Coating material for optical lithography, resist material, and pattern forming method

Abstract

The invention relates to a coating material for optical lithography, a resist material, and a pattern forming method. The present invention addresses the problem of providing: a resist material which contains a surfactant that does not have a perfluoroalkyl structure, has excellent film flatness after coating, and has few defects not only after coating but also after developing; and a pattern forming method using the resist material. [Solution] The coating material for optical lithography contains 0.0001-3 mass% of a surfactant comprising a resin having an aromatic group substituted with a fluorine atom, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group, or a difluoromethylthio group.

Description

Technical Field

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

[0002] With the high integration and high speed of LSI, the miniaturization of pattern rules is progressing rapidly. This is because the popularization of 5G high-speed communication and artificial intelligence (AI) is in progress, and high-performance devices are needed to process them. As for the most advanced miniaturization technology, mass production of 5nm node devices using extreme ultraviolet (EUV) lithography with a wavelength of 13.5nm has been implemented. Furthermore, discussions are underway on the use of EUV lithography even for the next-generation 3nm node and the next-generation 2nm node devices.

[0003] Materials used in optical lithography, such as resist materials, are applied by spin coating a solution, and then baked to evaporate the solvent to form a film. The film thickness after baking is required to be uniform and flat, and the requirements for uniformity and flatness are becoming more and more stringent every year.

[0004] 3D-NAND memory applications require thick resist films, and each layer must be flat. As the film thickness increases, it becomes difficult to achieve flatness. On the other hand, as miniaturization progresses, thinning is also progressing, and in this case, the risk of pinhole defects and the like increases.

[0005] During coating, if the solvent generates Marangoni convection, it will cause scratches. In order to prevent Marangoni convection, it is important to select a solvent with an optimal boiling point and low viscosity, and to select a surfactant for reducing surface tension.

[0006] Surfactants having fluoroalkyl or polysiloxane chains have a high effect of reducing surface tension, and fluoroalkyl surfactants are widely used, especially those with a low risk of generating silicon-derived particles after dry ashing of resist films (Patent Documents 1 and 2). Moreover, fluorinated surfactants are used not only in resist materials but also in surface coatings formed on the upper layer of resists and in anti-reflective films formed on the lower layer of resists (Patent Document 3).

[0007] In this regard, some people have criticized the health effects of perfluoroalkyl compounds (PFAS), and the European REACH has set restrictions on the manufacture and sale of PFAS compounds. The development of materials that do not have PFAS structures is an urgent task.

[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 without fluorine atoms, and a solvent are mixed, and after coating, the fluorine-containing resin is oriented on the surface layer, and a two-layer antireflection film is formed by a single coating.

[0009] Surfactants having a trifluoromethoxy group and a pentafluorosulfur group and uses thereof have been proposed (Patent Document 5).

[0010] Prior art literature

[0011] Patent Literature

[0012] [Patent Document 1] Japanese Patent Application Laid-Open No. 6-186735

[0013] [Patent Document 2] Japanese Patent Application Laid-Open No. 6-214380

[0014] [Patent Document 3] Japanese Patent Application Laid-Open No. 6-289620

[0015] [Patent Document 4] Japanese Patent Application Publication No. 2010-139822

[0016] [Patent Document 5] Japanese Patent Publication No. 2008-526792 Summary of the invention

[0017] [Problems to be solved by the invention]

[0018] 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 optical lithography containing a surfactant having no perfluoroalkyl structure, a resist material having excellent flatness of a film after coating and few defects after coating and development, and a pattern forming method using the same.

[0019] [Methods to solve the problem]

[0020] The inventors of this application have repeatedly and diligently reviewed surfactants for optical lithography coating materials in recent years in order to obtain the desired high flatness after coating, good coating properties at the outermost edge of the wafer, and few defects after coating, development, and even etching. As a result, it was found that by adding a surfactant 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 to the optical lithography coating material, it will show high flatness after coating and few defects after coating and development, and even complete the present invention. In addition, aromatic groups substituted with fluorine atoms, trifluoromethoxy groups, and difluoromethoxy groups 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.

[0021] That is, the present invention provides the following coating material for optical lithography, resist material, and pattern forming method.

[0022] 1. A coating material for optical lithography, comprising 0.0001 to 3% by mass of a surfactant 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.

[0023] 2. The coating material for optical lithography according to 1, wherein the resin is a polymer comprising 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.

[0024] 3. The coating material for optical lithography according to 2, wherein the repeating unit Sa is represented by any of the following formulae (Sa1) to (Sa5),

[0025] [Chemistry 1]

[0026]

[0027] In the formula, m is each independently an integer of 1 to 5, n is each independently an integer of 0 to 4, p is each 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, but q+s is an integer of 1 to 5,

[0028] R A are each independently a hydrogen atom or a methyl group,

[0029] X 1 are each independently a single bond, an ester bond, an ether bond, an amide bond or a phenylene group,

[0030] When p is 1, X 2 Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and when p is 2 or 3, X 2Each is independently a (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms, and the alkylene 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,

[0031] X 3A Each is independently a single bond, an ester bond, an ether bond, an amide bond, a sulfonate bond, a carbamate bond, a thiolcarbamate bond, a urea bond or -S(=O)-N(X 31 )-,X 31 is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms,

[0032] X 3B is a single bond or a carbonyl group,

[0033] X 4 is -O- or -S-,

[0034] X 5 is a single bond or an alkylene group having 1 to 12 carbon atoms, and the alkylene group may have at least one selected from a hydroxyl group, a saturated alkyloxy group having 1 to 6 carbon atoms, an ether bond, and an ester bond,

[0035] Circle R 1 are each independently a (m+n+1)-valent group derived from benzene or naphthalene,

[0036] R 2 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydrocarbonoxy group having 1 to 12 carbon atoms, a hydrocarbonoxycarbonyl group having 2 to 6 carbon atoms, a hydrocarboncarbonyloxy group having 2 to 12 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group,

[0037] R 3 are each independently trifluoromethyl or difluoromethyl,

[0038] R 4 each independently represents a hydrocarbon group having 1 to 6 carbon atoms, a hydrocarbonoxy group having 1 to 12 carbon atoms, a hydrocarbonoxycarbonyl group having 2 to 6 carbon atoms, a hydrocarboncarbonyloxy group having 2 to 12 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group,

[0039] Circle R 5 Each is independently a (q+r+2)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms,

[0040] Circle R 6 is a (s+1)-valent group derived from benzene or naphthalene,

[0041] R 7 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, which may also contain an oxygen atom. 7 Does not have -X 5 -X 4 -R 3 Represents the group.

[0042] 4. The coating material for optical lithography as described in 3, wherein X 1 and X 2 At least one of them is not a single bond.

[0043] 5. The coating material for optical lithography according to 3, which is a polymer comprising a repeating unit represented by formula (Sa1) and a repeating unit represented by formula (Sa2).

[0044] 6. The optical lithography coating material 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 hydroxyl group, a carboxyl group, a sulfonamide bond, a sulfonimide bond and a sulfonic acid group.

[0045] 7. The coating material for optical lithography as described in 6, wherein the polymer is a block copolymer.

[0046] 8. A resist material comprising the coating material for optical lithography according to any one of 1 to 7.

[0047] 9. The resist material as in 8 further comprises a base polymer and an organic solvent.

[0048] 10. A pattern forming method comprising the following steps: forming a resist film on a substrate using the resist material as described in 8 or 9, exposing the resist film to high-energy rays, and developing the exposed resist film using a developer.

[0049] 11. The pattern forming method of 10, wherein the high-energy ray is g-ray, i-ray, KrF excimer laser, ArF excimer laser, ultraviolet ray, electron beam or extreme ultraviolet ray with a wavelength of 3 to 15 nm.

[0050] [Effects of the Invention]

[0051] The surfactant used in the optical photolithography coating material of the present invention 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. The film obtained from the optical photolithography coating material containing the surfactant has the following effects: the flatness of the entire surface of the coated substrate and the uniformity of the film thickness are excellent, when the outermost part of the wafer is coated, the edge cutting can be cleanly performed by a solvent, and the substrate has excellent filling characteristics when it has uneven surfaces. In the case of a photosensitive material such as a resist material, it has the effect of reducing defects after coating, after development, and even after dry etching. For example, it can be applied not only to photolithography in semiconductor circuit formation, but also to the formation of mask circuit patterns, micromachines, and thin film head circuit formation. DETAILED DESCRIPTION

[0052] [Coating materials for optical lithography]

[0053] The coating material for optical lithography of the present invention comprises a surfactant 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.

[0054] The aforementioned 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.

[0055] As for the repeating unit Sa, it is preferably represented by the following formula (Sa1) (hereinafter, also referred to as repeating unit Sa1), the following formula (Sa2) (hereinafter, also referred to as repeating unit Sa2), the following formula (Sa3) (hereinafter, also referred to as repeating unit Sa3), the following formula (Sa4) (hereinafter, also referred to as repeating unit Sa4) or the following formula (Sa5) (hereinafter, also referred to as repeating unit Sa5).

[0056] [Chemistry 2]

[0057]

[0058] In formulae (Sa1) to (Sa5), m is an integer of 1 to 5, each independently. n is an integer of 0 to 4, each independently. p is an integer of 1 to 3, each independently. q is an integer of 0 to 3, r is an integer of 0 to 3, and s is an integer of 0 to 4. However, q+s is an integer of 1 to 5.

