Coating material for photolithography, resist material and pattern formation method

Abstract

To provide a coating material for photolithography which contains a surface active agent having no perfluoroalkyl structure, a resist material which is excellent in flatness of a film after coating and is reduced in defects not only after coating but also after development, and a pattern formation method using the same.SOLUTION: A coating material for photolithography contains 0.0001 to 3 mass% of a surface active agent which is composed of a resin having an aromatic group substituted with a fluorine atom, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group or a difluoromethylthio group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a coating material for photolithography, a resist material, and a pattern forming method. [Background technology]

[0002] As LSIs become more highly integrated and faster, pattern rules are becoming finer at a rapid pace. This is because 5G high-speed communications and artificial intelligence (AI) are becoming more widespread, and high-performance devices are needed to process these. The most advanced miniaturization technology is extreme ultraviolet (EUV) lithography with a wavelength of 13.5 nm, which is used to mass-produce 5 nm node devices. Furthermore, studies are underway to use EUV lithography for next-generation 3 nm node devices and the next-next generation 2 nm node devices.

[0003] Resist materials and other materials used in photolithography are applied in solution by spin coating or other methods, and then baked to evaporate the solvent to form a film. The film thickness after baking must be uniform and flat, and the requirements for uniformity and flatness are becoming stricter every year.

[0004] For 3D-NAND memory applications, thick resist films are required, and even greater flatness is required. As the film thickness increases, it becomes more difficult to achieve flatness. On the other hand, as miniaturization progresses, the film thickness is becoming thinner, and in this case the risk of pinhole defects is increasing.

[0005] During application, Marangoni convection of the solvent causes striations. To prevent Marangoni convection, it is important to select a solvent with an optimal boiling point and low viscosity, and a surfactant to reduce surface tension.

[0006] Surfactants having a fluoroalkyl group or silicone chain are highly effective in lowering surface tension, and in particular, fluoroalkyl group-based surfactants that have a low risk of generating silicon-derived particles after dry ashing of the resist film are widely used (Patent Documents 1 and 2). Fluorine-based surfactants are also used not only in resist materials but also in top coats formed on the top layer of the resist and in anti-reflective films formed on the bottom layer of the resist (Patent Document 3).

[0007] The health effects of perfluoroalkyl substances (PFAS) have been pointed out, and there are moves to impose restrictions on the manufacture and sale of PFAS compounds under the European REACH. There is an urgent need to develop materials that do not contain PFAS structures.

[0008] A resist underlayer film material using a polymer of phenylmethyl(meth)acrylate substituted with fluorine atoms or trifluoromethoxy groups has been proposed (Patent Document 4). A polymer of phenylmethyl(meth)acrylate substituted with fluorine atoms or trifluoromethoxy groups, a resin that does not contain fluorine atoms, and a solvent are mixed, and after coating, the fluorine-containing resin is oriented on the surface layer to form a two-layer anti-reflection film in a single coating.

[0009] Surfactants having a trifluoromethoxy group or a pentafluorosulfanyl group and the use thereof have been proposed (Patent Document 5). [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 6-186735 [Patent Document 2] Japanese Patent Application Publication No. 6-214380 [Patent Document 3] Japanese Patent Application Publication No. 6-289620 [Patent Document 4] JP 2010-139822 A [Patent Document 5] Special Publication No. 2008-526792 Summary of the Invention [Problem to be solved by the invention]

[0011] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a coating material for photolithography containing a surfactant that does not have a perfluoroalkyl structure, a resist material that has excellent flatness of a film after coating and has few defects not only after coating but also after development, and a pattern formation method using the same. [Means for solving the problem]

[0012] The present inventors have conducted intensive research to obtain a surfactant for photolithography coating materials that has high flatness after coating, good coating properties at the outermost edge of the wafer, and few defects after coating, development, and even etching, as has been demanded in recent years. As a result, they have found that by adding a surfactant made of a resin having an aromatic group, trifluoromethoxy group, difluoromethoxy group, trifluoromethylthio group, or difluoromethylthio group substituted with a fluorine atom to a photolithography coating material, the properties of high flatness after coating and few defects after coating and development are expressed, and have come to make the present invention. Note that aromatic groups, trifluoromethoxy groups, and difluoromethoxy groups substituted with fluorine atoms do not belong to the classification of PFAS in REACH. In addition, difluoromethoxy groups and aromatic groups substituted with fluorine atoms do not belong to the classification of PFAS in OECD.

[0013] That is, the present invention provides the following coating material for photolithography, resist material, and pattern forming method. 1. A coating material for photolithography comprising 0.0001 to 3 mass % of a surfactant made of a resin having an aromatic group substituted with a fluorine atom, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group or a difluoromethylthio group. 2. The coating material for photolithography according to 1, wherein the resin is a polymer containing a repeating unit Sa having an aromatic group substituted with a fluorine atom, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group or a difluoromethylthio group. 3. The coating material for photolithography according to 2, wherein the repeating unit Sa is represented by any one of the following formulas (Sa1) to (Sa5). [ka] (In the formula, each m is independently an integer of 1 to 5. Each n is independently an integer of 0 to 4. Each p is independently an integer of 1 to 3. Each q is an integer of 0 to 3. Each r is an integer of 0 to 3. And each s is an integer of 0 to 4. With the proviso that q+s is an integer of 1 to 5. R A are each independently a hydrogen atom or a methyl group. X 1 are each independently a single bond, an ester bond, an ether bond, an amide bond, or a phenylene group. X 2 each independently represents a single bond or a hydrocarbylene group having 1 to 20 carbon atoms when p is 1, and represents a (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms when p is 2 or 3, and the hydrocarbylene group and the (p+1)-valent hydrocarbon group may contain at least one atom selected from an oxygen atom, a sulfur atom, a nitrogen atom and a halogen atom. X 3A each independently represents a single bond, an ester bond, an ether bond, an amide bond, a sulfonate ester bond, a urethane bond, a thiourethane bond, a urea bond, or -S(=O)-N(X 31 )-. X 31 is a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. X 3B is a single bond or a carbonyl group. X 4 is -O- or -S-. X 5is a single bond or a hydrocarbylene group having 1 to 12 carbon atoms, and the hydrocarbylene group may have at least one bond selected from a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, an ether bond, and an ester bond. Circle R 1 are each independently a (m+n+1)-valent group derived from benzene or naphthalene. R 2 each independently represents a hydrogen atom, a hydrocarbyl group having 1 to 6 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a hydrocarbyloxycarbonyl group having 2 to 6 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 12 carbon atoms, a hydroxy group, a carboxy group, a halogen atom, a cyano group, or a nitro group. R 3 are each independently a trifluoromethyl group or a difluoromethyl group. R 4 each independently represents a hydrocarbyl group having 1 to 6 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a hydrocarbyloxycarbonyl group having 2 to 6 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 12 carbon atoms, a hydroxy group, a carboxy group, a halogen atom, a cyano group, or a nitro group. Circle R 5 are each independently an aromatic hydrocarbon group having 6 to 30 carbon atoms and a valence of (q+r+2). Circle R 6 is a (s+1)-valent group derived from benzene or naphthalene. R 7 is a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms, and the hydrocarbyl group may contain an oxygen atom. 7 -X 5 -X 4 -R 3 does not have a group represented by the following formula: 4.X 1 and X 2 3. A coating material for photolithography, wherein at least one of said groups is not a single bond. 5. A coating material for photolithography according to claim 3, which is a polymer containing a repeating unit represented by formula (Sa1) and a repeating unit represented by formula (Sa2). 6. The coating material for photolithography according to any one of 2 to 5, wherein the polymer further comprises a repeating unit Sb having a hydrophilic group selected from an ether bond, an ester bond, a hydroxy group, a carboxy group, a sulfonamide bond, a sulfonimide bond and a sulfo group. 7. The coating material for photolithography according to claim 6, wherein the polymer is a block copolymer. 8. A resist material comprising a coating material for photolithography according to any one of 1 to 7. 9. The resist material of 8 further comprising a base polymer and an organic solvent. 10. A pattern forming method comprising the steps of forming a resist film on a substrate using the resist material of 8 or 9, exposing the resist film to high-energy rays, and developing the exposed resist film using a developer. 11. The pattern formation method according to claim 10, wherein the high energy beam is g-ray, i-ray, KrF excimer laser, ArF excimer laser, ultraviolet ray, electron beam (EB) or EUV having a wavelength of 3 to 15 nm. Effect of the Invention

[0014] The surfactant used in the photolithography coating material of the present invention is made of a resin having an aromatic group, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group or a difluoromethylthio group substituted with a fluorine atom, and the film obtained from the photolithography coating material containing this has excellent flatness and uniformity of film thickness over the entire surface of the substrate to be coated, is cleanly cut when the outermost part of the wafer is edge-cut with a solvent during coating, and has excellent embedding properties when the substrate has irregularities. When this is a photosensitive material such as a resist material, it has the effect of reducing defects after coating, development, and even dry etching, and can be applied, for example, not only to lithography in semiconductor circuit formation, but also to the formation of mask circuit patterns, micromachines, and thin-film magnetic head circuits. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] [Coating materials for photolithography] The coating material for photolithography of the present invention contains a surfactant made of a resin having an aromatic group substituted with a fluorine atom, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group or a difluoromethylthio group.

