WO2025192513A1 - Composition pour former un film de sous-couche de réserve - Google Patents

Composition pour former un film de sous-couche de réserve

Info

Publication number
WO2025192513A1
WO2025192513A1 PCT/JP2025/008752 JP2025008752W WO2025192513A1 WO 2025192513 A1 WO2025192513 A1 WO 2025192513A1 JP 2025008752 W JP2025008752 W JP 2025008752W WO 2025192513 A1 WO2025192513 A1 WO 2025192513A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
underlayer film
resist underlayer
forming
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/008752
Other languages
English (en)
Japanese (ja)
Inventor
裕斗 緒方
祐希 加藤
康平 板岡
護 田村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Publication of WO2025192513A1 publication Critical patent/WO2025192513A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to a composition for forming a resist underlayer film, a resist underlayer film, a laminate, a method for manufacturing a semiconductor device, and a pattern formation method.
  • microfabrication using lithography with a resist composition has traditionally been performed.
  • This microfabrication process involves forming a thin film of photoresist composition on a semiconductor substrate, such as a silicon wafer, exposing it to actinic rays such as ultraviolet light through a mask pattern bearing a device pattern, developing the film, and then etching the substrate using the resulting photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the photoresist pattern.
  • a resist underlayer film-forming composition which contains a reaction product of a compound (A) represented by formula (1) (in formula (1), A represents an organic group containing an aliphatic ring, an aromatic ring, or a heterocyclic ring) dissolved in a solvent, a compound (B) having two functional groups reactive with epoxy groups, and a compound (C) having one functional group reactive with epoxy groups (see Patent Document 1).
  • the properties required for the resist underlayer film include, for example, not causing intermixing with the resist film formed on the upper layer (being insoluble in a resist solvent), and being able to form a good resist pattern by improving the sensitivity and adhesion of the resist pattern.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for forming a resist underlayer film that can improve sensitivity and adhesion to form a good resist pattern, as well as methods for producing a resist underlayer film, a laminate, and a semiconductor element, and a pattern forming method, all of which use the composition for forming a resist underlayer film.
  • a composition for forming a resist underlayer film comprising: a resin (A) having a polymerizable multiple bond and a carboxy group; and a solvent (B).
  • the resin (A) is a resin having a structural unit having a polymerizable multiple bond and a carboxy group, or a resin having a structural unit having a polymerizable multiple bond and a structural unit having a carboxy group.
  • L 11 represents a linking group.
  • L 12 represents the divalent group having a carboxy group.
  • L 13 represents the monovalent group having a polymerizable multiple bond.
  • composition for forming a resist underlayer film according to any one of [1] to [8], wherein the solvent (B) contains at least one selected from the group consisting of a carboxylic acid having a hydroxy group, a linear or cyclic alkyl ketone, a cyclic lactone, an alkylene glycol monoalkyl ether, a monocarboxylic acid ester of an alkylene glycol monoalkyl ether, and an alkoxycarboxylic acid ester of an alkylene glycol monoalkyl ether.
  • the solvent (B) contains at least one selected from the group consisting of a carboxylic acid having a hydroxy group, a linear or cyclic alkyl ketone, a cyclic lactone, an alkylene glycol monoalkyl ether, a monocarboxylic acid ester of an alkylene glycol monoalkyl ether, and an alkoxycarboxylic acid ester of an alkylene glycol monoalkyl ether.
  • the crosslinking agent (C) is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.
  • composition for forming a resist underlayer film according to any one of [1] to [12] which is used in an EUV (extreme ultraviolet) exposure process.
  • a semiconductor substrate; The resist underlayer film according to [14], A laminate comprising: [16] A step of forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to [13]; forming a resist film on the resist underlayer film; A method for manufacturing a semiconductor device, comprising: [17] A step of forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to [13]; forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam, and then developing the resist film to obtain a resist pattern; etching the resist underlayer film using the resist pattern as a mask; A pattern forming method comprising:
  • the present invention provides a composition for forming a resist underlayer film that can improve sensitivity and adhesion and form a good resist pattern, as well as methods for manufacturing a resist underlayer film, a laminate, and a semiconductor device, and a pattern formation method that use the composition for forming a resist underlayer film.