[0059] In formulas (Sa1) to (Sa3), R A Each is independently a hydrogen atom or a methyl group.

[0060] In formulas (Sa1) to (Sa3), X 1 Each is independently a single bond, an ester bond, an ether bond, an amide bond or a phenylene group.

[0061] In formulas (Sa1) to (Sa3), when p is 1, X 2 Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and when p is 2 or 3, X 2 Each is independently a (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms. 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.

[0062] X 2The alkylene group represented by may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkane diyl groups having 1 to 20 carbon atoms, such as methane diyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl; cyclic saturated alkylene groups having 3 to 20 carbon atoms, such as cyclopentane diyl, cyclohexane diyl, norbornane diyl, and adamantane diyl; unsaturated aliphatic alkylene groups having 2 to 20 carbon atoms, such as vinylene and propylene-1,3-diyl; arylene groups having 6 to 20 carbon atoms, such as phenylene and naphthylene; and groups obtained by combining these. In addition, X 2 The (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms represented by , may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include groups obtained by removing one or two hydrogen atoms from the aforementioned alkylene group, and groups obtained by replacing one or two hydrogen atoms in the aforementioned alkylene group with an alkylene group.

[0063] X 1 and X 2 Preferably, at least one of them is not a single bond.

[0064] In formula (Sa1) and (Sa2), X 3A Each is independently a single bond, an ester bond, an ether bond, an amide bond, a sulfonate bond, a carbamate bond, a thiolcarbamate bond, a urea bond or -S(=O)-N(X 31 )-.X 31 It is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms.

[0065] In formula (Sa3), X 3B A single bond or a carbonyl group.

[0066] In formulas (Sa2) to (Sa5), X 4 It is -O- or -S-.

[0067] In formula (Sa4) and (Sa5), X 5 It is a single bond or a hydrocarbylene group having 1 to 12 carbon atoms. The hydrocarbylene group may have at least one selected from the group consisting of a hydroxyl group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, an ether bond, and an ester bond.

[0068] In formula (Sa1) and (Sa2), circle R 1 Each is independently a (m+n+1)-valent group derived from benzene or naphthalene.

[0069] In formula (Sa1) and (Sa2), R 2Each is independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydrocarbonoxy group having 1 to 12 carbon atoms, a hydrocarbonoxycarbonyl group having 2 to 6 carbon atoms, a hydrocarboncarbonyloxy group having 2 to 12 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group.

[0070] In formulas (Sa2) to (Sa5), R 3 Each is independently trifluoromethyl or difluoromethyl.

[0071] In formula (Sa4) and (Sa5), R 4 Each is independently a hydrocarbon group having 1 to 6 carbon atoms, a hydrocarbonoxy group having 1 to 12 carbon atoms, a hydrocarbonoxycarbonyl group having 2 to 6 carbon atoms, a hydrocarboncarbonyloxy group having 2 to 12 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group.

[0072] In formula (Sa4) and (Sa5), circle R 5 Each is independently a (q+r+2)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms. The aforementioned (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, terphenyl, fluorenylenebisphenol, fluorenylenebisnaphthol, etc., and may have a substituted or unsubstituted hydroxyl group or a saturated hydrocarbon group having 1 to 12 carbon atoms, and may be bonded to benzene or naphthalene having a substituted or unsubstituted hydroxyl group.

[0073] In formula (Sa4), circle R 6 It is a (s+1)-valent group derived from benzene or naphthalene.

[0074] In formula (Sa5), R 7 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may also contain an oxygen atom. 7 Does not have -X 5 -X 4 -R 3 Represents the group.

[0075] The polymer is preferably a polymer including at least one selected from the repeating units Sa1, Sa2 and Sa3 (hereinafter, also referred to as polymer A).

[0076] The monomer having an aromatic group substituted with a fluorine atom which provides the repeating unit Sa1 includes the following, but is not limited thereto. A Same as above.

[0077] [Chemistry 3]

[0078]

[0079] [Chemistry 4]

[0080]

[0081] [Chemistry 5]

[0082]

[0083] [Chemistry 6]

[0084]

[0085] [Chemistry 7]

[0086]

[0087] [Chemistry 8]

[0088]

[0089] [Chemistry 9]

[0090]

[0091] [Chemistry 10]

[0092]

[0093] [Chemistry 11]

[0094]

[0095] [Chemistry 12]

[0096]

[0097] [Chemistry 13]

[0098]

[0099] [Chemistry 14]

[0100]

[0101] [Chemistry 15]

[0102]

[0103] [Chemistry 16]

[0104]

[0105] [Chemistry 17]

[0106]

[0107] [Chemistry 18]

[0108]

[0109] [Chemistry 19]

[0110]

[0111] [Chemistry 20]

[0112]

[0113] [Chemistry 21]

[0114]

[0115] Examples of the monomer having a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group or a difluoromethylthio group which provides the repeating unit Sa2 include the following, but are not limited thereto.

[0116] [Chemistry 22]

[0117]

[0118] [Chemistry 23]

[0119]

[0120] [Chemistry 24]

[0121]

[0122] [Chemistry 25]

[0123]

[0124] [Chemistry 26]

[0125]

[0126] [Chemistry 27]

[0127]

[0128] [Chemistry 28]

[0129]

[0130] [Chemistry 29]

[0131]

[0132] [Chemistry 30]

[0133]

[0134] [Chemistry 31]

[0135]

[0136] [Chemistry 32]

[0137]

[0138] [Chemistry 33]

[0139]

[0140] [Chemistry 34]

[0141]

[0142] [Chemistry 35]

[0143]

[0144] [Chemistry 36]

[0145]

[0146] [Chemistry 37]

[0147]

[0148] [Chemistry 38]

[0149]

[0150] [Chemistry 39]

[0151]

[0152] [Chemistry 40]

[0153]

[0154] [Chemistry 41]

[0155]

[0156] [Chemistry 42]

[0157]

[0158] [Chemistry 43]

[0159]

[0160] [Chemistry 44]

[0161]

[0162] [Chemistry 45]

[0163]

[0164] [Chemistry 46]

[0165]

[0166] [Chemistry 47]

[0167]

[0168] [Chemistry 48]

[0169]

[0170] [Chemistry 49]

[0171]

[0172] [Chemistry 50]

[0173]

[0174] [Chemistry 51]

[0175]

[0176] [Chemistry 52]

[0177]

[0178] [Chemistry 53]

[0179]

[0180] [Chemistry 54]

[0181]

[0182] [Chemistry 55]

[0183]

[0184] [Chemistry 56]

[0185]

[0186] [Chemistry 57]

[0187]

[0188] [Chemistry 58]

[0189]

[0190] [Chemistry 59]

[0191]

[0192] [Chemistry 60]

[0193]

[0194] [Chemistry 61]

[0195]

[0196] [Chemistry 62]

[0197]

[0198] [Chemistry 63]

[0199]

[0200] [Chemistry 64]

[0201]

[0202] The monomers that provide the repeating unit Sa3 include the following, but are not limited to these.

[0203] [Chemistry 65]

[0204]

[0205] [Chemistry 66]

[0206]

[0207] [Chemistry 67]

[0208]

[0209] [Chemistry 68]

[0210]

[0211] [Chemistry 69]

[0212]

[0213] The polymer A preferably further comprises a repeating unit having a hydrophilic group. By comprising a highly water-repellent repeating unit Sa having a fluorine atom and a repeating unit Sb having a hydrophilic group, the surface active effect can be fully exhibited.

[0214] The repeating unit Sb has a hydrophilic group selected from an ether bond, an ester bond, a hydroxyl group, a carboxyl group, a sulfonamide bond, a sulfonimide bond, a sulfonic acid group, a lactone ring, a sultone ring, a carbonate bond, a carbamate bond, and an amide bond.

[0215] Specific examples of the monomer providing the repeating unit Sb include those shown below, but are not limited to these.

[0216] [Chemistry 70]

[0217]

[0218] [Chemical formula 71]

[0219]

[0220] [Chemical formula 72]

[0221]

[0222] [Chemical formula 73]

[0223]

[0224] [Chemical formula 74]

[0225]

[0226] [Chemical formula 75]

[0227]

[0228] [Chemical formula 76]

[0229]

[0230] [Chemical formula 77]

[0231]

[0232] 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; still more preferably 0 ≤ Sa1 ≤ 0.8, 0 ≤ Sa2 ≤ 0.8, 0 ≤ Sa3 ≤ 0.8, 0.2 ≤ Sa1 + Sa2 + Sa3 ≤ 0.8, and 0.2 ≤ Sb ≤ 0.8. However, Sa1 + Sa2 + Sa3 + Sb = 1.0.

[0233] The polystyrene-equivalent weight average molecular weight (Mw) of polymer A measured by gel permeation chromatography (GPC) using THF as a solvent is preferably 1,000 to 500,000, and more preferably 2,000 to 30,000. Furthermore, in the case where the molecular weight distribution (Mw / Mn) of polymer A is wide, there are low molecular weight and high molecular weight polymers, so there is a concern that foreign matter may be visible on the pattern after exposure, or the shape of the pattern may deteriorate. As the pattern rules become finer, the influence of Mw and Mw / Mn tends to become greater, so in order to obtain a resist material suitable for a fine pattern size, the Mw / Mn of the above-mentioned polymer A is preferably 1.0 to 2.0, and a narrow dispersion of 1.0 to 1.5 is particularly preferred.