[0016] The resin is preferably a polymer containing a repeating unit Sa having an aromatic group substituted with a fluorine atom, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group or a difluoromethylthio group.

[0017] The repeating unit Sa is preferably one represented by the following formula (Sa1) (hereinafter also referred to as repeating unit Sa1), one represented by the following formula (Sa2) (hereinafter also referred to as repeating unit Sa2), one represented by the following formula (Sa3) (hereinafter also referred to as repeating unit Sa3), one represented by the following formula (Sa4) (hereinafter also referred to as repeating unit Sa4), or one represented by the following formula (Sa5) (hereinafter also referred to as repeating unit Sa5). [ka]

[0018] In formulae (Sa1) to (Sa5), m is independently an integer of 1 to 5. n is independently an integer of 0 to 4. p is independently an integer of 1 to 3. q is an integer of 0 to 3. r is an integer of 0 to 3. s is an integer of 0 to 4, with the proviso that q+s is an integer of 1 to 5.

[0019] In formulas (Sa1)~(Sa3), R A are each independently a hydrogen atom or a methyl group.

[0020] In formulas (Sa1)~(Sa3), X 1 are each independently a single bond, an ester bond, an ether bond, an amide bond, or a phenylene group.

[0021] In formulas (Sa1)~(Sa3), X 2 each independently represents a single bond or a hydrocarbylene group having 1 to 20 carbon atoms when p is 1, and represents a (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms when p is 2 or 3, and the hydrocarbylene group and the (p+1)-valent hydrocarbon group may contain at least one atom selected from an oxygen atom, a sulfur atom, a nitrogen atom and a halogen atom.

[0022] X 2 The hydrocarbylene group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include a methanediyl group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, and a dodecane-1,12-diyl group. alkanediyl groups having 1 to 20 carbon atoms; cyclic saturated hydrocarbylene groups having 3 to 20 carbon atoms, such as cyclopentanediyl group, cyclohexanediyl group, norbornanediyl group, and adamantanediyl group; unsaturated aliphatic hydrocarbylene groups having 2 to 20 carbon atoms, such as vinylene group and propene-1,3-diyl group; arylene groups having 6 to 20 carbon atoms, such as phenylene group and naphthylene group; and groups obtained by combining these. 2 The (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms and represented by the formula (1) may be saturated or unsaturated, and may be linear, branched or cyclic. Specific examples thereof include a group obtained by further removing one or two hydrogen atoms from the above-mentioned hydrocarbylene group, a group obtained by substituting one or two hydrogen atoms of the above-mentioned hydrocarbylene group with a hydrocarbylene group, and the like.

[0023] X 1 and X 2 It is preferable that at least one of the following is not a single bond.

[0024] In formulas (Sa1) and (Sa2), X 3Aeach independently represents a single bond, an ester bond, an ether bond, an amide bond, a sulfonate ester bond, a urethane bond, a thiourethane bond, a urea bond, or -S(=O)-N(X 31 )-. X 31 is a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms.

[0025] In formula (Sa3), X 3B is a single bond or a carbonyl group.

[0026] In formulas (Sa2)~(Sa5), X 4 is -O- or -S-.

[0027] In formulas (Sa4) and (Sa5), X 5 is a single bond or a hydrocarbylene group having 1 to 12 carbon atoms, and the hydrocarbylene group may have at least one bond selected from a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, an ether bond, and an ester bond.

[0028] In the formulas (Sa1) and (Sa2), circle R 1 are each independently a (m+n+1)-valent group derived from benzene or naphthalene.

[0029] In formulas (Sa1) and (Sa2), R 2 each independently represents a hydrogen atom, a hydrocarbyl group having 1 to 6 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a hydrocarbyloxycarbonyl group having 2 to 6 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 12 carbon atoms, a hydroxy group, a carboxy group, a halogen atom, a cyano group, or a nitro group.

[0030] In formulas (Sa2)~(Sa5), R 3 are each independently a trifluoromethyl group or a difluoromethyl group.

[0031] In formulas (Sa4) and (Sa5), R 4each independently represents a hydrocarbyl group having 1 to 6 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a hydrocarbyloxycarbonyl group having 2 to 6 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 12 carbon atoms, a hydroxy group, a carboxy group, a halogen atom, a cyano group, or a nitro group.

[0032] In formulas (Sa4) and (Sa5), circle R 5 are each independently a (q+r+2)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms. The (q+r+2)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms is preferably derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, biphenyl, diphenylmethane, trisphenyl, fluorene bisphenol, fluorene bisnaphthol, or the like, and may have a substituted or unsubstituted hydroxy group or a saturated hydrocarbyl group having 1 to 12 carbon atoms, to which a benzene or naphthalene having a substituted or unsubstituted hydroxy group may be bonded.

[0033] In formula (Sa4), circle R 6 is a (s+1)-valent group derived from benzene or naphthalene.

[0034] In formula (Sa5), R 7 is a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms, and the hydrocarbyl group may contain an oxygen atom. 7 -X 5 -X 4 -R 3 The compound does not have a group represented by the following formula:

[0035] The polymer is preferably a polymer containing at least one selected from repeating units Sa1, Sa2 and Sa3 (hereinafter, also referred to as polymer A).

[0036] Examples of monomers having an aromatic group substituted with a fluorine atom that provide the repeating unit Sa1 include, but are not limited to, those shown below. A is the same as above.

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[0050] [ka]

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[0053] [ka]

[0054] [ka]

[0055] Examples of monomers having a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group, or a difluoromethylthio group that provide the repeating unit Sa2 include, but are not limited to, those shown below. [ka]

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[0088] [ka]

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[0090] [ka]

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[0097] [ka]

[0098] Examples of monomers that provide the repeating unit Sa3 include, but are not limited to, those shown below. [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] It is preferable that the polymer A further contains a repeating unit having a hydrophilic group. By containing the repeating unit Sa having a highly water-repellent fluorine atom and the repeating unit Sb having a hydrophilic group, the polymer A can fully exhibit a surface active effect.

[0104] The repeating unit Sb has a hydrophilic group selected from an ether bond, an ester bond, a hydroxy group, a carboxy group, a sulfonamide bond, a sulfonimide bond, a sulfo group, a lactone ring, a sultone ring, a carbonate bond, a urethane bond, and an amide bond.

[0105] Specific examples of monomers that provide the repeating unit Sb include, but are not limited to, those shown below. [ka]

[0106] [ka]

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[0113] In polymer A, the content ratios of the repeating units Sa1, Sa2, Sa3 and Sb are preferably 0 ≦ Sa1 < 1.0, 0 ≦ Sa2 < 1.0, 0 ≦ Sa3 < 1.0, 0 < Sa1 + Sa2 + Sa3 < 1.0 and 0 < Sb < 1.0, more preferably 0 ≦ Sa1 ≦ 0.9, 0 ≦ Sa2 ≦ 0.9, 0 ≦ Sa3 ≦ 0.9, 0.1 ≦ Sa1 + Sa2 + Sa3 ≦ 0.9 and 0.1 ≦ Sb ≦ 0.9, and still more preferably 0 ≦ Sa1 ≦ 0.8, 0 ≦ Sa2 ≦ 0.8, 0 ≦ Sa3 ≦ 0.8, and 0.2 ≦ Sa1 + Sa2 + Sa3 ≦ 0.8 and 0.2 ≦ Sb ≦ 0.8. However, Sa1 + Sa2 + Sa3 + Sb = 1.0.

[0114] The weight average molecular weight (Mw) of the polymer A in terms of polystyrene measured by gel permeation chromatography (GPC) using THF as a solvent is preferably 1000 to 500000, more preferably 2000 to 30000. Furthermore, when the molecular weight distribution (Mw / Mn) of the polymer A is broad, there is a risk that foreign matter may be observed on the pattern after exposure or the shape of the pattern may be deteriorated due to the presence of low molecular weight or high molecular weight polymers. As the pattern rule becomes finer, the influence of Mw and Mw / Mn tends to become greater, so in order to obtain a resist material suitable for use with fine pattern dimensions, it is preferable that the Mw / Mn of the polymer A is narrowly distributed, 1.0 to 2.0, particularly 1.0 to 1.5.