  • composition for forming resist underlayer film contains a resin (A) and a solvent (B).
  • the composition for forming a resist underlayer film may contain a crosslinking agent (C), a curing catalyst (D), and the like.
  • the resin (A) has a polymerizable multiple bond and a carboxy group.
  • the resin (A) has a polymerizable multiple bond and a carboxy group.
  • the polymerizable multiple bond include a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-nitrogen double bond, a carbon-nitrogen triple bond, etc.
  • a carbon-carbon double bond and a carbon-carbon triple bond are preferred.
  • the group having a polymerizable multiple bond include a (meth)acryloyl group, a (meth)acrylamide group, a vinylaryl group (for example, a styryl group), a vinyloxy group, and an allyl group.
  • the resin (A) is not particularly limited, but examples include vinyl polymers and epoxy resin derivatives.
  • the resin (A) may be a resin having a structural unit having a polymerizable multiple bond and a carboxy group, or a resin having a structural unit having a polymerizable multiple bond and a structural unit having a carboxy group.
  • resins having a structural unit having a polymerizable multiple bond and a carboxy group include resins having a structural unit having a group represented by the following formula (A).
  • resins having a structural unit having a polymerizable multiple bond and a structural unit having a carboxy group include resins (e.g., vinyl polymers) having a structural unit having a (meth)acryloyl group and a structural unit having a carboxy group.
  • the resin (A) has, for example, a group represented by the following formula (A).
  • L1 represents a linking group
  • L2 represents a divalent group having a carboxy group
  • L3 represents a monovalent group having a polymerizable multiple bond
  • * represents a bond.
  • Examples of the linking group in L 1 include an ether bond, an ester bond, and an amide bond.
  • Examples of the divalent group having a carboxy group for L2 include divalent groups represented by the following formula (L2-1).
  • R represents a single bond or an organic group having 1 to 20 carbon atoms. * represents a bond.
  • Examples of the organic group having 1 to 20 carbon atoms for R in formula (L2-1) include divalent hydrocarbon groups.
  • the divalent hydrocarbon group may be an aromatic hydrocarbon group or a non-aromatic hydrocarbon group.
  • Examples of the non-aromatic hydrocarbon group include a saturated hydrocarbon group and an unsaturated hydrocarbon group.
  • R in formula (L2-1) is, for example, a residue obtained by removing two carboxy groups from a dicarboxylic acid, or a residue obtained by removing an acid anhydride group from a dicarboxylic acid anhydride.
  • Examples of dicarboxylic acids and dicarboxylic acid anhydrides include saturated dicarboxylic acids, unsaturated dicarboxylic acids, aromatic dicarboxylic acids, and anhydrides thereof.
  • saturated dicarboxylic acids and unsaturated dicarboxylic acids are non-aromatic dicarboxylic acids.
  • saturated dicarboxylic acids include oxalic acid, succinic acid, adipic acid, dodecanedioic acid, dodecenylsuccinic acid, pentadecenylsuccinic acid, and octadecenylsuccinic acid.
  • unsaturated dicarboxylic acids include tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, maleic acid, citraconic acid, 2,3-dimethylmaleic acid, and itaconic acid.
  • dicarboxylic acid anhydrides include succinic anhydride, dodecenyl succinic anhydride, pentadecenyl succinic anhydride, octadecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, and itaconic anhydride.
  • R in formula (L2-1) examples include the following groups. (* represents a bond.)
  • the number of carbon atoms of the monovalent group having a polymerizable multiple bond in L3 is not particularly limited, and may be, for example, 2 to 20.
  • Examples of the monovalent group having a polymerizable multiple bond in L3 include a (meth)acryloyl group, a (meth)acrylamide group, a vinylaryl group (for example, a styryl group), a vinyloxy group, and an allyl group.
  • examples of L3 include monovalent groups represented by the following formula (L3-A). (In formula (L3-A), X represents a single bond, an ether bond, an ester bond, or an amide bond.
  • L3-1 represents any of groups represented by the following formulae (L3-1) to (L3-81).)
