldimethylsilane. The Mn and PDI values ​​of polymer precursors 4 to 7 were 5,000 and 1.04, respectively.

[0062] <Synthesis of Polymer A-2> 5 g of polymer precursor 1 and dichloromethane (10 wt% solution) were placed in a 100 mL glass tube, and 4-dimethylaminopyridine (0.075 molar equivalents / polymer end group), triethylamine (3 molar equivalents / polymer end group), and diethyl chlorophosphate (3 molar equivalents / polymer end group) were added in sequence. The mixture was stirred at room temperature for 6 hours to synthesize polymer A-2. The synthesized polymer A-2 was added to methanol and reprecipitation was performed. After filtering the solid precipitate, it was dried under reduced pressure at 40°C to obtain polymer A-2 as a white powder. The Mn and dispersion (PDI = Mw / Mn) of polymer A-2, as measured by size exclusion chromatography (SEC), were 5,000 and 1.04, respectively. 1H NMR(400MHz,CDCl3,δ,ppm):1.22-1.34(br,-OP(=O)(O-CH2-CH3)),1.23-1.69(br,backbone,-CH2-CH-,PS,br,-CH2-CH2-O-),1.74-2.02(br,backbone,-CH2-CH-,PS), 3.24-3.45(br,-CH2-CH2-OH),3.59-3.82(br,-CH2-CH2-O-),3.90-4.05(br,-OP(=O )(O-CH2-CH3)),6.39-6.85(m,o-aromatic,PS),6.91-7.42(m,m-,p-aromatic,PS).

[0063] <Synthesis of polymers A-1, A-3, and A-7 to A-10> Polymers A-1, A-3, and A-7 to A-10 were synthesized in the same manner as polymer A-2, except that polymer precursor 2 (for polymer A-1), polymer precursor 3 (for polymer A-3), polymer precursor 4 (for polymer A-7), polymer precursor 5 (for polymer A-8), polymer precursor 6 (for polymer A-9), or polymer precursor 7 (for polymer A-10) was used instead of polymer precursor 1. The Mn and PDI values ​​of polymer A-1 were 3,000 and 1.05, respectively; the Mn and PDI values ​​of polymer A-3 were 10,000 and 1.04, respectively; and the Mn and PDI values ​​of polymers A-7 to A-10 were 5,000 and 1.04, respectively.

[0064] <Synthesis of Polymers A-4 to A-6> Polymers A-4 to A-6 were synthesized in the same manner as polymer A-2, except that dimethyl chlorophosphate (for polymer A-4), diisopropyl chlorophosphate (for polymer A-5), or diphenyl chlorophosphate (for polymer A-6) were used as terminal modifiers instead of diethyl chlorophosphate. The Mn and PDI values ​​of polymers A-4 to A-6 were 5,000 and 1.04, respectively.

[0065] <Preparation of Composition> The polymers of the types listed in Table 1 were mixed with propylene glycol monomethyl ether acetate (PGMEA) to a concentration of 1.0% by mass to prepare the compositions for each example.

[0066] <Evaluation of the composition> (Surface treatment of the substrate) The tungsten (W) substrate was immersed in 0.2% by mass hydrofluoric acid, rinsed with pure water, and then dried using a nitrogen flow. The silicon dioxide (SiO2) substrate was surface-treated with isopropanol.

[0067] (Membrane formation) The compositions for each example were applied to a surface-treated tungsten substrate by spin coating at 1500 rpm. The substrates coated with the compositions were baked on a hot plate at 200°C for 5 minutes in an air atmosphere. Subsequently, the substrates were rinsed with PGMEA to remove unreacted polymers. Furthermore, the substrates were baked at 100°C for 1 minute to remove the solvent and form a film on the tungsten substrate. Similarly, a film was formed on a silicon oxide substrate.

[0068] (Evaluation of contact angle) Using a DropMaster700 (manufactured by Kyowa Interface Science Co., Ltd.), a 2.0 μL drop of pure water was placed on the surface of a substrate with a film formed on it, and the contact angle of the substrate was measured once per second for a total of 10 times. Measurements were taken at three different points on the substrate, and the average of 30 measurements was taken as the water contact angle. As a reference example, the contact angle of the substrate before film formation was also measured in the same manner. The results are shown in Table 1.

[0069] (Evaluation of film thickness) The film thickness of the formed film was measured using a spectroscopic ellipsometer (JAWoollam M-2000). The results are shown in Table 1.

[0070] (Evaluation of brush density) 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 polymer density was assumed to be 1.05 g / cm³. 3 (The density of polystyrene) was used. σ = d × L × NA × 10 -21 / Mn [σ: Brush density (number of chains / nm] 2 ), d: density of the polymer (g / cm³) 3 [L: film thickness (nm), NA: Avogadro's number, Mn: number-average molecular weight of polymer (g / chain)]

[0071] (Evaluation of heat resistance) The tungsten substrate with the film formed on it was baked in an air atmosphere at 280°C on a hot plate for 5 minutes. The baked substrate was rinsed with PGMEA and then baked again at 100°C for 1 minute. After these processes were performed on the substrate, the film thickness was measured and the brush density was calculated. A change of 5% or more in the brush density of the substrate before processing was evaluated as "B," and no change of 5% or more was evaluated as "A." The results are shown in Table 1.

[0072] [Table 1]

[0073] As shown in Table 1, in Examples 1 to 10, which used the specified polymer, good selectivity for metal surfaces was confirmed from the change in water contact angle compared to the reference example. Furthermore, compared to Comparative Examples 1 to 4, the film thickness and brush density of the formed film were confirmed to be thicker. In addition, good heat resistance was also confirmed.

Claims

1. A composition used for selective modification of a substrate having a surface that includes two or more regions of different materials, It contains a polymer (A) and a solvent (S), The polymer (A) has constituent units derived from styrene and / or constituent units derived from styrene derivatives, The polymer (A) is given by the following formula (1): -R １ -O-P(=O)(OR ２ ) ２ (1) (In formula (1), R １ R is a divalent hydrocarbon group having 1 to 10 carbon atoms, which may have substituents. ２ (This is a monovalent hydrocarbon group.) A composition having a group represented by at the end of its main chain.

2. The aforementioned R １ The composition according to claim 1, wherein the linear alkylene group has 1 to 10 carbon atoms.

3. The aforementioned R ２ The composition according to claim 1 or 2, wherein the alkyl group is.

4. The composition according to claim 1 or 2, wherein the polymer (A) does not have a structural unit containing the group represented by formula (1).

5. The composition according to claim 1 or 2, wherein the number average molecular weight of the polymer (A) is 1,000 or more and 20,000 or less.

6. Having constituent units derived from styrene and / or constituent units derived from styrene derivatives, The following formula (1): -R １ -O-P(=O)(OR ２ ) ２ (1) (In formula (1), R １ R is a divalent hydrocarbon group having 1 to 10 carbon atoms, which may have substituents. ２ (This is a monovalent hydrocarbon group.) A polymer having a group represented by at the end of its main chain.

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