[0115] The polymer A may include two or more polymers having different composition ratios, Mw, or Mw / Mn. Also, polymers having different repeating units Sa1, Sa2, and Sb may be blended together.

[0116] The polymer A can be obtained by polymerizing a monomer that gives a repeating unit selected from the repeating units Sa1, Sa2, Sa3 and Sb by a method such as radical polymerization, anionic polymerization or cationic polymerization.

[0117] When the polymer A contains two or more kinds of repeating units, it may be a random copolymer or a block copolymer, but the block copolymer has the characteristic of being more effective as a surfactant. In particular, it is preferable that the polymer A is a block copolymer containing repeating units Sa and Sb. The block copolymer may be a diblock copolymer consisting of two units, a triblock copolymer consisting of three units, or a tetrablock copolymer consisting of four units.

[0118] In the case of random copolymerization by radical polymerization, it is common to mix the monomers to be copolymerized and a radical initiator and polymerize them by heating. If the first monomer is polymerized in the presence of a radical initiator and then the second monomer is added, the polymer molecule will have a block of the first monomer polymerized on one side and a block of the second monomer polymerized on the other side. However, in this case, the repeating units derived from the first and second monomers are mixed in the middle part, and the morphology is different from that of a block copolymer. Living radical polymerization is preferably used to form block copolymers by radical polymerization. In the living radical polymerization method called Reversible Addition Fragmentation chain Transfer (RAFT) polymerization, the radicals at the terminals of the polymer are always alive, so it is possible to form a block copolymer consisting of the first and second repeating units by starting polymerization with the first monomer and adding the second monomer when the first monomer is consumed. If the polymerization is started with the first monomer, the second monomer is added when the first monomer is consumed, and then the third monomer is added, a triblock copolymer can be formed. Another feature of RAFT polymerization is that it produces narrow-dispersity polymers with a narrow dispersity.

[0119] Examples of the organic solvent used during polymerization include toluene, benzene, tetrahydrofuran (THF), diethyl ether, and dioxane. Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. The temperature during polymerization is preferably 50 to 80°C. The reaction time is preferably 2 to 100 hours, and more preferably 5 to 20 hours.

[0120] A chain transfer agent is required to carry out RAFT polymerization, and specific examples thereof include 2-cyano-2-propyl benzothioate, 4-cyano-4-phenylcarbonothioylthiopentanoic acid, 2-cyano-2-propyldodecyltrithiocarbonate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, 2-(dodecylthiocarbonothioylthio)-2-methylpropanoic acid, cyanomethyldodecylthiocarbonate, cyanomethylN-methyl-N-phenylcarbamothioate, bis(thiobenzoyl)disulfide, and bis(dodecylsulfanylthiocarbonyl)disulfide. Of these, 2-cyano-2-propyl benzothioate is the most preferred.

[0121] When the monomer is added all at once and RAFT polymerization is performed, a narrow polydispersity polymer can be synthesized.

[0122] When the polymer contains at least one repeating unit selected from Sa4 and Sa5, the polymer is a novolak resin (hereinafter, also referred to as polymer B). Polymer B can be obtained by a polycondensation reaction between a phenol compound and an aldehyde compound. At least one of the phenol compound and the aldehyde compound has a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group, or a difluoromethylthio group.

[0123] The phenol compound is a compound having a hydroxy group bonded to an aromatic ring, and examples thereof include phenol, cresol, naphthol, dihydroxynaphthalene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(6-hydroxynaphthyl)fluorene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)adamantane, 4,4',4''-trihydroxytriphenylmethane, and 9-hydroxy-9-phenylfluorene.

[0124] Examples of the aldehyde compound include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, etc. Among these, formaldehyde is particularly suitable. These aldehyde compounds can be used alone or in combination of two or more.

[0125] At least one of the phenolic compound and the aldehyde compound has a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group, or a difluoromethylthio group. Examples of the phenolic compound having these groups include trifluoromethoxyphenol, difluoromethoxyphenol, trifluoromethylthiophenol, difluoromethylthiophenol, 9,9-bis(4-hydroxyphenyl)fluorene monotrifluoromethoxybenzmethanol, 9,9-bis(4-hydroxyphenyl)fluorene monodifluoromethoxybenzmethanol, 9,9-bis(4-hydroxyphenyl)fluorene monotrifluoromethylthiobenzmethanol, 9,9-bis(4-hydroxyphenyl)fluorene monodifluoromethylthiobenzmethanol, 9,9-bis(6-hydroxynaphthyl)fluorene monotrifluoromethoxybenzmethanol, 9,9-bis(6-hydroxynaphthyl)fluorene monodifluoromethoxybenzmethanol, and 9,9-bis(6-hydroxynaphthyl)fluorene monotrifluoromethyl Thiobenzmethanol, 9,9-bis(6-hydroxynaphthyl)fluorene monodifluoromethylthiobenzmethanol, 1,1,1-tris(4-hydroxyphenyl)ethane monotrifluoromethoxybenzmethanol, 1,1,1-tris(4-hydroxyphenyl)ethane monodifluoromethoxybenzmethanol, 1,1,1-tris(4-hydroxyphenyl)ethane monotrifluoromethylthiobenzmethanol, 1,1,1-tris(4-hydroxyphenyl)ethane monodifluoromethylthiobenzmethanol, 2,7-dihydroxynaphthalene monotrifluoromethoxybenzmethanol, 2,7-dihydroxynaphthalene monodifluoromethoxybenzmethanol, 2,7-dihydroxynaphthalene monotrifluoromethylthiobenzmethanol, 2,7-dihydroxynaphthalene monodifluoromethylthiobenzmethanol, and the like. Examples of aldehyde compounds having these groups include trifluoromethoxybenzaldehyde, difluoromethoxybenzaldehyde, trifluoromethylthiobenzaldehyde, and difluoromethylthiobenzaldehyde.

[0126] The phenol compounds may be used alone or in combination of two or more, and the aldehyde compounds may be used alone or in combination of two or more. The amount of the aldehyde compound used is preferably 0.2 to 5 mol, more preferably 0.5 to 2 mol, per mol of the phenol compound.

[0127] A catalyst may be used in the polycondensation reaction of the phenol compound and the aldehyde. Examples of the catalyst include acid catalysts such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, camphorsulfonic acid, tosylic acid, and trifluoromethanesulfonic acid. The amount of these acid catalysts used is 1×10 per mole of the phenol compound. -5 ~5×10 -1 Molar is preferred.

[0128] As the reaction solvent in the polycondensation, water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, or a mixed solvent thereof can be used. These solvents are preferably used in the range of 0 to 2000 parts by mass per 100 parts by mass of the raw materials. The reaction temperature can be appropriately selected depending on the reactivity of the raw materials, but is usually in the range of 10 to 200°C.

[0129] In the polycondensation reaction, the phenol compound, the aldehyde compound, and the catalyst may be charged all at once, or the phenol compound and the aldehyde compound may be added dropwise in the presence of a catalyst. After the polycondensation reaction is completed, the temperature of the reaction vessel is raised to 130 to 230°C, and the volatile matter may be removed at about 1 to 50 mmHg in order to remove unreacted raw materials, catalyst, etc., present in the system.

[0130] The weight average molecular weight (Mw) of polymer B in terms of polystyrene measured by gel permeation chromatography (GPC) using THF as a solvent is preferably 1000 to 500000, more preferably 1500 to 30000. Furthermore, if the molecular weight distribution (Mw / Mn) of polymer B is broad, there is a risk that foreign matter may be found on the pattern after exposure or the shape of the pattern may be deteriorated due to the presence of low molecular weight or high molecular weight polymers. As the pattern rule becomes finer, the influence of Mw and Mw / Mn tends to become greater. Therefore, in order to obtain a resist material suitable for use with fine pattern dimensions, it is preferable that the Mw / Mn of polymer A is narrowly distributed, 1.0 to 5.0, particularly 1.5 to 3.5.

[0131] Polymer B may contain two or more polymers having different composition ratios, Mw, and Mw / Mn.

[0132] Materials used in semiconductor photolithography, including the surfactants, must have reduced metal impurities because the presence of metal impurities adversely affects the operation of devices manufactured using them. To reduce metals, washing with pure water and ion exchange resins are used. In the case of resist materials, the amount of metal impurities is preferably 100 ppm or less, more preferably 100 ppb or less.

[0133] The coating material for photolithography of the present invention contains the surfactant in an amount of 0.0001 to 3% by mass, preferably 0.0001 to 2% by mass, and more preferably 0.0002 to 1% by mass.