  • X is a single bond or an ether bond.
  • the terminal on the X side of formulae (L3-1) to (L3-81) is an ester group, an ether group, or a nitrogen atom, X is a single bond.
  • X is a single bond, an ether bond, an ester bond, or an amide bond.
  • the vinyl polymer (A1) has, for example, a structural unit represented by the following formula (1):
  • the structural unit represented by formula (1) is a structural unit having a polymerizable multiple bond and a carboxy group.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • L 11 represents a linking group.
  • L 12 represents a divalent group having a carboxy group.
  • L 13 represents a monovalent group having a polymerizable multiple bond.
  • L 11 include the specific examples of L 1 in formula (A).
  • Specific examples of L 12 include the specific examples of L 2 in formula (A).
  • Specific examples of L 13 include the specific examples of L 3 in formula (A).
  • Specific examples of the -L 11 -L 12 -L 13 group in formula (1) include the specific examples of the group represented by formula (A).
  • R1 is preferably a hydrogen atom or a methyl group.
  • the vinyl polymer (A1) may have a structural unit other than the structural unit having a polymerizable multiple bond and a carboxy group, such as a structural unit represented by the following formula (B-11), a structural unit represented by the following formula (B-12), or a structural unit represented by the following formula (B-13).
  • the vinyl polymer (A1) may also have a structural unit represented by the formula (B-21) described below as a structural unit other than the structural unit having a polymerizable multiple bond and a carboxy group.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • L 53 represents a monovalent group having 1 to 20 carbon atoms.
  • R2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • Ar represents a benzene ring or a naphthalene ring
  • L54 represents a hydroxy group, a cyano group, a nitro group, or an amino group ( -NH2 ).
  • L55 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • m1 represents an integer of 0 to 3.
  • m2 represents an integer of 0 to 5, provided that the sum of m1 and m2 is 0 to 5. When m1 is 2 or 3, multiple L54s may be the same or different.
  • R2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • L56 represents a monovalent organic group selected from alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 40 carbon atoms
  • at least one hydrogen atom of the alkyl group and the aryl group may be substituted with a hydroxy group or an alkoxy group having 1 to 6 carbon atoms.
  • Each R2 is preferably independently a hydrogen atom or a methyl group.
  • the monovalent group having 1 to 20 carbon atoms for L 53 in formula (B-11) represents, for example, a monovalent organic group selected from an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 40 carbon atoms, and at least one hydrogen atom of the alkyl group and the aryl group may be substituted with a hydroxy group.
  • the alkyl group may have an oxygen atom inserted between carbon atoms.
  • Examples of the monovalent group having 1 to 20 carbon atoms for L 53 include groups represented by the following formula (B-11-1).
  • L 3a represents an optionally substituted alkyl group having 1 to 6 carbon atoms or an optionally substituted aromatic hydrocarbon group.
  • X represents a single bond or a carbonyl group.
  • Examples of the aromatic hydrocarbon group in L 3a include a phenyl group and a naphthyl group.
  • Examples of the substituent in the optionally substituted alkyl group having 1 to 6 carbon atoms of L3a include a halogen atom and a hydroxy group.
  • the number of substituents may be one or more. When there are more than one substituent, the multiple substituents may be the same or different.
  • Examples of the substituent in the optionally substituted aromatic hydrocarbon group of L3a include a halogen atom, a hydroxy group, and an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom.
  • the number of substituents may be one or more. When there are multiple substituents, the multiple substituents may be the same or different.
  • L 3a is an alkyl group having 1 to 6 carbon atoms which may be substituted, for example, X represents a carbonyl group.
  • Examples of the halogen atom in L 55 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkyl group having 1 to 6 carbon atoms for L 55 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, and an i-butyl group.
  • Examples of the alkoxy group having 1 to 6 carbon atoms for L 55 include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • m1 represents an integer of 0 to 3, and may be 0, 1, 2, or 3.
  • m2 represents an integer of 0 to 5, and may be 0, 1, 2, 3, 4, or 5.