[0234] The polymer A may include two or more polymers having different composition ratios, Mw, and Mw / Mn. In addition, polymers including different repeating units Sa1, Sa2, and Sb may be mixed.

[0235] The polymer A can be obtained by polymerizing a monomer providing a repeating unit selected from the repeating units Sa1, Sa2, Sa3 and Sb by a method such as free radical polymerization, anionic polymerization, or cationic polymerization.

[0236] When polymer A comprises two or more repeating units, it can be a random copolymer or a block copolymer, and a block copolymer has a high characteristic of being effective as a surfactant. In particular, a block copolymer containing repeating units Sa and Sb is preferred. A block copolymer can be a diblock copolymer consisting of two units, a triblock copolymer consisting of three units, or a tetrablock copolymer consisting of four units.

[0237] When random copolymerization is performed by free radical polymerization, it is generally a method of polymerizing by mixing the monomers to be copolymerized and the free radical initiator and heating them. When the first monomer is polymerized in the presence of a free radical initiator and then the second monomer is added, one side of the polymer molecule has a block polymerized with the first monomer and the other side has a block polymerized with the second monomer. However, in this case, the repeating units from the first monomer and the second monomer are mixed in the middle part, which is different from the block copolymer form. In order to form a block copolymer by free radical polymerization, it is preferable to use active free radical polymerization. In the active free radical polymerization method called Reversible Addition Fragmentation chain Transfer (RAFT) polymerization, the free radicals at the end of the polymer are always active, so the polymerization is started by the first monomer, and the second monomer is added at the stage of consuming them, so a block copolymer composed of the first repeating unit and the second repeating unit can be formed. In the case where the polymerization is started by the first monomer, the second monomer is added at the point of consuming it, and then the third monomer is added, a triblock copolymer can be formed. During RAFT polymerization, a narrow dispersion polymer having a narrow dispersion degree is also formed.

[0238] As for the organic solvent used in the polymerization, toluene, benzene, tetrahydrofuran (THF), ether, dioxane, etc. can be mentioned. As for the polymerization initiator, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-methylpropionic acid) dimethyl ester, benzoyl peroxide, lauroyl peroxide, etc. can be mentioned. The temperature during the polymerization is preferably 50 to 80°C. The reaction time is preferably 2 to 100 hours, and more preferably 5 to 20 hours.

[0239] A chain transfer agent is required for RAFT polymerization, and specific examples thereof include 2-cyano-2-propylthiobenzoate, 4-cyano-4-phenylthiocarbonylthiopentanoic acid, 2-cyano-2-propyldodecyl trithiocarbonate, 4-cyano-4-[(dodecylthiocarbonylmercapto)mercapto]pentanoic acid, 2-(dodecylthiocarbonylthio)-2-methylpropionic acid, cyanomethyldodecylthiocarbonate, cyanomethyl N-methyl-N-phenylthiocarbamate, bis(thiophenyl)disulfide, and bis(dodecylthiocarbonylthio)disulfide. Among them, 2-cyano-2-propylthiobenzoate is the most preferred.

[0240] When adding a primary monomer for RAFT polymerization, a narrowly dispersed polymer can be synthesized.

[0241] When the polymer comprises at least one selected from the repeating units Sa4 and Sa5, the polymer is a novolac resin (hereinafter, also referred to as polymer B). Polymer B can be obtained by polycondensation reaction of a phenol compound and an aldehyde compound. Furthermore, 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.

[0242] The aforementioned phenol compound is a compound having a hydroxyl 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-tri(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.

[0243] As for the above-mentioned aldehyde compound, for example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, 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, p-n-butylbenzaldehyde, furfural, etc. can be listed. Among them, formaldehyde is particularly suitable. These aldehyde compounds can be used alone or in combination of two or more.

[0244] 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. Examples of the phenol compound having these groups include trifluoromethoxyphenol, difluoromethoxyphenol, trifluoromethylthiophenol, difluoromethylthiophenol, 9,9-bis(4-hydroxyphenyl)fluorene monotrifluoromethoxybenzyl alcohol, 9,9-bis(4-hydroxyphenyl)fluorene monodifluoromethoxybenzyl alcohol, 9,9-bis(4-hydroxyphenyl)fluorene monotrifluoromethylthiobenzyl alcohol, 9,9-bis(4-hydroxyphenyl)fluorene monodifluoromethylthiobenzyl alcohol, 9,9-bis(4-hydroxyphenyl)fluorene monotrifluoromethoxybenzyl alcohol, 9,9-bis(4-hydroxyphenyl)fluorene monodifluoromethylthiobenzyl alcohol, 9,9-bis(6-hydroxynaphthyl)fluorene monotrifluoromethoxybenzyl alcohol, 9,9-bis(6-hydroxynaphthyl)fluorene monotri ... 1,1,1-tris(4-hydroxyphenyl)ethane monotrifluoromethoxybenzyl alcohol, 1,1,1-tris(4-hydroxyphenyl)ethane monotrifluoromethoxybenzyl alcohol, 1,1,1-tris(4-hydroxyphenyl)ethane monotrifluoromethylthiobenzyl alcohol, 1,1,1-tris(4-hydroxyphenyl)ethane monotrifluoromethylthiobenzyl alcohol, 2,7-dihydroxynaphthyl monotrifluoromethoxybenzyl alcohol, 2,7-dihydroxynaphthyl monotrifluoromethoxybenzyl alcohol, 2,7-dihydroxynaphthyl monotrifluoromethylthiobenzyl alcohol, 2,7-dihydroxynaphthyl monotrifluoromethylthiobenzyl alcohol, etc. Examples of the aldehyde compounds having these groups include trifluoromethoxybenzaldehyde, difluoromethoxybenzaldehyde, trifluoromethylthiobenzaldehyde, and difluoromethylthiobenzaldehyde.

[0245] The phenol compound may be used alone or in combination of two or more thereof, and the aldehyde compound may be used alone or in combination of two or more thereof. The amount of the aldehyde compound used is preferably 0.2 to 5 mol, more preferably 0.5 to 2 mol, relative to 1 mol of the phenol compound.

[0246] A catalyst may also be used in the polycondensation reaction of the phenol compound and the aldehyde. Examples of the catalyst include acidic catalysts such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, camphorsulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid. The amount of these acidic catalysts used is preferably 1×10 -5 ~5×10 -1 Moore.

[0247] As for 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 relative to 100 parts by mass of the raw materials. The reaction temperature can be appropriately selected depending on the reactivity of the raw materials, and is usually in the range of 10 to 200°C.

[0248] In the polycondensation reaction, there are two methods: a method of adding the phenol compound, the aldehyde compound and the catalyst together, and a method of adding the phenol compound and the aldehyde compound dropwise in the presence of the catalyst. After the polycondensation reaction is completed, in order to remove the unreacted raw materials, catalyst, etc. in the system, the temperature of the reactor can be raised to 130 to 230° C. and the volatile components can be removed at about 1 to 50 mmHg.

[0249] The polystyrene-equivalent weight average molecular weight (Mw) of polymer B measured by gel permeation chromatography (GPC) using THF as a solvent is preferably 1,000 to 500,000, and more preferably 1,500 to 30,000. Furthermore, when the molecular weight distribution (Mw / Mn) of polymer B is wide, there are concerns that foreign matter may be visible on the pattern after exposure or the shape of the pattern may deteriorate due to the presence of low-molecular-weight and high-molecular-weight polymers. As the pattern rules become finer, the influence of Mw and Mw / Mn tends to become greater. Therefore, in order to obtain a resist material suitable for a fine pattern size, the Mw / Mn of the above-mentioned polymer B is preferably 1.0 to 5.0, and a narrow dispersion of 1.5 to 3.5 is particularly preferred.

[0250] The polymer B may include two or more polymers having different composition ratios, Mw, and Mw / Mn.

[0251] The material containing the above-mentioned surfactant and used for optical lithography of semiconductors must have low metal impurities. Because if metal impurities exist, the operation of the device manufactured using it will be adversely affected. In order to reduce metal, cleaning with pure water and ion exchange resin can be used. In the case of resist materials, the amount of metal impurities is preferably 100 ppm or less, and more preferably 100 ppb or less.

[0252] The coating material for optical lithography of the present invention contains 0.0001 to 3% by mass of the above-mentioned surfactant. The content of the above-mentioned surfactant is preferably 0.0001 to 2% by mass, and more preferably 0.0002 to 1% by mass.

[0253] The aforementioned coating material for optical lithography can be used as a component of a photosensitive or non-photosensitive resist material, a material for forming a surface coating layer formed on a resist film, a material for forming a resist underlayer film, etc. As the underlayer film material, hydrocarbon-based materials and silicon-containing materials can be cited. As the resist material, it can be any of a chemically amplified resist and a non-chemically amplified resist, a resist composed of a hydrocarbon system, or a metal-based resist containing silicon, titanium, zirconium, hafnium, selenium, germanium, zinc, iron, cobalt, nickel, copper, tin, antimony, molybdenum, tungsten, indium, etc.