[0134] The photolithography coating material can be used as a component of a photosensitive or non-photosensitive resist material, a material for forming a topcoat formed on a resist film, a material for forming a resist underlayer film, etc. Examples of underlayer film materials include hydrocarbon-based materials and silicon-containing materials. The resist material may be either a chemically amplified resist or a non-chemically amplified resist, a hydrocarbon-based resist, or a metal-based resist containing silicon, titanium, zirconium, hafnium, selenium, germanium, zinc, iron, cobalt, nickel, copper, tin, antimony, molybdenum, tungsten, indium, etc.

[0135] [Resist material] The resist material of the present invention contains the above-mentioned coating material for photolithography. The resist material of the present invention may further contain a conventional surfactant. Examples of the conventional surfactant include those described in paragraphs

[0165] to

[0166] of JP 2008-111103 A. When the resist material of the present invention contains a conventional surfactant, the content of the conventional surfactant is not particularly limited as long as it does not impair the effects of the present invention.

[0136] The resist material of the present invention may further include a base polymer. The base polymer is not particularly limited as long as it is used in resist materials.

[0137] Specifically, in the case of a positive resist material for a chemically amplified resist, the base polymer contains a repeating unit containing an acid labile group. The repeating unit containing an acid labile group is preferably a repeating unit represented by the following formula (a1) (hereinafter also referred to as repeating unit a1) or a repeating unit represented by the following formula (a2) (hereinafter also referred to as repeating unit a2). [ka]

[0138] In formulas (a1) and (a2), R B Each of Y is independently a hydrogen atom or a methyl group.1 Y is a linking group having 1 to 12 carbon atoms and containing at least one bond selected from a single bond, a phenylene group, a naphthylene group, an ester bond, an ether bond, and a lactone ring. 2 is a single bond or an ester bond. 3 R is a single bond, an ether bond or an ester bond. 11 and R 12 are each independently an acid labile group. When the base polymer contains both the repeating unit a1 and the repeating unit a2, R 11 and R 12 may be the same or different. 13 R is a fluorine atom, a trifluoromethyl group, a cyano group, or a saturated hydrocarbyl group having 1 to 6 carbon atoms. 14 is a single bond or an alkanediyl group having 1 to 6 carbon atoms, and a part of the -CH2- in the alkanediyl group may be substituted with an ether bond or an ester bond. a is 1 or 2. b is an integer of 0 to 4, with the proviso that 1≦a+b≦5.

[0139] Specific examples of monomers that provide the repeating unit a1 include, but are not limited to, those shown below. B and R 11 is the same as above. [ka]

[0140] Specific examples of monomers that provide the repeating unit a2 include, but are not limited to, those shown below. B and R 12 is the same as above. [ka]

[0141] R 11 and R 12Examples of the acid labile group represented by the formula (I) include those described in JP-A-2013-80033 and JP-A-2013-83821.

[0142] Specific examples of the acid labile group include those represented by any of the following formulae (AL-1) to (AL-3). [ka] (In the formula, the dashed lines represent bonds.)

[0143] In formulas (AL-1) and (AL-2), R L1 and R L2 are each independently a hydrocarbyl group having 1 to 40 carbon atoms, which may contain a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a fluorine atom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. The hydrocarbyl group is preferably a saturated hydrocarbyl group having 1 to 40 carbon atoms, more preferably a saturated hydrocarbyl group having 1 to 20 carbon atoms.

[0144] In formula (AL-1), c is an integer of 0 to 10, and an integer of 1 to 5 is preferable.

[0145] In formula (AL-2), R L3 and R L4 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, and may contain a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a fluorine atom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. The hydrocarbyl group is preferably a saturated hydrocarbyl group having 1 to 20 carbon atoms. L2 , R L3 and R L4 Any two of these may be bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom or the carbon atom and oxygen atom to which they are bonded. As the ring, a ring having 4 to 16 carbon atoms is preferable, and an alicyclic ring is particularly preferable.

[0146] In formula (AL-3), RL5 , R L6 and R L7 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, which may contain a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a fluorine atom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. The hydrocarbyl group is preferably a saturated hydrocarbyl group having 1 to 20 carbon atoms. L5 , R L6 and R L7 Any two of these may be bonded to each other to form, together with the carbon atom to which they are bonded, a ring having 3 to 20 carbon atoms. As the ring, a ring having 4 to 16 carbon atoms is preferable, and an alicyclic ring is particularly preferable.

[0147] The base polymer may contain a repeating unit b containing a phenolic hydroxy group as an adhesive group. Specific examples of monomers that provide the repeating unit b include, but are not limited to, those shown below. In the following formula, R B is the same as above. [ka]

[0148] [ka]

[0149] [ka]

[0150] The base polymer may contain a repeating unit c containing a hydroxy group other than a phenolic hydroxy group, a lactone ring, a sultone ring, an ether bond, an ester bond, a sulfonic acid ester bond, a carbonyl group, a sulfonyl group, a cyano group, or a carboxy group as another adhesive group. Specific examples of monomers that provide the repeating unit c include, but are not limited to, those shown below. In the following formula, R B is the same as above. [ka]

[0151] [ka]

[0152] [ka]

[0153] [ka]

[0154] [ka]

[0155] [ka]

[0156] [ka]

[0157] [ka]

[0158] [ka]

[0159] The base polymer may include a repeat unit d derived from indene, benzofuran, benzothiophene, acenaphthylene, chromone, coumarin, norbornadiene, or a derivative thereof. Specific examples of monomers that provide the repeat unit d include, but are not limited to, the following: [ka]

[0160] The base polymer may include repeat units e derived from styrene, vinyl naphthalene, vinyl anthracene, vinyl pyrene, methylene indane, vinyl pyridine, or vinyl carbazole.

[0161] The base polymer may contain a repeating unit f derived from an onium salt containing a polymerizable unsaturated bond. Specific examples of preferred repeating units f include a repeating unit represented by the following formula (f1) (hereinafter also referred to as repeating unit f1), a repeating unit represented by the following formula (f2) (hereinafter also referred to as repeating unit f2), and a repeating unit represented by the following formula (f3) (hereinafter also referred to as repeating unit f3). The repeating units f1 to f3 may be used alone or in combination of two or more. [ka]

[0162] In formulas (f1) to (f3), R B are each independently a hydrogen atom or a methyl group. 1 represents a single bond, an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining these groups, or -OZ 11 -, -C(=O)-OZ 11 - or -C(=O)-NH-Z 11 -It is. 11 Z is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining these groups, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. 2 is a single bond or an ester bond. 3 is a single bond, -Z 31 -C(=O)-O-, -Z 31 -O- or -Z31 -OC(=O)-. Z 31 Z is an aliphatic hydrocarbylene group having 1 to 12 carbon atoms, a phenylene group, or a group having 7 to 18 carbon atoms obtained by combining these, and may contain a carbonyl group, an ester bond, an ether bond, an iodine atom, or a bromine atom. 4 is a methylene group, a 2,2,2-trifluoro-1,1-ethanediyl group, or a carbonyl group. 5 is a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, -OZ 51 -, -C(=O)-OZ 51 - or -C(=O)-NH-Z 51 -It is. 51 represents an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may contain a carbonyl group, an ester bond, an ether bond, a halogen atom, or a hydroxy group.

[0163] In formulas (f1) to (f3), R 21 ~R 28 are each independently a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom.

[0164] R 21 ~R 28 Specific examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0165] R 21 ~R 28The hydrocarbyl group represented by the formula (I) may be saturated or unsaturated and may be linear, branched or cyclic. Specific examples of such alkyl groups include alkyl groups having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, or an icosyl group; cyclic saturated hydrocarbyl groups having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, or an adamantyl group; alkenyl groups having 2 to 20 carbon atoms, such as a vinyl group, a propenyl group, a butenyl group, or a hexenyl group; and an ethynyl group. alkynyl groups having 2 to 20 carbon atoms, such as a propynyl group or a butynyl group; cyclic unsaturated aliphatic hydrocarbyl groups having 3 to 20 carbon atoms, such as a cyclohexenyl group or a norbornenyl group; aryl groups having 6 to 20 carbon atoms, such as a phenyl group, a methylphenyl group, an ethylphenyl group, a n-propylphenyl group, an isopropylphenyl group, a n-butylphenyl group, an isobutylphenyl group, a sec-butylphenyl group, a tert-butylphenyl group, a naphthyl group, a methylnaphthyl group, an ethylnaphthyl group, a n-propylnaphthyl group, an isopropylnaphthyl group, a n-butylnaphthyl group, an isobutylnaphthyl group, a sec-butylnaphthyl group or a tert-butylnaphthyl group; aralkyl groups having 7 to 20 carbon atoms, such as a benzyl group or a phenethyl group; and groups obtained by combining these.

[0166] The hydrocarbyl group may have some or all of its hydrogen atoms substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, or may have some of its -CH- groups substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, or the like.