  • Examples of the aryl group having 6 to 40 carbon atoms represented by L 53 and L 56 include a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-nitrophenyl group, a p-cyanophenyl group, an ⁇ -naphthyl group, a ⁇ -naphthyl group, an o-biphenylyl group, an m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a
  • Examples of the monomer used to derive the formula (B-11) include the following compounds:
  • Examples of the monomer used to derive the formula (B-12) include the following compounds: Me represents a methyl group.
  • Examples of the monomer used to derive the formula (B-13) include the following compounds:
  • the proportion of the structural unit having a polymerizable multiple bond and a carboxy group (for example, the structural unit represented by formula (1)) in the vinyl polymer (A1) is not particularly limited, but the molar ratio of the structural unit having a polymerizable multiple bond and a carboxy group to all structural units in the vinyl polymer (A1) may be, for example, 20 mol % to 100 mol %, 40 mol % to 100 mol %, or 60 mol % to 100 mol %.
  • the proportion of the total (S1) of the structural units represented by formula (B-11), the structural units represented by formula (B-12), and the structural units represented by formula (B-13) in the vinyl polymer (A1) is not particularly limited, and the molar ratio of the total (S1) to all structural units in the vinyl polymer (A1) may be, for example, 0 mol % to 80 mol %, or may be more than 0 mol % and not more than 60 mol %.
  • the vinyl polymer (A1) may contain structural units other than the structural unit having a polymerizable multiple bond and a carboxy group, the structural unit represented by formula (B-11), the structural unit represented by formula (B-12), and the structural unit represented by formula (B-13).
  • the molar ratio of the other structural units to the total structural units of the vinyl polymer (A1) is, for example, more than 0 mol % and not more than 40 mol %.
  • An example of the vinyl polymer (A1) can be obtained, for example, by reacting a vinyl polymer having an epoxy group (e.g., polyglycidyl methacrylate) with methacrylic acid, and then reacting the resulting hydroxy group with a dicarboxylic acid anhydride, as shown below. (In the formula, R has the same meaning as R in formula (L2-1).)
  • an epoxy group e.g., polyglycidyl methacrylate
  • the vinyl polymer (A2) has, for example, a structural unit represented by the following formula (B-21) and a structural unit represented by the following formula (B-22).
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • L 61 represents a single bond or a linking group.
  • L 62 represents a monovalent group having a polymerizable multiple bond.
  • R4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R3 and R4 are each preferably independently a hydrogen atom or a methyl group.
  • L 61 is a linking group
  • the number of carbon atoms in the linking group is not particularly limited, but may be, for example, 1 to 10.
  • examples of the linking group include a linking group having a structure obtained by reacting an epoxy group with a nucleophilic functional group, and a linking group having a structure obtained by reacting an isocyanate group with a nucleophilic functional group.
  • L 61 examples include the following linking groups (L61-1) to (L61-11). (In the formula, *1 represents a bond bonded to the carbon atom bonded to R3 in formula (B-21). *2 represents a bond bonded to L62 in formula (B-21).)
  • L 62 is a monovalent group having a polymerizable multiple bond.
  • the monovalent group may be the polymerizable multiple bond itself.
  • the number of carbon atoms in the monovalent group is not particularly limited, but may be, for example, 1 to 20 or 1 to 10.
  • L 62 examples include the groups represented by the above formulae (L3-1) to (L3-81).
  • Examples of the -L 61 -L 62 group in formula (B-21) include groups represented by the following formulas.
  • Ra represents a hydrogen atom or a methyl group. * represents a bond.
  • the vinyl polymer (A2) may have structural units other than the structural unit having a polymerizable multiple bond and the structural unit having a carboxy group.
  • Examples of such structural units include the structural unit represented by the aforementioned formula (B-11), the structural unit represented by the aforementioned formula (B-12), and the structural unit represented by the aforementioned formula (B-13).
  • the proportion of structural units having a polymerizable multiple bond (e.g., structural units represented by formula (B-21)) in vinyl polymer (A2) is not particularly limited, but the molar ratio of structural units having a polymerizable multiple bond relative to all structural units in vinyl polymer (A2) may be, for example, 10 mol% or more and less than 100 mol%, 20 mol% to 80 mol%, or 30 mol% to 70 mol%.