[0254] [Resist material]

[0255] The resist material of the present invention is a material containing the aforementioned optical lithography coating material. The resist material of the present invention may also further contain a known surfactant. As for the known surfactant, the ones described in paragraphs

[0165] to

[0166] of Japanese Patent Publication No. 2008-111103 can be cited. In the case where the resist material of the present invention contains a known surfactant, its content is not particularly limited as long as it does not impair the effect of the present invention.

[0256] The resist material of the present invention may further include a base polymer. The base polymer is not particularly limited as long as it can be used in the resist material.

[0257] Specifically, when the base polymer is a positive resist material of a chemically amplified resist, it 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).

[0258] [Chemistry 78]

[0259]

[0260] In formula (a1) and (a2), R B Each is independently a hydrogen atom or a methyl group. 1 Y is a single bond, a phenylene group or a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing at least one selected from an ester bond, an ether bond, and a lactone ring. 2 is a single bond or an ester bond. 3 is a single bond, an ether bond or an ester bond. 11 and R 12 Each independently represents an acid-labile group. When the base polymer comprises both repeating unit a1 and repeating unit a2, R 11 and R 12 , can be the same or different. 13 , is a fluorine atom, a trifluoromethyl group, a cyano group or a saturated hydrocarbon group having 1 to 6 carbon atoms. 14 , is a single bond or an alkanediyl group having 1 to 6 carbon atoms, and a portion of -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 from 0 to 4. However, 1≤a+b≤5.

[0261] Specific examples of the monomer providing the repeating unit a1 include the following, but are not limited thereto. B and R 11 Same as above.

[0262] [Chemistry 79]

[0263]

[0264] Specific examples of monomers providing repeating unit a2 include the following, but are not limited thereto. B and R 12 Same as above.

[0265] [Chemistry 80]

[0266]

[0267] Just R 11 and R 12 Examples of the acid-labile group represented by include those described in JP-A-2013-80033 and JP-A-2013-83821.

[0268] Specific examples of the acid-labile group include those represented by any of the following formulae (AL-1) to (AL-3).

[0269] [Chemistry 81]

[0270]

[0271] In the formula, the dotted lines represent atomic bonds.

[0272] In formula (AL-1) and (AL-2), R L1 and R L2 Each is independently a hydrocarbon group having 1 to 40 carbon atoms, and may also contain heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and fluorine atoms. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be linear, branched, or cyclic. As for the aforementioned hydrocarbon group, a saturated hydrocarbon group having 1 to 40 carbon atoms is preferred, and a saturated hydrocarbon group having 1 to 20 carbon atoms is more preferred.

[0273] In formula (AL-1), c is an integer of 0 to 10, preferably an integer of 1 to 5.

[0274] In formula (AL-2), R L3 and R L4 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may also contain heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and fluorine atoms. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be linear, branched, or cyclic. As for the aforementioned hydrocarbon group, it is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms. In addition, R L2 , R L3 and R L4 Any two of them may be bonded to each other and 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. The aforementioned ring is preferably a ring having 4 to 16 carbon atoms, and is particularly preferably an alicyclic ring.

[0275] In formula (AL-3), R L5 , R L6 and R L7 Each is independently a hydrocarbon group having 1 to 20 carbon atoms, and may also contain heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and fluorine atoms. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be linear, branched, or cyclic. The aforementioned hydrocarbon group is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms. L5 , R L6 and R L7 Any two of the above may be bonded to each other and together with the carbon atoms to which they are bonded form a ring having 3 to 20 carbon atoms. The above ring is preferably a ring having 4 to 16 carbon atoms, and is particularly preferably an alicyclic ring.

[0276] The base polymer may also include a repeating unit b containing a phenolic hydroxyl group as an adhesive group. Specific examples of monomers providing the repeating unit b include the following, but are not limited to these. B Same as above.

[0277] [Chemistry 82]

[0278]

[0279] [Chemistry 83]

[0280]

[0281] [Chemistry 84]

[0282]

[0283] The aforementioned base polymer may also contain a repeating unit c containing a hydroxyl group other than a phenolic hydroxyl group, a lactone ring, a sultone ring, an ether bond, an ester bond, a sulfonate bond, a carbonyl group, a sulfonyl group, a cyano group or a carboxyl group as another adhesive group. Specific examples of monomers providing the repeating unit c include those shown below, but are not limited to these. In the following formula, R B Same as above.

[0284] [Chemistry 85]

[0285]

[0286] [Chemistry 86]

[0287]

[0288] [Chemistry 87]

[0289]

[0290] [Chemistry 88]

[0291]

[0292] [Chemistry 89]

[0293]

[0294] [Chemistry 90]

[0295]

[0296] [Chemistry 91]

[0297]

[0298] [Chemistry 92]

[0299]

[0300] [Chemistry 93]

[0301]

[0302] The base polymer may also include a repeating unit d derived from indene, benzofuran, benzothiophene, acenaphthylene, chromone, coumarin, norbornadiene or a derivative thereof. Specific examples of the monomer providing the repeating unit d include the following, but are not limited thereto.

[0303] [Chemistry 94]

[0304]

[0305] The aforementioned base polymer may also include a repeating unit e derived from styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, methylenedihydroindane, vinylpyridine or vinylcarbazole.

[0306] The aforementioned base polymer may also 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). Furthermore, the repeating units f1 to f3 may be used alone or in combination of two or more.

[0307] [Chemistry 95]

[0308]

[0309] In formulas (f1) to (f3), R B Each is independently a hydrogen atom or a methyl group.1 , is a single bond, an aliphatic alkylene 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 them, or -OZ 11 -、-C(=O)-OZ 11 -or-C(=O)-NH-Z 11 -.Z 11 , is an aliphatic alkylene 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 them, and may also 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 -Z 31 -OC(=O)-. Z 31 , is an aliphatic alkylene group having 1 to 12 carbon atoms, a phenylene group, or a group having 7 to 18 carbon atoms obtained by combining them, and may also contain a carbonyl group, an ester bond, an ether bond, an iodine atom, or a bromine atom. 4 , is methylene, 2,2,2-trifluoro-1,1-ethanediyl or carbonyl. 5 , is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, phenylene substituted with trifluoromethyl, -OZ 51 -、-C(=O)-OZ 51 -or-C(=O)-NH-Z 51 -.Z 51 , is an aliphatic alkylene 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 also contain a carbonyl group, an ester bond, an ether bond, a halogen atom or a hydroxyl group.

[0310] In formulas (f1) to (f3), R 21 ~R 28 Each is independently a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.

[0311] Just R 21 ~R 28 Specific examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0312] R 21 ~R 28The hydrocarbon group represented by may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecanyl, tridecyl, tetradecyl, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, propenyl, butenyl, and hexenyl; Alkynyl groups having 2 to 20 carbon atoms, such as ethynyl, propynyl, and butynyl; cyclic unsaturated aliphatic hydrocarbon groups having 3 to 20 carbon atoms, such as cyclohexenyl and norbornenyl; aryl groups having 6 to 20 carbon atoms, such as phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, sec-butylnaphthyl, and tert-butylnaphthyl; aralkyl groups having 7 to 20 carbon atoms, such as benzyl and phenethyl; and groups obtained by combining these.

[0313] The aforementioned hydrocarbon group may have a part or all of its hydrogen atoms substituted by a group containing a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and a part of its -CH2- may be substituted by a group containing a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. As a result, it may also contain a hydroxyl 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 bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, and the like.

[0314] Again, R 23 and R 24 or R 26 and R 27 , may also be bonded to each other and form a ring together with the sulfur atom to which they are bonded. In this case, the aforementioned ring is preferably a structure shown below.

[0315] [Chemistry 96]

[0316]

[0317] In the formula, the dotted lines represent atomic bonds.

[0318] In formula (f1), M -It is a non-nucleophilic counter ion. Specific examples of the non-nucleophilic counter ions include halogen ions such as chloride ion and bromide ion; fluoroalkyl sulfonate ions such as trifluoromethanesulfonate ion, 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion; aryl sulfonate ions such as toluenesulfonate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkyl sulfonate ions such as methanesulfonate ion and butanesulfonate ion; imide ions such as bis(trifluoromethylsulfonyl)imide ion, bis(perfluoroethylsulfonyl)imide ion and bis(perfluorobutylsulfonyl)imide ion; methide ions such as tris(trifluoromethylsulfonyl)methide ion and tris(perfluoroethylsulfonyl)methide ion.

[0319] As specific examples of the aforementioned non-nucleophilic relative ions, further examples include a sulfonate ion represented by the following formula (f1-1) in which the α-position is substituted with a fluorine atom, 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, and the like.

[0320] [Chemistry 97]

[0321]

[0322] In formula (f1-1), R 31 , is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may also contain at least one selected from an ether bond, an ester bond, a carbonyl group, a lactone ring, and a fluorine atom. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be linear, branched, or cyclic.

[0323] In formula (f1-2), R 32 , is a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon carbonyl group having 6 to 20 carbon atoms. The hydrocarbon group and hydrocarbon carbonyl group may also contain an ether bond, an ester bond, a carbonyl group, or a lactone ring. The hydrocarbon portion of the aforementioned hydrocarbon group and hydrocarbon carbonyl group may be saturated or unsaturated, and may be straight chain, branched, or cyclic.