[0167] Also, R 23 and R 24 or R 26 and R 27 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. In this case, the ring is preferably one having the structure shown below. [ka] (In the formula, the dashed lines represent bonds.)

[0168] In formula (f1), M - is a non-nucleophilic counter ion. Specific examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkylsulfonate ions such as triflate ion, 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkylsulfonate ions such as mesylate ion and butanesulfonate ion; imide ions such as bis(trifluoromethylsulfonyl)imide ion, bis(perfluoroethylsulfonyl)imide ion and bis(perfluorobutylsulfonyl)imide ion; and methide ions such as tris(trifluoromethylsulfonyl)methide ion and tris(perfluoroethylsulfonyl)methide ion.

[0169] Further specific examples of the non-nucleophilic counter ion include a sulfonate ion represented by the following formula (f1-1) in which the α-position is substituted with a fluorine atom, and a sulfonate ion represented by the following formula (f1-2) in which the α-position is substituted with a fluorine atom and the β-position is substituted with a trifluoromethyl group. [ka]

[0170] In formula (f1-1), R 31 is a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, and the hydrocarbyl group may contain at least one selected from an ether bond, an ester bond, a carbonyl group, a lactone ring, and a fluorine atom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic.

[0171] In formula (f1-2), R 32 is a hydrogen atom, a hydrocarbyl group having 1 to 30 carbon atoms, or a hydrocarbylcarbonyl group having 6 to 20 carbon atoms, and the hydrocarbyl group and the hydrocarbylcarbonyl group may contain an ether bond, an ester bond, a carbonyl group, or a lactone ring. The hydrocarbyl moiety of the hydrocarbyl group and the hydrocarbylcarbonyl group may be saturated or unsaturated, and may be linear, branched, or cyclic.

[0172] Specific examples of the cation of the monomer that gives the repeating unit f1 include, but are not limited to, those shown below. B is the same as above. [ka]

[0173] Examples of the anion of the monomer that gives the repeating unit f2 include, but are not limited to, those shown below. In the following formula, R B is the same as above.

change

[0174]

change

[0175]

change

[0176]

change

[0177]

change

[0178]

change

[0179]

change

[0180]

change

[0181]

change

[0182]

change

[0183]

change

[0184] [ka]

[0185] [ka]

[0186] [ka]

[0187] Examples of the anion of the monomer that gives the repeating unit f3 include, but are not limited to, those shown below. In the following formula, R B is the same as above. [ka]

[0188] [ka]

[0189] Specific examples of the cation of the repeating unit f2 or f3 include the sulfonium salts described in paragraphs 0063 to 0080 and the iodonium salt described in paragraph 0082 of JP-A-2023-3926.

[0190] The repeating units f1 to f3 function as an acid generator. By bonding the acid generator to the polymer main chain, acid diffusion is reduced, and a decrease in resolution due to blurring caused by acid diffusion can be prevented. Furthermore, the acid generator is uniformly dispersed, improving LWR and CDU. When a base polymer containing the repeating unit f is used, the incorporation of an additive-type acid generator, which will be described later, can be omitted.

[0191] In the case of negative resist materials or non-chemically amplified resist materials, the repeating units a1 and a2 are not necessarily required in the base polymer.

[0192] As the base polymer, in addition to the above-mentioned polymers, resins such as novolak resin, polyimide, polyamide, polyvinylpyrrolidone, polyvinyl alcohol, polythiophene, and polyaniline can also be used.

[0193] [Organic solvents] The photolithography coating material or resist material of the present invention may contain an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the above-mentioned components and the components described below. Specific examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone, and 2-heptanone, as described in paragraphs

[0144] to

[0145] of JP-A-2008-111103; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol monoethyl ether. Examples of the suitable organic solvents include ethers such as glycol dimethyl ether and anisole; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono tert-butyl ether acetate; lactones such as γ-butyrolactone; lactams such as pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, and N-hydroxyethyl-2-pyrrolidone; water; and dimethyl sulfoxide.

[0194] In the resist material of the present invention, the content of the organic solvent is preferably 100 to 10,000 parts by mass, more preferably 200 to 8,000 parts by mass, based on 100 parts by mass of the base polymer. The organic solvent may be used alone or in combination of two or more kinds.

[0195] The resist material of the present invention may contain an additive acid generator. Examples of the additive acid generator include sulfonium salts or iodonium salts, sulfonium diazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate described in paragraphs

[0122] to

[0142] of JP-A-2008-111103 and paragraphs

[0077] to

[0148] of JP-A-2023-62677. When the resist material of the present invention contains the additive acid generator, the content is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, relative to 100 parts by mass of the base polymer. The additive acid generator may be used alone or in combination of two or more kinds.

[0196] The resist material of the present invention may contain a quencher. The quencher refers to a compound that can trap the acid generated by the acid generator in the resist material, thereby preventing the acid from diffusing into unexposed areas.

[0197] The quencher may be a conventional basic compound. Examples of conventional basic compounds include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amides, imides, and carbamates. In particular, the primary, secondary, and tertiary amine compounds described in paragraphs

[0146] to

[0164] of JP-A-2008-111103, particularly amine compounds having a hydroxy group, an ether bond, an ester bond, a lactone ring, a cyano group, or a sulfonic acid ester bond, or compounds having a carbamate group described in JP-A-3790649 are preferred. By adding such a basic compound, for example, the diffusion rate of the acid in the resist film can be further suppressed or the shape can be corrected.

[0198] Further, the quencher may be an onium salt such as a sulfonium salt, an iodonium salt, or an ammonium salt of a sulfonic acid or a carboxylic acid not fluorinated at the α-position, as described in JP-A-2008-158339. A sulfonic acid, an imide acid, or a methide acid having a fluorinated α-position is necessary for deprotecting an acid labile group of a carboxylic acid ester, but a sulfonic acid or a carboxylic acid not fluorinated at the α-position is released by salt exchange with an onium salt having a fluorinated α-position. A sulfonic acid or a carboxylic acid not fluorinated at the α-position does not cause a deprotection reaction, and therefore functions as a quencher.

[0199] Further examples of the quencher include polymer-type quenchers described in JP 2008-239918 A. These improve the rectangularity of the resist pattern by being oriented on the surface of the resist film. Polymer-type quenchers also have the effect of preventing film loss of the pattern and rounding of the pattern top when a protective film for immersion exposure is applied.

[0200] When the resist composition of the present invention contains the quencher, the content thereof is preferably 0 to 5 parts by mass, more preferably 0 to 4 parts by mass, based on 100 parts by mass of the base polymer. The quencher may be used alone or in combination of two or more kinds.

[0201] In the case of a negative resist, the resist material of the present invention may contain a crosslinking agent. By blending a crosslinking agent, the difference in dissolution rate between the exposed and unexposed parts can be further increased, but there is also a risk of increased swelling in the developer. Specific examples of crosslinking agents include those described in paragraphs

[0170] to

[0177] of JP 2020-027297 A. When the resist material of the present invention contains the crosslinking agent, the content thereof is preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by mass, relative to 100 parts by mass of the base polymer.

[0202] The photolithography coating material or resist material of the present invention may contain a water repellency improver for improving the water repellency of the resist film surface. The water repellency improver can be used in immersion lithography without using a topcoat. As the water repellency improver, a polymer containing a fluorinated alkyl group, a polymer containing a 1,1,1,3,3,3-hexafluoro-2-propanol residue of a specific structure, and the like are preferred, and those exemplified in JP-A-2007-297590 and JP-A-2008-111103 are more preferred. The water repellency improver needs to be dissolved in an alkaline developer or an organic solvent developer. The water repellency improver having the specific 1,1,1,3,3,3-hexafluoro-2-propanol residue described above has good solubility in the developer. As a water repellency improver, a polymer containing a repeating unit containing an amino group or an amine salt is highly effective in preventing the evaporation of acid during post-exposure baking (PEB) and preventing poor opening of a hole pattern after development. When the coating material or resist material for photolithography of the present invention contains the water repellency improver, the content thereof is preferably 0 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the base polymer. The water repellency improver may be used alone or in combination of two or more kinds.

[0203] The surfactant contained in the coating material for photolithography of the present invention can also be used as the water repellency improver. In this case, in addition to the surfactant having a high water repellency improving function, a surfactant having a high surface activity effect can also be combined.

[0204] The resist material of the present invention may contain acetylene alcohols. Specific examples of the acetylene alcohols include those described in paragraphs

[0179] to

[0182] of JP 2008-122932 A. When the resist material of the present invention contains the acetylene alcohols, the content is preferably 0 to 5 parts by mass relative to 100 parts by mass of the base polymer. The acetylene alcohols may be used alone or in combination of two or more kinds.