  • the proportion of structural units having a carboxy group (e.g., structural units represented by formula (B-22)) in vinyl polymer (A2) is not particularly limited, but the molar ratio of structural units having a carboxy group relative to all structural units in vinyl polymer (A2) may be, for example, 10 mol% or more and less than 100 mol%, 20 mol% to 80 mol%, or 30 mol% to 70 mol%.
  • the molar ratio of the total (S11) of the structural units having a polymerizable multiple bond and the structural units having a carboxy group in the vinyl polymer (A2) is not particularly limited, but the molar ratio of the total (S11) relative to all structural units in the vinyl polymer (A2) may be, for example, 20 mol% to 100 mol%, 40 mol% to 100 mol%, or 50 mol% to 100 mol%.
  • Vinyl polymer (A2) may contain structural units other than the structural unit having a polymerizable multiple bond, the structural unit having a carboxy group, the structural unit represented by formula (B-11), the structural unit represented by formula (B-12), and the structural unit represented by formula (B-13).
  • the molar ratio of the other structural units to the total structural units of vinyl polymer (A2) is, for example, more than 0 mol % and not more than 40 mol %.
  • An example of the vinyl polymer (A2) can be obtained by reacting some of the carboxy groups of a polymer having carboxy groups with glycidyl methacrylate, as shown below.
  • Epoxy resin derivatives An example of the resin (A) is an epoxy resin derivative having a polymerizable multiple bond and a carboxy group. Epoxy resin derivatives are different from vinyl polymers.
  • Epoxy resin derivatives can be obtained, for example, by reacting the epoxy groups in an epoxy resin (Ep) with the carboxy groups of a compound (a0) having a polymerizable multiple bond and a carboxy group to open the epoxy groups and generate hydroxy groups, and then reacting some or all of these hydroxy groups with a polycarboxylic acid or polycarboxylic anhydride (b0).
  • Epoxy resin derivatives can be obtained, for example, by reacting the epoxy groups in an epoxy resin (Ep) with the carboxy groups of a compound (a0) having a polymerizable multiple bond and a carboxy group to open the epoxy groups and generate hydroxy groups, and then reacting some or all of these hydroxy groups with a polycarboxylic acid or polycarboxylic anhydride (b0).
  • the epoxy resin derivative has, for example, a group represented by the following formula (2).
  • L 21 represents a linking group
  • L 22 represents a divalent group having a carboxy group
  • L 23 represents a monovalent group having a polymerizable multiple bond
  • * represents a bond.
  • L 21 include the specific examples of L 1 in formula (A).
  • Specific examples of L 22 include the specific examples of L 2 in formula (A).
  • Specific examples of L 23 include the specific examples of L 3 in formula (A).
  • Specific examples of the group represented by formula (2) include the specific examples of the group represented by formula (A).
  • epoxy resins examples include aliphatic epoxy resins [e.g., YH-300, PG-207GS (all manufactured by Nippon Steel Chemical & Material Co., Ltd.)], alicyclic epoxy resins [e.g., CY-179, CY-177, CY-175 (all manufactured by Asahi Kasei Epoxy Corporation)], aromatic epoxy resins [e.g., phenol novolac epoxy resin, cresol novolac epoxy resin [e.g., EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.)], bisphenol A epoxy resin, biphenyl-type epoxy resin, glycidyl-modified polyvinylphenol, etc.], and the like.
  • aliphatic epoxy resins e.g., YH-300, PG-207GS (all manufactured by Nippon Steel Chemical & Material Co., Ltd.)
  • alicyclic epoxy resins e.g., CY-179, CY-177,
  • Examples of compounds having a polymerizable multiple bond and a carboxy group include (meth)acryloyl group-containing monocarboxylic acids (a1) [(meth)acrylic acid], and unsaturated monocarboxylic acids (a2) other than (a1) having 4 to 30 carbon atoms [e.g., crotonic acid, sorbic acid, cinnamic acid, etc.].
  • polycarboxylic acids or polycarboxylic anhydrides examples include the dicarboxylic acids and dicarboxylic anhydrides mentioned above.