[0324] Specific examples of the cation of the monomer providing the repeating unit f1 include those shown below, but are not limited to these. B Same as above.

[0325] [Chemistry 98]

[0326]

[0327] The anion of the monomer providing the repeating unit f2 may be exemplified by the following, but is not limited thereto. B Same as above.

[0328] [Chemistry 99]

[0329]

[0330] [Chemical 100]

[0331]

[0332] [Chemistry 101]

[0333]

[0334] [Chemistry 102]

[0335]

[0336] [Chemistry 103]

[0337]

[0338] [Chemistry 104]

[0339]

[0340] [Chemistry 105]

[0341]

[0342] [Chemistry 106]

[0343]

[0344] [Chemistry 107]

[0345]

[0346] [Chemistry 108]

[0347]

[0348] [Chemistry 109]

[0349]

[0350] [Chemistry 110]

[0351]

[0352] [Chemistry 111]

[0353]

[0354] [Chemistry 112]

[0355]

[0356] The anion of the monomer providing the repeating unit f3 may be exemplified by the following, but is not limited thereto. B Same as above.

[0357] [Chemistry 113]

[0358]

[0359] [Chemistry 114]

[0360]

[0361] Specific examples of the cation of the repeating unit f2 or f3 include the same sulfonium salts described in paragraphs 0063 to 0080 and the iodonium salts described in paragraph 0082 of JP-A-2023-3926.

[0362] Repeating units f1 to f3 function as an acid generator. By bonding the acid generator to the polymer main chain, the acid diffusion is reduced, and the resolution reduction caused by blurring due to acid diffusion can be prevented. In addition, by uniformly dispersing the acid generator, LWR and CDU are improved. In addition, when a base polymer containing repeating units f is used, the addition of the additive acid generator described below can be omitted.

[0363] In the case of a negative resist material or a non-chemically amplified resist material, the base polymer does not necessarily need to contain the repeating units a1 and a2.

[0364] As the base polymer, in addition to the above-mentioned polymers, resins such as novolac resin, polyimide, polyamide, polyvinyl pyrrolidone, polyvinyl alcohol, polythiophene, and polyaniline may be used.

[0365] [Organic solvents]

[0366] The coating material and resist material for optical lithography of the present invention may also contain an organic solvent. The aforementioned organic solvent is not particularly limited as long as it can dissolve the aforementioned components and the components described below. Specific examples of the aforementioned organic solvent include ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentanone, and 2-heptanone described in paragraphs

[0144] to

[0145] of Japanese Patent Gazette No. 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 monomethyl ether, propylene ... Ethers such as alcohol dimethyl ether, diethylene glycol dimethyl ether, and anisole; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, 3-methoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; lactones such as γ-butyrolactone; lactams such as pyrrolone, N-methylpyrrolone, N-ethylpyrrolone, and N-hydroxyethyl-2-pyrrolone; water; dimethyl sulfoxide, etc.

[0367] 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.

[0368] The anti-etching material of the present invention may also contain an additive acid generator. As for the aforementioned additive acid generator, sulfonium salts or iodonium salts described in paragraphs

[0122] to

[0142] of Japanese Patent Gazette No. 2008-111103 and paragraphs

[0077] to

[0148] of Japanese Patent Gazette No. 2023-62677, sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate can be listed. When the anti-etching material of the present invention contains the aforementioned additive acid generator, its content is preferably 0.1 to 50 parts by mass, and more preferably 1 to 40 parts by mass, relative to 100 parts by mass of the base polymer. The aforementioned additive acid generator may be used alone or in combination of two or more.

[0369] The resist material of the present invention may also contain a quencher. The quencher refers to a compound that can prevent diffusion to the unexposed portion by capturing the acid generated by the acid generator in the resist material.

[0370] As for the above-mentioned quencher, known basic compounds can be cited. As for the known basic compounds, primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having carboxyl groups, nitrogen-containing compounds having sulfonyl groups, nitrogen-containing compounds having hydroxyl groups, nitrogen-containing compounds having hydroxyphenyl groups, alcoholic nitrogen-containing compounds, amides, imides, and carbamates can be cited. In particular, primary, secondary, and tertiary amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Publication No. 2008-111103 are particularly preferably amine compounds having hydroxyl groups, ether bonds, ester bonds, lactone rings, cyano groups, and sulfonate bonds, or compounds having carbamate groups described in Japanese Patent Publication No. 3790649. By adding such basic compounds, for example, the diffusion rate of acid in the resist film can be further suppressed, or the shape can be corrected.

[0371] In addition, as for the above-mentioned quencher, onium salts such as sulfonium salts, iodonium salts, and ammonium salts of sulfonic acids and carboxylic acids not fluorinated at the α-position described in Japanese Patent Application Laid-Open No. 2008-158339 can be cited. In order to deprotect the acid-labile group of the carboxylate, a sulfonic acid, imidic acid, or methide acid that is fluorinated at the α-position is required, but by salt exchange with an onium salt that is not fluorinated at the α-position, the sulfonic acid or carboxylic acid that is not fluorinated at the α-position is released. The sulfonic acid and carboxylic acid that are not fluorinated at the α-position do not undergo a deprotection reaction, and thus function as a quencher.

[0372] As for the aforementioned quencher, a polymer type quencher described in Japanese Patent Application Publication No. 2008-239918 can be further cited. This improves the rectangularity of the resist pattern by orienting the surface of the resist film. The polymer type quencher also has the effect of preventing film loss and doming of the pattern when applied to a protective film for wet exposure.

[0373] When the resist material 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, relative to 100 parts by mass of the base polymer. The quencher may be used alone or in combination of two or more.

[0374] When the resist material of the present invention is a negative resist, it may also contain a crosslinking agent. By mixing a crosslinking agent, the difference in dissolution rate between the exposed portion and the unexposed portion can be further enlarged, but there is also a risk of increased swelling in the developer. As specific examples of crosslinking agents, those described in paragraphs

[0170] to

[0177] of Japanese Patent Publication No. 2020-027297 can be cited. When the resist material of the present invention contains the aforementioned crosslinking agent, its content is preferably 0 to 30 parts by mass relative to 100 parts by mass of the base polymer, and 0 to 20 parts by mass is more preferred.

[0375] The coating material and resist material for optical lithography of the present invention may also include a water repellency enhancer for enhancing the water repellency of the resist film surface. The aforementioned water repellency enhancer can be used for immersion lithography without using a surface coating. As for the aforementioned water repellency enhancer, it is preferably 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 ones exemplified by Japanese Patent Publication No. 2007-297590 and Japanese Patent Publication No. 2008-111103 are better. The aforementioned water repellency enhancer needs to be dissolved in an alkaline developer or an organic solvent developer. The aforementioned water repellency enhancer having a specific 1,1,1,3,3,3-hexafluoro-2-propanol residue has good solubility in a developer. As for the water repellency enhancer, the polymer containing repeating units containing amino groups and ammonium salts has a high effect of preventing the evaporation of the acid in the post-exposure bake (PEB) and preventing the poor opening of the hole pattern after development. When the optical lithography coating material or resist material of the present invention contains the aforementioned water repellency enhancer, its content is preferably 0 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the base polymer. The aforementioned water repellency enhancer can be used alone or in combination of two or more.

[0376] The surfactant contained in the optical lithography coating material of the present invention can also be used as the aforementioned water repellency enhancing material. In this case, in addition to the surfactant having a high water repellency enhancing function, a surfactant having a high surface active effect can also be combined.

[0377] The resist material of the present invention may also contain acetylene alcohols. Specific examples of the acetylene alcohols include those described in paragraphs

[0179] to

[0182] of Japanese Patent Application Laid-Open No. 2008-122932. When the resist material of the present invention contains the acetylene alcohols, the content thereof 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.

[0378] [Pattern Formation Method]

[0379] When the resist material of the present invention is used in the manufacture of various integrated circuits, known photolithography techniques can be used. For example, as for the pattern forming method, a method comprising the following steps can be cited: using the resist material to form a resist film on a substrate, exposing the resist film to high-energy rays, and developing the exposed resist film using a developer.

[0380] First, the resist material of the present invention is applied to a substrate (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective film, etc.) for integrated circuit manufacturing or a substrate (Cr, CrO, CrON, CrN, MoSi2, SiO2, Ta, MoSi laminated film, Ru, Ni, Co, W, Mo, V and their alloys, etc.) for mask circuit manufacturing by appropriate coating methods such as spin coating, roller coating, flow coating, dip coating, spray coating, scraping coating, etc. It is placed on a hot plate, preferably at 60-150° C., 10 seconds to 30 minutes, more preferably at 80-150° C., 30 seconds to 20 minutes pre-baking to form a resist film.

[0381] Before applying the resist material of the present invention, the substrate may be treated by irradiating light, EB, plasma, etc., or by CVD, ozone, hexamethyldisilazane (HMDS), etc.

[0382] The thickness of the resist film is preferably 1 nm to 200 μm, more preferably 2 nm to 100 μm.

[0383] A protective film may also be formed on the resist film. The protective film preferably has functions such as environmental protection, light absorption, antistatic, resist pattern defect reduction, and resist pattern shape correction.