[0205] [Pattern formation method] When the resist material of the present invention is used for manufacturing various integrated circuits, known lithography techniques can be applied.For example, as a pattern forming method, there can be mentioned a method including the steps of forming a resist film on a substrate using the above-mentioned resist material, exposing the resist film to high-energy radiation, and developing the exposed resist film using a developer.

[0206] First, the resist material of the present invention is applied to a substrate for integrated circuit manufacturing (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective coating, etc.) or a substrate for mask circuit manufacturing (Cr, CrO, CrON, CrN, MoSi2, SiO 2、 The resist is applied onto a surface of the resist pattern (Ta, MoSi laminated film, Ru, Ni, Co, W, Mo, V, and alloys thereof, etc.) by a suitable application method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc. This is pre-baked on a hot plate at preferably 60 to 150° C. for 10 seconds to 30 minutes, more preferably 80 to 150° C. for 30 seconds to 20 minutes, to form a resist film.

[0207] Before applying the resist material of the present invention, the substrate may be treated by exposure to light, EB, plasma, or the like, or may be treated with CVD, ozone, hexamethyldisilazane (HMDS), or the like.

[0208] The thickness of the resist film is preferably from 1 nm to 200 μm, and more preferably from 2 nm to 100 μm.

[0209] A protective film may be formed on the resist film. The protective film preferably has functions such as environmental protection, light absorption, antistatic, reducing resist pattern defects, and correcting the resist pattern shape.

[0210] Next, the resist film is exposed to high-energy radiation. Specific examples of the high-energy radiation include ultraviolet radiation, far ultraviolet radiation, EB, EUV radiation with a wavelength of 3 to 15 nm, X-rays, soft X-rays, excimer laser light, gamma rays, synchrotron radiation, etc. When ultraviolet radiation, far ultraviolet radiation, EUV, X-rays, soft X-rays, excimer laser light, gamma rays, synchrotron radiation, etc. are used as the high-energy radiation, the exposure dose is preferably 1 to 200 mJ / cm2, either directly or using a mask for forming a desired pattern. 2 Approximately, more preferably 10 to 100 mJ / cm 2 When EB is used as the high energy beam, the exposure dose is preferably 0.1 to 1000 μC / cm 2 Approximately, more preferably 0.5 to 900 μC / cm 2 The resist material of the present invention is suitable for fine patterning using high energy rays such as g-rays, i-rays, KrF excimer laser light, ArF excimer laser light, EB, EUV, X-rays, soft X-rays, γ-rays, and synchrotron radiation.

[0211] After the exposure, PEB may be performed on a hot plate, preferably at 40 to 150° C. for 10 seconds to 30 minutes, more preferably at 50 to 120° C. for 30 seconds to 20 minutes.

[0212] After exposure or PEB, the substrate is developed using a developer for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes, by a standard method such as a dip method, a puddle method, or a spray method, to form a desired pattern on the substrate.

[0213] The developer may be an organic solvent developer or an alkaline aqueous developer. Examples of the organic solvent developer include 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, 3-ethoxypropionate, Examples of the developer include ethyl lactate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, 2-phenylethyl acetate, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, xylene, toluene, anisole, methanol, ethanol, isopropanol, n-butyl alcohol, isobutyl alcohol, acetic anhydride, and acetic acid. Specific examples of the alkaline aqueous solution developer include aqueous solutions of potassium hydroxide, sodium hydroxide, and the like, and alkaline aqueous solutions of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline hydroxide. The developer may be used alone or in a mixture of two or more.

[0214] At the end of the development, rinsing is performed. As the rinsing liquid, a solvent that is miscible with the developer and does not dissolve the resist film is preferable. As such a solvent, alcohols having 3 to 10 carbon atoms, ether compounds having 8 to 12 carbon atoms, alkanes, alkenes, alkynes having 6 to 12 carbon atoms, aromatic solvents, and pure water are preferably used.

[0215] Specific examples of the alcohol having 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tert-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, and 3-hexanol. Examples of such an alcohol include 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, and 1-octanol.

[0216] Specific examples of the ether compound having 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, di-n-pentyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-pentyl ether, and di-n-hexyl ether.

[0217] Specific examples of the alkanes having 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, cyclononane, etc. Specific examples of the alkes having 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, cyclooctene, etc. Specific examples of the alkynes having 6 to 12 carbon atoms include hexyne, heptine, octyne, etc.

[0218] Examples of aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, and mesitylene.

[0219] Rinsing can reduce the occurrence of resist pattern collapse and defects. Rinsing is not always necessary, and not performing rinsing can reduce the amount of solvent used.

[0220] The developed hole pattern or trench pattern can also be shrunk by thermal flow, RELACS technology, or DSA technology. A shrink agent is applied onto the hole pattern, and the shrink agent crosslinks on the surface of the resist film due to the diffusion of an acid catalyst from the resist film during baking, and the shrink agent adheres to the sidewalls of the hole pattern. The baking temperature is preferably 70 to 180°C, more preferably 80 to 170°C, and the baking time is preferably 10 to 300 seconds, and excess shrink agent is removed to reduce the hole pattern. EXAMPLES

[0221] The present invention will be specifically described below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples.

[0222] [1] Synthesis of surfactant polymers Monomers Sa-1 to Sa-33 and monomers Sb-1 to Sb-5 used in the synthesis of surfactant polymers are as follows: The Mw of the polymers is a polystyrene-equivalent measured value by GPC using THF as a solvent. [ka]

[0223] [ka]

[0224] [ka]

[0225] [ka]

[0226] [ka]

[0227] [ka]