  • the reaction temperature for the reaction between the epoxy resin (Ep) and the compound (a0) in the production of the epoxy resin derivative is not particularly limited, but is preferably 70°C to 110°C.
  • the reaction time is also not particularly limited, but is preferably 5 to 30 hours.
  • a catalyst e.g., triphenylphosphine, etc.
  • a radical polymerization inhibitor hydroquinone, p-methoxyphenol, etc.
  • the reaction temperature for the reaction between the adduct obtained by adding compound (a0) to epoxy resin (Ep) and polycarboxylic acid or polycarboxylic acid anhydride (b0) is not particularly limited, but is preferably 70°C to 110°C.
  • the reaction time is also not particularly limited, but is preferably 3 to 10 hours.
  • epoxy resin derivatives having polymerizable multiple bonds and carboxy groups can be used.
  • Commercially available products include acid-modified phenol novolac epoxy acrylates [PCR-1222H, PCR-1173H, PCR-1221H, PCR-1220H (all manufactured by Nippon Kayaku Co., Ltd.), etc.], acid-modified resol novolac epoxy acrylates [CCR-1171H, CCR-1235, CCR-1291H, CCR-1307H, CCR-1309H, CCR-1325H (all manufactured by Nippon Kayaku Co., Ltd.), etc.], acid-modified bisphenol A epoxy acrylates [ZAR-1035, ZAR-1494, ZAR-2000, ZAR-2001H (all manufactured by Nippon Kayaku Co., Ltd.), etc.], acid-modified bisphenol F epoxy acrylates [ZFR-1122, ZFR-1401H, ZFR-1491H (all manufactured by Nippon Kayaku Co., Ltd.), etc.), acid-modified biphenyl type epoxy
  • the lower limit of the weight average molecular weight of the resin (A) is, for example, 500, 1,000, or 1,500.
  • the upper limit of the weight average molecular weight of the resin (A) is, for example, 50,000, 30,000, or 20,000.
  • the content of the resin (A) in the composition for forming a resist underlayer film is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 40% by mass to 95% by mass, more preferably 45% by mass to 90% by mass, and particularly preferably 50% by mass to 85% by mass, based on the film-constituting components.
  • the film-constituting components refer to components other than the solvent contained in the composition.
  • the solvent (B) is not particularly limited, and may be water or an organic solvent.
  • organic solvents include carboxylic acids having a hydroxy group, linear or cyclic alkyl ketones, cyclic lactones, alkylene glycol alkyl ethers, and alkylene glycol monoalkyl ether carboxylic acid esters (monocarboxylic acid esters of alkylene glycol monoalkyl ethers, and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers).
  • carboxylic acids having a hydroxy group examples include ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, and methyl 2-hydroxy-3-methylbutyrate.
  • alkylene glycol alkyl ethers include alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers.
  • alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol, and propylene glycol monobutyl ether.
  • alkylene glycol dialkyl ethers examples include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether.
  • alkylene glycol monoalkyl ether carboxylic acid esters include monocarboxylic acid esters of alkylene glycol monoalkyl ethers and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers.
  • alkylene glycol monoalkyl ether carboxylic acid esters include monocarboxylic acid esters of alkylene glycol monoalkyl ethers and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers.
  • the monocarboxylic acid ester of alkylene glycol monoalkyl ether include alkylene glycol monoalkyl ether acetate.
  • alkylene glycol monoalkyl ether acetates examples include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate.
  • alkoxycarboxylic acid ester of alkylene glycol monoalkyl ether examples include 2-methoxyethyl methyl carbonate, 2-ethoxyethyl methyl carbonate, 2-ethoxyethyl ethyl carbonate, and 2-propoxyethyl methyl carbonate.
  • solvents include toluene, xylene, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl
  • alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers are preferred.
  • solvents (B) can be used alone or in combination of two or more.
  • the mass proportion of the organic solvent in solvent (B) is not particularly limited, but is preferably 50% to 100% by mass.
  • the content of solvent (B) in the composition for forming a resist underlayer film is not particularly limited, but is preferably 50% by mass to 99.99% by mass, more preferably 75% by mass to 99.95% by mass, and particularly preferably 90% by mass to 99.9% by mass.