[0384] Then, the resist film is exposed using high-energy radiation. Specific examples of the high-energy radiation include ultraviolet rays, far ultraviolet rays, EB, EUV with a wavelength of 3 to 15 nm, X-rays, soft X-rays, excimer lasers, gamma rays, synchrotron radiation, etc. When using ultraviolet rays, far ultraviolet rays, EUV, X-rays, soft X-rays, excimer lasers, gamma rays, synchrotron radiation, etc. as the high-energy radiation, irradiation is performed directly or using a mask for forming a target pattern, so that the exposure amount is about 1 to 200 mJ / cm 2 Preferably, more preferably about 10 to 100 mJ / cm 2 When EB is used as high energy ray, the exposure amount is preferably about 0.1 to 1000 μC / cm 2 , preferably about 0.5 to 900 μC / cm 2 The resist material of the present invention is particularly suitable for fine patterning by g-rays, i-rays, KrF excimer lasers, ArF excimer lasers, EB, EUV, X-rays, soft X-rays, gamma-rays, and synchrotron radiation among high-energy rays.

[0385] 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.

[0386] After exposure or PEB, a developer is used to develop the target pattern on the substrate by a common method such as dipping, puddle, or spraying for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes.

[0387] The developer may be an organic solvent developer or an alkaline aqueous solution 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, methyl acetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butyl acetate, isoamyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, and ethyl propionate. , ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenyl acetate, benzyl formate, phenyl ethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenyl acetate, 2-phenylethyl acetate, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, xylene, toluene, anisole, methanol, ethanol, isopropanol, n-butanol, isobutanol, acetic anhydride, acetic acid, etc. Specific examples of the alkaline aqueous developer include aqueous solutions of potassium hydroxide, sodium hydroxide, etc., alkaline aqueous solutions of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, etc. The developer may be used alone or in combination of two or more.

[0388] When the development is finished, rinsing is performed. As for the rinsing liquid, a solvent that is miscible with the developer and does not dissolve the resist film is preferred. As for 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.

[0389] Specific examples of the alcohol having 3 to 10 carbon atoms include n-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, tert-pentanol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 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, 1-octanol, etc.

[0390] 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-amyl ether, diisoamyl ether, di-sec-amyl ether, di-tert-amyl ether, and di-n-hexyl ether.

[0391] Specific examples of the aforementioned 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 aforementioned alkenes having 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, cyclooctene, etc. Specific examples of the aforementioned alkynes having 6 to 12 carbon atoms include hexyne, heptyne, octyne, etc.

[0392] Examples of the aromatic solvent include toluene, xylene, ethylbenzene, cumene, tert-butylbenzene, and mesitylene.

[0393] By performing rinsing, the occurrence of collapse and defects of the resist pattern can be reduced. In addition, rinsing is not essential, and the amount of solvent used can be reduced by not performing rinsing.

[0394] The developed hole pattern and groove pattern can also be shrunk by heat flow, RELACS technology or DSA technology. A shrinking agent is coated on the hole pattern. Due to the diffusion of the acid catalyst from the resist film during baking, the shrinking agent cross-links on the surface of the resist film, and the shrinking agent adheres to the side wall 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 to remove the excess shrinking agent and shrink the hole pattern.

[0395] [Example]

[0396] Hereinafter, the present invention will be specifically described with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

[0397] [1] Synthesis of surfactant polymers

[0398] The monomers Sa-1 to Sa-33 and monomers Sb-1 to Sb-5 used in the synthesis of the surfactant polymer are as follows: The Mw of the polymer is a polystyrene-equivalent value measured by GPC using THF as a solvent.

[0399] [Chemistry 115]

[0400]

[0401] [Chemistry 116]

[0402]

[0403] [Chemistry 117]

[0404]

[0405] [Chemistry 118]

[0406]

[0407] [Chemistry 119]

[0408]

[0409] [Chemistry 120]

[0410]

[0411] [Synthesis Example 1] Synthesis of Polymer SP-1

[0412] Under a nitrogen environment, 0.42 g of 2-cyano-2-propylbenzodisulfate and 0.10 g of 2,2'-azobisisobutyronitrile (AIBN) were dissolved in 37.5 g of methanol, and the obtained solution was stirred at 64°C for 3 hours under a nitrogen environment. A solution of 9.5 g of monomer Sa-1 dissolved in 32.2 g of methanol was added dropwise to the solution over a period of 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 a period of 2 hours. After the addition was completed, the mixture was stirred at 64°C for 4 hours. After cooling to room temperature, 1000 g of hexane was added dropwise while stirring vigorously. The resulting solid was filtered and dried in vacuo at 50°C for 15 hours to obtain a red solid polymer SP-1 as a diblock copolymer. 19 F-NMR and 1 The composition of the polymer SP-1 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0413] [Chemistry 121]

[0414]

[0415] [Synthesis Example 2] Synthesis of Polymer SP-2

[0416] Under nitrogen, 0.42 g of 2-cyano-2-propylbenzodisulfate and 0.10 g of AIBN were dissolved in 37.5 g of methanol, and the solution was stirred at 64°C for 3 hours under nitrogen. 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. 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, and after the addition was completed, the mixture was stirred at 64°C for 4 hours. Thereafter, 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 addition was completed, the mixture was stirred at 64°C for 4 hours. After cooling to room temperature, 1000 g of hexane was added dropwise while stirring vigorously. The generated solid was filtered and vacuum dried at 50°C for 15 hours to obtain a red solid polymer SP-2 as a triblock copolymer in which monomer Sb-1 was polymerized in the center and monomer Sa-1 was polymerized on both sides. 19 F-NMR and 1 The composition of the polymer SP-2 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0417] [Chemistry 122]

[0418]

[0419] [Synthesis Example 3] Synthesis of Polymer SP-3

[0420] Add 11.2g of monomer Sa-2, 28.9g of monomer Sb-2, and 60g of THF as solvent to the reaction container. Cool the reaction container to -70°C under nitrogen environment, and repeat degassing under reduced pressure and nitrogen purging 3 times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-3 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-3 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0421] [Chemistry 123]

[0422]

[0423] [Synthesis Example 4] Synthesis of Polymer SP-4

[0424] Add 12.4g of monomer Sa-3, 28.9g of monomer Sb-2, and 60g of THF as solvent to the reaction container. Cool the reaction container to -70°C under nitrogen, and repeat degassing under reduced pressure and nitrogen purging three times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-4 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-4 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0425] [Chemistry 124]

[0426]

[0427] [Synthesis Example 5] Synthesis of Polymer SP-5

[0428] Add 10.0g of monomer Sa-4, 28.9g of monomer Sb-2, and 60g of THF as solvent to the reaction container. Cool the reaction container to -70°C under nitrogen, and repeat degassing under reduced pressure and nitrogen purging three times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-5 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-5 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0429] [Chemistry 125]

[0430]

[0431] [Synthesis Example 6] Synthesis of Polymer SP-6

[0432] Add 23.1g of monomer Sa-5, 39.5g of monomer Sb-3, and 100g of THF as solvent to the reaction container. Cool the reaction container to -70°C under nitrogen, and repeat degassing under reduced pressure and nitrogen purging three times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-6 as a random copolymer.19 F-NMR and 1 The composition of the polymer SP-6 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0433] [Chemistry 126]

[0434]

[0435] [Synthesis Example 7] Synthesis of Polymer SP-7

[0436] 13.8 g of monomer Sa-6, 42.8 g of monomer Sb-3, and 100 g of THF as solvent were added to the reaction container. The reaction container was cooled to -70°C under nitrogen, and degassing under reduced pressure and nitrogen purging were repeated three times. After warming to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and the reaction was carried out for 15 hours. The reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-7 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-7 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0437] [Chemistry 127]

[0438]

[0439] [Synthesis Example 8] Synthesis of Polymer SP-8

[0440] Add 9.8g of monomer Sa-7, 21.0g of monomer Sb-4, and 60g of THF as solvent to the reaction container. Cool the reaction container to -70°C under nitrogen environment, and repeat degassing under reduced pressure and nitrogen purging 3 times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-8 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-8 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0441] [Chemistry 128]

[0442]

[0443] [Synthesis Example 9] Synthesis of Polymer SP-9

[0444] 13.6 g of monomer Sa-8, 21.0 g of monomer Sb-4, and 60 g of THF as a solvent were added to the reaction container. The reaction container was cooled to -70°C under a nitrogen environment, and the reduced pressure degassing and nitrogen purging were repeated 3 times. After warming to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and the reaction was carried out for 15 hours. The reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-9 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-9 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0445] [Chemistry 129]

[0446]

[0447] [Synthesis Example 10] Synthesis of Polymer SP-10

[0448] 13.6 g of monomer Sa-9, 28.9 g of monomer Sb-2, and 60 g of THF as a solvent were added to the reaction container. The reaction container was cooled to -70°C under a nitrogen environment, and the reduced pressure degassing and nitrogen purging were repeated 3 times. After warming to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and the reaction was carried out for 15 hours. The reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-10 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-10 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0449] [Chemistry 130]

[0450]

[0451] [Synthesis Example 11] Synthesis of Polymer SP-11

[0452] 11.0 g of monomer Sa-10, 28.9 g of monomer Sb-2, and 60 g of THF as a solvent were added to the reaction container. The reaction container was cooled to -70°C under a nitrogen environment, and the reduced pressure degassing and nitrogen purging were repeated 3 times. After warming to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and the reaction was carried out for 15 hours. The reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-11 as a random copolymer. 19 F-NMR and1 The composition of the polymer SP-11 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0453] [Chemistry 131]