[0228] [Synthesis Example 1] Synthesis of polymer SP-1 Under a nitrogen atmosphere, 0.42 g of 2-cyano-2-propylbenzodithioate and 0.10 g of 2,2'-azobisisobutyronitrile (AIBN) were dissolved in 37.5 g of methanol, and the resulting solution was stirred at 64°C for 3 hours under a nitrogen atmosphere. A solution of 9.5 g of monomer Sa-1 dissolved in 32.2 g of methanol was added dropwise to the solution over 2 hours. Then, a solution of 13.1 g of monomer Sb-1 dissolved in 48.2 g of methanol was added dropwise to the solution over 2 hours. After the dropwise addition, the mixture was stirred at 64°C for 4 hours. After cooling to room temperature, the mixture was added dropwise to 1000 g of hexane with vigorous stirring. The resulting solid was filtered and vacuum dried at 50°C for 15 hours to obtain polymer SP-1, a red solid diblock copolymer. The composition of polymer SP-1 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0229] [Synthesis Example 2] Synthesis of Polymer SP-2 Under a nitrogen atmosphere, 0.42 g of 2-cyano-2-propylbenzodithioate and 0.10 g of AIBN were dissolved in 37.5 g of methanol, and the solution was stirred at 64° C. under a nitrogen atmosphere for 3 hours. A solution of 4.3 g of monomer Sa-1 dissolved in 16.1 g of methanol was added dropwise to the solution over 2 hours. Next, a solution of 13.1 g of monomer Sb-1 dissolved in 48.2 g of methanol was added dropwise to the solution over 2 hours, and after the dropwise addition, the solution was stirred at 64° C. for 4 hours. After that, a solution of 4.3 g of monomer Sa-1 dissolved in 16.1 g of methanol was added dropwise to the solution over 2 hours, and after the dropwise addition, the solution was stirred at 64° C. for 4 hours. After cooling to room temperature, the solution was added dropwise to 1000 g of hexane with vigorous stirring. The resulting solid was filtered and dried in vacuum at 50°C for 15 hours to obtain polymer SP-2, a red solid triblock copolymer in which monomer Sb-1 was polymerized in the center and monomer Sa-1 was polymerized on both sides. The composition of polymer SP-2 was: 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0230] [Synthesis Example 3] Synthesis of polymer SP-3 A reaction vessel was charged with 11.2 g of monomer Sa-2, 28.9 g of monomer Sb-2, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-3, which is a random copolymer. The composition of polymer SP-3 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0231] [Synthesis Example 4] Synthesis of polymer SP-4 A reaction vessel was charged with 12.4 g of monomer Sa-3, 28.9 g of monomer Sb-2, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-4, which is a random copolymer. The composition of polymer SP-4 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0232] [Synthesis Example 5] Synthesis of polymer SP-5 A reaction vessel was charged with 10.0 g of monomer Sa-4, 28.9 g of monomer Sb-2, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-5, which is a random copolymer. The composition of polymer SP-5 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0233] [Synthesis Example 6] Synthesis of polymer SP-6 A reaction vessel was charged with 23.1 g of monomer Sa-5, 39.5 g of monomer Sb-3, and 100 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-6, which is a random copolymer. The composition of polymer SP-6 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0234] [Synthesis Example 7] Synthesis of polymer SP-7 A reaction vessel was charged with 13.8 g of monomer Sa-6, 42.8 g of monomer Sb-3, and 100 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-7, which is a random copolymer. The composition of polymer SP-7 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0235] [Synthesis Example 8] Synthesis of polymer SP-8 A reaction vessel was charged with 9.8 g of monomer Sa-7, 21.0 g of monomer Sb-4, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-8, which is a random copolymer. The composition of polymer SP-8 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0236] [Synthesis Example 9] Synthesis of polymer SP-9 A reaction vessel was charged with 13.6 g of monomer Sa-8, 21.0 g of monomer Sb-4, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-9, which is a random copolymer. The composition of polymer SP-9 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0237] [Synthesis Example 10] Synthesis of polymer SP-10 A reaction vessel was charged with 13.6 g of monomer Sa-9, 28.9 g of monomer Sb-2, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-10, which is a random copolymer. The composition of polymer SP-10 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0238] [Synthesis Example 11] Synthesis of Polymer SP-11 A reaction vessel was charged with 11.0 g of monomer Sa-10, 28.9 g of monomer Sb-2, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-11, which is a random copolymer. The composition of polymer SP-11 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0239] [Synthesis Example 12] Synthesis of polymer SP-12 A reaction vessel was charged with 11.0 g of monomer Sa-11, 28.9 g of monomer Sb-2, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-12, which is a random copolymer. The composition of polymer SP-12 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0240] [Synthesis Example 13] Synthesis of polymer SP-13 A reaction vessel was charged with 19.8 g of monomer Sa-12, 42.8 g of monomer Sb-3, and 100 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-13, which is a random copolymer. The composition of polymer SP-13 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0241] [Synthesis Example 14] Synthesis of polymer SP-14 A reaction vessel was charged with 12.8 g of monomer Sa-13, 28.9 g of monomer Sb-2, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-14, which is a random copolymer. The composition of polymer SP-14 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0242] [Synthesis Example 15] Synthesis of polymer SP-15 A reaction vessel was charged with 11.6 g of monomer Sa-14, 28.9 g of monomer Sb-2, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-15, which is a random copolymer. The composition of polymer SP-15 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0243] [Synthesis Example 16] Synthesis of polymer SP-16 A reaction vessel was charged with 33.2 g of monomer Sa-15 and 80 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-16. The composition of polymer SP-16 was as follows: 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0244] [Synthesis Example 17] Synthesis of polymer SP-17 To a reaction vessel, 34.8 g of monomer Sa-16 and 80 g of THF as a solvent were added. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-17. The composition of polymer SP-17 was as follows: 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0245] [Synthesis Example 18] Synthesis of polymer SP-18 A reaction vessel was charged with 17.0 g of monomer Sa-17, 10.9 g of monomer Sb-1, and 80 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-18, which is a random copolymer. The composition of polymer SP-18 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0246] [Synthesis Example 19] Synthesis of polymer SP-19 A reaction vessel was charged with 19.4 g of monomer Sa-18, 10.9 g of monomer Sb-1, and 80 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-19, which is a random copolymer. The composition of polymer SP-19 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0247] [Synthesis Example 20] Synthesis of Polymer SP-20 A reaction vessel was charged with 24.3 g of Monomer Sa-9, 4.0 g of Monomer Sa-20, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain Polymer SP-20, which is a random copolymer. The composition of Polymer SP-20 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0248] [Synthesis Example 21] Synthesis of Polymer SP-21 A reaction vessel was charged with 24.3 g of Monomer Sa-9, 7.3 g of Monomer Sa-21, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain Polymer SP-21, which is a random copolymer. The composition of Polymer SP-21 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0249] [Synthesis Example 22] Synthesis of polymer SP-22 A reaction vessel was charged with 24.3 g of Monomer Sa-9, 4.4 g of Monomer Sa-22, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain Polymer SP-22, which is a random copolymer. The composition of Polymer SP-22 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0250] [Synthesis Example 23] Synthesis of Polymer SP-23 A reaction vessel was charged with 35.5 g of Monomer Sa-23, 19.1 g of Monomer Sa-24, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain Polymer SP-23, which is a random copolymer. The composition of Polymer SP-23 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0251] [Synthesis Example 24] Synthesis of polymer SP-24 A reaction vessel was charged with 24.3 g of Monomer Sa-9, 10.3 g of Monomer Sa-25, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain Polymer SP-24, which is a random copolymer. The composition of Polymer SP-24 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0252] [Synthesis Example 25] Synthesis of Polymer SP-25 A reaction vessel was charged with 24.3 g of Monomer Sa-9, 9.8 g of Monomer Sa-26, and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain Polymer SP-25, which is a random copolymer. The composition of Polymer SP-25 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0253] [Synthesis Example 26] Synthesis of Polymer SP-26 17.8 g of p-trifluoromethoxyphenol, 90 g of 37% by mass aqueous formalin solution, and 5 g of oxalic acid were added to a reaction vessel, and reacted at 100° C. for 24 hours while stirring. This reaction solution was dissolved in 500 mL of methyl isobutyl ketone, thoroughly washed with water to remove the catalyst and metal impurities, and the solvent was removed under reduced pressure. The temperature was reduced to 150° C. and 2 mmHg to remove water and unreacted monomers, and polymer SP-26 was obtained. The composition of polymer SP-26 was as follows: 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0254] [Synthesis Example 27] Synthesis of polymer SP-27 In a reaction vessel, 17.8 g of p-trifluoromethoxyphenol, 20 g of 3-trifluoromethoxybenzaldehyde, and 5 g of oxalic acid were added and reacted at 100°C for 24 hours while stirring. This reaction solution was dissolved in 500 mL of methyl isobutyl ketone, thoroughly washed with water to remove the catalyst and metal impurities, and the solvent was removed under reduced pressure. The temperature was reduced to 150°C and 2 mmHg to remove water and unreacted monomers, yielding polymer SP-27. The composition of polymer SP-27 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0255] [Synthesis Example 28] Synthesis of Polymer SP-28 35.0 g of 9,9-bis(4-hydroxyphenyl)fluorene monotrifluoromethoxybenzmethanol, 20 g of 4-trifluoromethoxybenzaldehyde, and 5 g of oxalic acid were added to a reaction vessel, and the mixture was reacted at 100°C for 24 hours while stirring. The reaction solution was dissolved in 500 mL of methyl isobutyl ketone, and the catalyst and metal impurities were removed by thorough washing with water, and the solvent was removed under reduced pressure. The mixture was then heated to 150°C and the pressure was reduced to 2 mmHg to remove moisture and unreacted monomers, yielding polymer SP-28. The composition of polymer SP-28 was as follows: 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0256] [Synthesis Example 29] Synthesis of Polymer SP-29 45.0 g of 9,9-bis(6-hydroxynaphthyl)fluorene monotrifluoromethoxybenzmethanol, 20 g of 4-trifluoromethoxybenzaldehyde, and 5 g of oxalic acid were added to a reaction vessel, and the mixture was reacted at 100°C for 24 hours with stirring. The reaction solution was dissolved in 500 mL of methyl isobutyl ketone, and the catalyst and metal impurities were removed by thorough washing with water, and the solvent was removed under reduced pressure. The mixture was then heated to 150°C and the pressure was reduced to 2 mmHg to remove moisture and unreacted monomers, yielding polymer SP-29. The composition of polymer SP-29 was as follows: 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0257] [Synthesis Example 30] Synthesis of Polymer SP-30 44.0 g of 1,1,1-tris(4-hydroxyphenyl)ethane monotrifluoromethoxybenzmethanol, 20 g of 4-trifluoromethoxybenzaldehyde, and 5 g of oxalic acid were added to a reaction vessel, and the mixture was reacted at 100°C for 24 hours with stirring. The reaction solution was dissolved in 500 mL of methyl isobutyl ketone, and the catalyst and metal impurities were removed by thorough washing with water, and the solvent was removed under reduced pressure. The mixture was then heated to 150°C and the pressure was reduced to 2 mmHg to remove moisture and unreacted monomers, yielding polymer SP-30. The composition of polymer SP-30 was as follows: 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0258] [Synthesis Example 31] Synthesis of polymer SP-31 38.0 g of 2,7-dihydroxynaphthalene monotrifluoromethoxybenzmethanol, 20 g of 4-trifluoromethoxybenzaldehyde, and 5 g of oxalic acid were added to a reaction vessel, and the mixture was reacted at 100°C for 24 hours with stirring. The reaction solution was dissolved in 500 mL of methyl isobutyl ketone, and the catalyst and metal impurities were removed by thorough washing with water, and the solvent was removed under reduced pressure. The mixture was then heated to 150°C and the pressure was reduced to 2 mmHg to remove water and unreacted monomers, yielding polymer SP-31. The composition of polymer SP-31 was as follows: 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0259] [Synthesis Example 32] Synthesis of polymer SP-32 A reaction vessel was charged with 14.7 g of monomer Sa-27, 2.3 g of hydroxyethyl acrylate, and 20 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-32, which is a random copolymer. The composition of polymer SP-32 was as follows: 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0260] [Synthesis Example 33] Synthesis of polymer SP-33 A reaction vessel was charged with 29.5 g of monomer Sa-28, 2.2 g of mono(2-acryloyloxyethyl) succinate, and 50 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-33, which is a random copolymer. The composition of polymer SP-33 was 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0261] [Synthesis Example 34] Synthesis of polymer SP-34 A reaction vessel was charged with 15.2 g of monomer Sa-29, 5.8 g of monomer Sb-5, and 20 g of 1,2-dichloroethane as a solvent. 0.2 g of trifluoroboron was added as a polymerization initiator under a nitrogen atmosphere, and the reaction was allowed to proceed for 15 hours after heating to 60°C. The reaction solution was concentrated to 1 / 2 and precipitated in a mixed solution of 1.5 L of methanol and 0.2 L of water. The resulting white solid was filtered and dried under reduced pressure at 60°C to obtain polymer SP-34, which is a random copolymer. The composition of polymer SP-34 is as follows: 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0262] [Synthesis Example 35] Synthesis of Polymer SP-35 A reaction vessel was charged with 14.9 g of monomer Sa-30, 5.8 g of monomer Sb-5, and 20 g of 1,2-dichloroethane as a solvent. The reaction vessel was placed in a nitrogen atmosphere, and 0.2 g of trifluoroboron was added as a polymerization initiator. The reaction vessel was heated to 60°C and reacted for 15 hours. The reaction solution was concentrated to 1 / 2 and precipitated in a mixed solution of 1.5 L of methanol and 0.2 L of water. The resulting white solid was filtered and dried under reduced pressure at 60°C to obtain polymer SP-35, a random copolymer. The composition of polymer SP-35 was as follows: 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0263] [Synthesis Example 36] Synthesis of polymer SP-36 A reaction vessel was charged with 38.1 g of monomer Sa-31 and 60 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-36. The composition of polymer SP-36 was as follows: 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0264] [Synthesis Example 37] Synthesis of polymer SP-37 To a reaction vessel, 38.7 g of monomer Sa-32 and 60 g of THF as a solvent were added. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-37. The composition of polymer SP-37 was as follows: 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0265] [Synthesis Example 38] Synthesis of polymer SP-38 Polymer SP-27 was glycidylated and then reacted with p-trifluoromethoxybenzoic acid to obtain polymer SP-38. The composition of polymer SP-38 is 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0266] [Synthesis Example 39] Synthesis of polymer SP-39 A reaction vessel was charged with 29.4 g of monomer Sa-33 and 80 g of THF as a solvent. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After heating to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 15 hours. This reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered off. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-39. The composition of polymer SP-39 was as follows: 19 F-NMR and 1 Mw and Mw / Mn were confirmed by H-NMR and GPC, respectively. [ka]