[0454]

[0455] [Synthesis Example 12] Synthesis of Polymer SP-12

[0456] 11.0 g of monomer Sa-11, 28.9 g of monomer Sb-2, and 60 g of THF as a solvent were added to the reaction container. The reaction container was cooled to -70°C under a nitrogen environment, and the reduced pressure degassing and nitrogen purging were repeated 3 times. After warming to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and the reaction was carried out for 15 hours. The reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-12 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-12 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0457] [Chemistry 132]

[0458]

[0459] [Synthesis Example 13] Synthesis of Polymer SP-13

[0460] 19.8 g of monomer Sa-12, 42.8 g of monomer Sb-3, and 100 g of THF as a solvent were added to a reaction vessel. The reaction vessel was cooled to -70°C under a nitrogen environment, and degassing under reduced pressure and nitrogen purging were repeated three times. After warming to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and the reaction was carried out for 15 hours. The reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-13 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-13 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0461] [Chemistry 133]

[0462]

[0463] [Synthesis Example 14] Synthesis of Polymer SP-14

[0464] Add 12.8g of monomer Sa-13, 28.9g of monomer Sb-2, and 60g of THF as solvent to the reaction container. Cool the reaction container to -70°C under nitrogen environment, and repeat degassing under reduced pressure and nitrogen purging 3 times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-14 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-14 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0465] [Chemistry 134]

[0466]

[0467] [Synthesis Example 15] Synthesis of Polymer SP-15

[0468] Add 11.6g of monomer Sa-14, 28.9g of monomer Sb-2, and 60g of THF as solvent to the reaction container. Cool the reaction container to -70°C under nitrogen environment, and repeat the reduced pressure degassing and nitrogen purging 3 times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-15 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-15 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0469] [Chemistry 135]

[0470]

[0471] [Synthesis Example 16] Synthesis of Polymer SP-16

[0472] 33.2 g of monomer Sa-15 and 80 g of THF as solvent were added to the reaction container. The reaction container was cooled to -70°C under nitrogen atmosphere, and degassing under reduced pressure and nitrogen purging were repeated 3 times. After warming to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and the reaction was carried out for 15 hours. The reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-16. 19 F-NMR and 1The composition of the polymer SP-16 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0473] [Chemistry 136]

[0474]

[0475] [Synthesis Example 17] Synthesis of Polymer SP-17

[0476] 34.8 g of monomer Sa-16 and 80 g of THF as solvent were added to the reaction container. The reaction container was cooled to -70°C under nitrogen atmosphere, and degassing under reduced pressure and nitrogen purging were repeated 3 times. After warming to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and the reaction was carried out for 15 hours. The reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-17. 19 F-NMR and 1 The composition of the polymer SP-17 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0477] [Chemistry 137]

[0478]

[0479] [Synthesis Example 18] Synthesis of Polymer SP-18

[0480] 17.0 g of monomer Sa-17, 10.9 g of monomer Sb-1, and 80 g of THF as a solvent were added to the reaction container. The reaction container was cooled to -70°C under a nitrogen environment, and the reduced pressure degassing and nitrogen purging were repeated 3 times. After warming to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and the reaction was carried out for 15 hours. The reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-18 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-18 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0481] [Chemistry 138]

[0482]

[0483] [Synthesis Example 19] Synthesis of Polymer SP-19

[0484] 19.4 g of monomer Sa-18, 10.9 g of monomer Sb-1, and 80 g of THF as a solvent were added to the reaction container. The reaction container was cooled to -70°C under a nitrogen environment, and the reduced pressure degassing and nitrogen purging were repeated 3 times. After warming to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and the reaction was carried out for 15 hours. The reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-19 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-19 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0485] [Chemistry 139]

[0486]

[0487] [Synthesis Example 20] Synthesis of Polymer SP-20

[0488] Add 24.3g of monomer Sa-9, 4.0g of monomer Sa-20, and 60g of THF as solvent to the reaction container. Cool the reaction container to -70°C under nitrogen environment, and repeat degassing under reduced pressure and nitrogen purging 3 times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-20 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-20 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0489] [Chemistry 140]

[0490]

[0491] [Synthesis Example 21] Synthesis of Polymer SP-21

[0492] Add 24.3g of monomer Sa-9, 7.3g of monomer Sa-21, and 60g of THF as solvent to the reaction container. Cool the reaction container to -70°C under nitrogen environment, and repeat degassing under reduced pressure and nitrogen purging 3 times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-21 as a random copolymer. 19F-NMR and 1 The composition of the polymer SP-21 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0493] [Chemistry 141]

[0494]

[0495] [Synthesis Example 22] Synthesis of Polymer SP-22

[0496] Add 24.3g of monomer Sa-9, 4.4g of monomer Sa-22, and 60g of THF as solvent to the reaction container. Cool the reaction container to -70°C under nitrogen environment, repeat degassing under reduced pressure and nitrogen purging 3 times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-22 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-22 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0497] [Chemistry 142]

[0498]

[0499] [Synthesis Example 23] Synthesis of Polymer SP-23

[0500] Add 35.5g of monomer Sa-23, 19.1g of monomer Sa-24, and 60g of THF as solvent to the reaction container. Cool the reaction container to -70°C under nitrogen environment, and repeat degassing under reduced pressure and nitrogen purging 3 times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-23 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-23 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0501] [Chemistry 143]

[0502]

[0503] [Synthesis Example 24] Synthesis of Polymer SP-24

[0504] Add 24.3g of monomer Sa-9, 10.3g of monomer Sa-25, and 60g of THF as solvent to the reaction container. Cool the reaction container to -70°C under nitrogen environment, and repeat the reduced pressure degassing and nitrogen purging 3 times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-24 as a random copolymer. 19 F-NMR and 1 The composition of polymer SP-24 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0505] [Chemistry 144]

[0506]

[0507] [Synthesis Example 25] Synthesis of Polymer SP-25

[0508] Add 24.3g of monomer Sa-9, 9.8g of monomer Sa-26, and 60g of THF as a solvent to a reaction container. Cool the reaction container to -70°C under a nitrogen environment, and repeat the reduced pressure degassing and nitrogen purging three times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-25 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-25 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0509] [Chemistry 145]

[0510]

[0511] [Synthesis Example 26] Synthesis of Polymer SP-26

[0512] 17.8 g of p-trifluoromethoxyphenol, 90 g of 37 mass % formalin aqueous solution and 5 g of oxalic acid were added to a reaction container, 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 sufficient water washing, and the solvent was removed under reduced pressure. At 150°C, the pressure was reduced to 2 mmHg to remove water and unreacted monomers, and polymer SP-26 was obtained. 19 F-NMR and 1The composition of polymer SP-26 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0513] [Chemistry 146]

[0514]

[0515] [Synthesis Example 27] Synthesis of Polymer SP-27

[0516] 17.8 g of p-trifluoromethoxyphenol, 20 g of 3-trifluoromethoxybenzaldehyde and 5 g of oxalic acid were added to a reaction container, 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 sufficient water washing. The solvent was removed under reduced pressure, and the pressure was reduced to 2 mmHg at 150°C to remove water and unreacted monomers, thereby obtaining polymer SP-27. 19 F-NMR and 1 The composition of the polymer SP-27 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0517] [Chemistry 147]

[0518]

[0519] [Synthesis Example 28] Synthesis of Polymer SP-28

[0520] 35.0 g of 9,9-bis(4-hydroxyphenyl)fluorene monotrifluoromethoxybenzyl alcohol, 20 g of 4-trifluoromethoxybenzaldehyde and 5 g of oxalic acid were added to the reaction container, 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 sufficient water washing, and the solvent was removed under reduced pressure. Then, the mixture was heated to 150°C and the pressure was reduced to 2 mmHg to remove water and unreacted monomers, and polymer SP-28 was obtained. 19 F-NMR and 1 The composition of polymer SP-28 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0521] [Chemistry 148]

[0522]

[0523] [Synthesis Example 29] Synthesis of Polymer SP-29

[0524] 45.0 g of 9,9-bis(6-hydroxynaphthyl)fluorene monotrifluoromethoxybenzyl alcohol, 20 g of 4-trifluoromethoxybenzaldehyde and 5 g of oxalic acid were added to the 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, the catalyst and metal impurities were removed by sufficient water washing, and the solvent was removed under reduced pressure. Then, the mixture was heated to 150°C and the pressure was reduced to 2 mmHg to remove water and unreacted monomers, and polymer SP-29 was obtained. 19 F-NMR and 1 The composition of polymer SP-29 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0525] [Chemistry 149]

[0526]

[0527] [Synthesis Example 30] Synthesis of Polymer SP-30

[0528] 44.0 g of 1,1,1-tris(4-hydroxyphenyl)ethane monotrifluoromethoxybenzyl alcohol, 20 g of 4-trifluoromethoxybenzaldehyde and 5 g of oxalic acid were added to the 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, the catalyst and metal impurities were removed by sufficient water washing, and the solvent was removed under reduced pressure. Then, the mixture was heated to 150°C and the pressure was reduced to 2 mmHg to remove water and unreacted monomers, and polymer SP-30 was obtained. 19 F-NMR and 1 The composition of the polymer SP-30 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0529] [Chemistry 150]

[0530]

[0531] [Synthesis Example 31] Synthesis of Polymer SP-31

[0532] 38.0 g of 2,7-dihydroxynaphthyl monotrifluoromethoxybenzyl alcohol, 20 g of 4-trifluoromethoxybenzaldehyde and 5 g of oxalic acid were added to the 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 sufficient water washing, and the solvent was removed under reduced pressure. Then, the mixture was heated to 150°C and the pressure was reduced to 2 mmHg to remove water and unreacted monomers, and polymer SP-31 was obtained. 19 F-NMR and 1 The composition of the polymer SP-31 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0533] [Chemistry 151]

[0534]

[0535] [Synthesis Example 32] Synthesis of Polymer SP-32

[0536] 14.7 g of monomer Sa-27, 2.3 g of hydroxyethyl acrylate, and 20 g of THF as a solvent were added to the reaction container. The reaction container was cooled to -70°C under a nitrogen environment, and the vacuum degassing and nitrogen purging were repeated 3 times. After warming to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and the reaction was carried out for 15 hours. The reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain the polymer SP-32 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-32 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0537] [Chemistry 152]

[0538]

[0539] [Synthesis Example 33] Synthesis of Polymer SP-33

[0540] 29.5 g of monomer Sa-28, 2.2 g of mono(2-acryloyloxyethyl) succinate, and 50 g of THF as a solvent were added to a reaction vessel. The reaction vessel was cooled to -70°C under a nitrogen environment, and degassing under reduced pressure and nitrogen purging were repeated three times. After warming to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and the reaction was allowed to proceed for 15 hours. The reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-33 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-33 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0541] [Chemistry 153]

[0542]

[0543] [Synthesis Example 34] Synthesis of Polymer SP-34

[0544] 15.2 g of monomer Sa-29, 5.8 g of monomer Sb-5, and 20 g of 1,2-dichloroethane were added to the reaction container as a solvent. 0.2 g of boron trifluoride was added to the reaction container as a polymerization initiator under a nitrogen atmosphere, and the temperature was raised to 60°C and the reaction was carried out 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 obtained white solid was filtered and dried under reduced pressure at 60°C to obtain polymer SP-34 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-34 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0545] [Chemistry 154]

[0546]

[0547] [Synthesis Example 35] Synthesis of Polymer SP-35

[0548] 14.9 g of monomer Sa-30, 5.8 g of monomer Sb-5, and 20 g of 1,2-dichloroethane as a solvent were added to the reaction container. 0.2 g of boron trifluoride was added to the reaction container under a nitrogen atmosphere as a polymerization initiator, and the temperature was raised to 60°C and the reaction was allowed to proceed 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 obtained white solid was filtered and dried under reduced pressure at 60°C to obtain polymer SP-35 as a random copolymer. 19 F-NMR and 1 The composition of the polymer SP-35 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0549] [Chemistry 155]

[0550]

[0551] [Synthesis Example 36] Synthesis of Polymer SP-36

[0552] Add 38.1g of monomer Sa-31 and 60g of THF as solvent to the reaction container. Cool the reaction container to -70°C under nitrogen, repeat degassing under reduced pressure and nitrogen purging three times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-36. 19 F-NMR and 1The composition of polymer SP-36 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0553] [Chemistry 156]

[0554]

[0555] [Synthesis Example 37] Synthesis of Polymer SP-37

[0556] 38.7 g of monomer Sa-32 and 60 g of THF as solvent were added to the reaction vessel. The reaction vessel was cooled to -70°C under nitrogen atmosphere, and degassing under reduced pressure and nitrogen purging were repeated 3 times. After warming to room temperature, 0.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60°C and the reaction was carried out for 15 hours. The reaction solution was added to 1 L of hexane, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer SP-37. 19 F-NMR and 1 The composition of the polymer SP-37 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0557] [Chemistry 157]

[0558]

[0559] [Synthesis Example 38] Synthesis of Polymer SP-38

[0560] By glycidylating polymer SP-27 and then reacting it with trifluoromethoxybenzoic acid, polymer SP-38 was obtained. 19 F-NMR and 1 The composition of polymer SP-38 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0561] [Chemistry 158]

[0562]

[0563] [Synthesis Example 39] Synthesis of Polymer SP-39

[0564] Add 29.4g of monomer Sa-33 and 80g of THF as solvent to the reaction container. Cool the reaction container to -70°C under nitrogen atmosphere, repeat degassing under reduced pressure and nitrogen purging 3 times. After warming to room temperature, add 0.1g of AIBN as a polymerization initiator, and heat to 60°C and react for 15 hours. Add the reaction solution to 1L of hexane, and filter the precipitated white solid. Dry the obtained white solid under reduced pressure at 60°C to obtain polymer SP-39. 19 F-NMR and1 The composition of polymer SP-39 was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC.

[0565] [Chemistry 159]

[0566]

[0567] [Synthesis Examples 40 to 44] Synthesis of Base Polymers (Polymers P-1 to P-5)

[0568] Various monomers were combined and copolymerized in THF as a solvent, which was 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. 1 The composition of the obtained base polymer was confirmed by H-NMR, and Mw and Mw / Mn were confirmed by GPC (solvent: THF, standard substance: polystyrene).

[0569] [Chemistry 160]

[0570]

[0571] In Table 1, the components are as follows.

[0572] Organic solvent: PGMEA (propylene glycol monomethyl ether acetate) DAA (diacetone alcohol)

[0573] EL(ethyl lactate)

[0574] Acid generator (PAG-1), quencher (Q-1)

[0575] [Chemistry 161]

[0576]

[0577] [Examples 1 to 40, Comparative Example 1]

[0578] A solution in which each component was dissolved in the composition shown in Tables 1 and 2 was filtered through a polyethylene filter having a pore size of 3 nm to prepare a resist material.

[0579] Each resist material described in Tables 1 and 2 was provided on a silicon substrate with a diameter of 300 mm and then spin-coated. It was pre-baked at 110°C for 30 seconds on a hot plate to form a resist film with a thickness of 60 nm. The film thickness of the resist film was measured at 225 concentric points on the wafer surface using an optical film thickness meter to obtain the difference between the maximum and minimum film thicknesses. The results are recorded in Tables 1 and 2. In addition, Examples 1 to 39 and Comparative Example 1 are positive resist materials, and Example 40 is a negative resist material.

[0580] [Table 1]

[0581]

[0582]

[0583] [Table 2]

[0584]

[0585]

[0586] From the results shown in Tables 1 and 2, it can be seen that the film thickness of the resist film obtained by the resist material of the present invention comprising a surfactant 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, a base polymer and an organic solvent is uniform.

Claims

1. A coating material for optical lithography, comprising 0.0001 to 3% by mass of a surfactant 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.

2. The coating material for optical lithography according to claim 1, wherein The resin is a polymer including 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 optical lithography according to claim 2, wherein The repeating unit Sa is represented by any of the following formulae (Sa1) to (Sa5), In the formula, m is each independently an integer of 1 to 5, n is each independently an integer of 0 to 4, p is each 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, but 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, When p is 1, X 2 Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and when p is 2 or 3, X 2 Each is independently a (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms, and the alkylene 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 is independently a single bond, an ester bond, an ether bond, an amide bond, a sulfonate bond, a carbamate bond, a thiolcarbamate bond, a urea bond or -S(=O)-N(X 31 )-,X 31 is a hydrogen atom or a saturated hydrocarbon 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 is a single bond or an alkylene group having 1 to 12 carbon atoms, and the alkylene group may have at least one selected from a hydroxyl group, a saturated alkyloxy 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 hydrocarbon group having 1 to 6 carbon atoms, a hydrocarbonoxy group having 1 to 12 carbon atoms, a hydrocarbonoxycarbonyl group having 2 to 6 carbon atoms, a hydrocarboncarbonyloxy group having 2 to 12 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group, R 3 are each independently trifluoromethyl or difluoromethyl, R 4 each independently represents a hydrocarbon group having 1 to 6 carbon atoms, a hydrocarbonoxy group having 1 to 12 carbon atoms, a hydrocarbonoxycarbonyl group having 2 to 6 carbon atoms, a hydrocarboncarbonyloxy group having 2 to 12 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group, Circle R 5 Each is independently a (q+r+2)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms, Circle R 6 is a (s+1)-valent group derived from benzene or naphthalene, R 7 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, which may also contain an oxygen atom. 7 Does not have -X 5 -X 4 -R 3 Represents the group.

4. The coating material for optical lithography according to claim 3, wherein X 1 and X 2 At least one of them is not a single bond. 5 . The coating material for optical lithography according to claim 3 , which is a polymer comprising a repeating unit represented by formula (Sa1) and a repeating unit represented by formula (Sa2).

6. The coating material for optical lithography according to claim 2, wherein The polymer further comprises a repeating unit Sb having a hydrophilic group selected from ether bond, ester bond, hydroxyl group, carboxyl group, sulfonamide bond, sulfonimide bond and sulfonic acid group.

7. The coating material for optical lithography according to claim 6, wherein The polymer is a block copolymer. 8 . A resist material comprising the coating material for optical lithography according to claim 1 . 9 . The resist material according to claim 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 according to claim 8 or 9, exposing the resist film to high-energy rays, and developing the exposed resist film using a developer.

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

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