[0267] [Synthesis Examples 40 to 44] Synthesis of base polymers (polymers P-1 to P-5) Each monomer was combined and copolymerized in THF, a solvent, and then added to methanol. The precipitated solid was washed with hexane, isolated, and dried to obtain base polymers (polymers P-1 to P-5) with the following compositions. The compositions of the obtained base polymers were as follows: 1 Mw and Mw / Mn were confirmed by H-NMR and GPC (solvent: THF, standard: polystyrene). [ka]

[0268] In Table 1, the components are as follows: Organic solvent: PGMEA (propylene glycol monomethyl ether acetate) DAA (Diacetone Alcohol) EL (Ethyl lactate)

[0269] Acid generator (PAG-1), quencher (Q-1) [ka]

[0270] [Examples 1 to 40, Comparative Example 1] A solution in which each component was dissolved according to the composition shown in Tables 1 and 2 was filtered through a polyethylene filter having an aperture of 3 nm to prepare a resist material. Each resist material shown in Tables 1 and 2 was dispensed onto a silicon substrate having a diameter of 300 mm, followed by spin coating and pre-baking on a hot plate at 110°C for 30 seconds to form a resist film having a thickness of 60 nm. The thickness of the resist film was measured at 225 concentric points on the wafer surface using an optical film thickness meter, and the difference between the maximum and minimum film thicknesses was calculated. The results are shown in Tables 1 and 2. Examples 1 to 39 and Comparative Example 1 are positive resist materials, and Example 40 is a negative resist material.

[0271] [Table 1]

[0272] [Table 2]

[0273] The results shown in Tables 1 and 2 demonstrate that the resist film obtained from the resist material containing a surfactant made of a resin having a fluorine atom-substituted aromatic group, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group, or a difluoromethylthio group of the present invention, a base polymer, and an organic solvent has a uniform thickness.

Claims

1. A coating material for photolithography, comprising 0.0001 to 3 mass % of a surfactant made of a resin having an aromatic group substituted with a fluorine atom, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group or a difluoromethylthio group.

2. 2. The coating material for photolithography according to claim 1, wherein the resin is a polymer containing a repeating unit Sa having a fluorine-substituted aromatic group, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group or a difluoromethylthio group.

3. 3. The coating material for photolithography according to claim 2, wherein the repeating unit Sa is represented by any one of the following formulas (Sa1) to (Sa5): 【Chemistry 1】 (In the formula, each m is independently an integer of 1 to 5. Each n is independently an integer of 0 to 4. Each p is independently an integer of 1 to 3. Each q is an integer of 0 to 3. Each r is an integer of 0 to 3. Each s is an integer of 0 to 4. With the proviso that q+s is an integer of 1 to 5. R A are each independently a hydrogen atom or a methyl group. X 1 are each independently a single bond, an ester bond, an ether bond, an amide bond, or a phenylene group. X 2 each independently represents a single bond or a hydrocarbylene group having 1 to 20 carbon atoms when p is 1, and represents a (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms when p is 2 or 3, and the hydrocarbylene group and the (p+1)-valent hydrocarbon group may contain at least one atom selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a halogen atom. X 3A each independently represents a single bond, an ester bond, an ether bond, an amide bond, a sulfonate ester bond, a urethane bond, a thiourethane bond, a urea bond, or -S(=O)-N(X 31 )-. X 31 is a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. X 3B is a single bond or a carbonyl group. X 4 is —O— or —S—. X 5 represents a single bond or a hydrocarbylene group having 1 to 12 carbon atoms, and the hydrocarbylene group may have at least one bond selected from a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, an ether bond, and an ester bond. Yen R 1 are each independently a (m+n+1)-valent group derived from benzene or naphthalene. R 2 each independently represents a hydrogen atom, a hydrocarbyl group having 1 to 6 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a hydrocarbyloxycarbonyl group having 2 to 6 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 12 carbon atoms, a hydroxy group, a carboxy group, a halogen atom, a cyano group, or a nitro group. R 3 are each independently a trifluoromethyl group or a difluoromethyl group. R 4 each independently represents a hydrocarbyl group having 1 to 6 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a hydrocarbyloxycarbonyl group having 2 to 6 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 12 carbon atoms, a hydroxy group, a carboxy group, a halogen atom, a cyano group, or a nitro group. Yen R 5 are each independently a (q+r+2)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms. Yen R 6 is a (s+1)-valent group derived from benzene or naphthalene. R 7 is a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms, and the hydrocarbyl group may contain an oxygen atom. 7 is -X 5 -X 4 -R 3 does not have a group represented by the following formula:

4. X 1 and X 2 4. The coating material for photolithography according to claim 3, wherein at least one of the following is not a single bond.

5. 4. The coating material for photolithography according to claim 3, which is a polymer containing a repeating unit represented by formula (Sa1) and a repeating unit represented by formula (Sa2).

6. 3. The coating material for photolithography according to claim 2, wherein the polymer further comprises a repeating unit Sb having a hydrophilic group selected from the group consisting of an ether bond, an ester bond, a hydroxy group, a carboxy group, a sulfonamide bond, a sulfonimide bond and a sulfo group.

7. 7. The coating material for photolithography according to claim 6, wherein the polymer is a block copolymer.

8. A resist material comprising the coating material for photolithography according to claim 1.

9. The resist material according to claim 8, further comprising a base polymer and an organic solvent.

10. 10. A method for forming a pattern, comprising the steps of: forming a resist film on a substrate using the resist material according to claim 8; exposing the resist film to high-energy radiation; and developing the exposed resist film using a developer.

11. 11. The pattern forming method according to claim 10, wherein the high energy beam is g-ray, i-ray, KrF excimer laser, ArF excimer laser, ultraviolet ray, electron beam or extreme ultraviolet ray having a wavelength of 3 to 15 nm.

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