  • the crosslinking agent (C) is not particularly limited.
  • the crosslinking agent (C) has a structure different from that of the resin (A).
  • an aminoplast crosslinking agent or a phenoplast crosslinking agent is preferred.
  • Aminoplast crosslinking agents are addition condensation products of a compound having an amino group, such as melamine or guanamine, and formaldehyde.
  • the phenoplast crosslinking agent is an addition condensation product of a compound having a phenolic hydroxy group and formaldehyde.
  • the crosslinking agent may also be a compound having two or more epoxy groups, such as a homopolymer or copolymer of a (meth)acrylic monomer having an epoxy group, or another compound having two or more epoxy groups.
  • An example of the (meth)acrylic monomer having an epoxy group is glycidyl (meth)acrylate.
  • An example of a homopolymer or copolymer of a (meth)acrylic monomer having an epoxy group is polyglycidyl (meth)acrylate.
  • Other compounds having two or more epoxy groups are roughly divided into compounds having an aromatic ring and compounds having no aromatic ring, for example.
  • epoxy compounds having an aromatic ring examples include epoxy compounds having a bisphenol skeleton such as bisphenol A type, bisphenol F type, or bisphenol S type; epoxy compounds having a dicyclopentadiene skeleton such as dicyclopentadiene dioxide or a phenol novolak epoxy compound having a dicyclopentadiene skeleton; epoxy compounds having a naphthalene skeleton such as 1-glycidylnaphthalene, 2-glycidylnaphthalene, 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, 1,7-diglycidylnaphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene, or 1,2,5,6-tetraglycidylnaphthalene; 9,9-bis(4-glycidyloxyphenyl)fluorene, 9,9-bis(4
  • Examples of the crosslinking agent (C) include compounds having two or more of the following structures.
  • R 101 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond.
  • the bond is bonded to, for example, a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.
  • R 101 is preferably a hydrogen atom, a methyl group, an ethyl group, or a group represented by the following structure.
  • R 102 represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bond.
  • R 1 represents a methyl group or an ethyl group.
  • glycoluril derivatives represented by formula (2E) include compounds represented by formulas (2E-1) to (2E-4) below.
  • examples of compounds represented by formula (3d) include compounds represented by formulas (3d-1) and (3d-2) below.
  • urea compounds include tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea compounds in which one to four methylol groups are methoxymethylated, or mixtures thereof, and tetramethoxyethyl urea.
  • Examples of the compound having a phenolic hydroxy group include compounds represented by the following formula (G-1) or (G-2).
  • Q1 represents a single bond or an m1-valent organic group.
  • R 1 and R 4 each represent an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms.
  • R2 and R5 each represent a hydrogen atom or a methyl group.
  • R3 and R6 each represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.
  • n1 is an integer satisfying 1 ⁇ n1 ⁇ 3, n2 is an integer satisfying 2 ⁇ n2 ⁇ 5, n3 is an integer satisfying 0 ⁇ n3 ⁇ 3, n4 is an integer satisfying 0 ⁇ n4 ⁇ 3, and 3 ⁇ ( n1 + n2 + n3 + n4 ) ⁇ 6.
  • n5 is an integer satisfying 1 ⁇ n5 ⁇ 3, n6 is an integer satisfying 1 ⁇ n6 ⁇ 4, n7 is an integer satisfying 0 ⁇ n7 ⁇ 3, n8 is an integer satisfying 0 ⁇ n8 ⁇ 3, and 2 ⁇ ( n5 + n6 + n7 + n8 ) ⁇ 5.
  • m1 represents an integer of 2 to 10.
  • Examples of compounds having a phenolic hydroxy group include compounds represented by the following formula (G-3) or (G-4).
  • the compound represented by formula (G-1) or formula (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or formula (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms.
  • Q2 represents a single bond or an m2-valent organic group.
  • R 8 , R 9 , R 11 and R 12 each represent a hydrogen atom or a methyl group.
  • R7 and R10 each represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.
  • n9 is an integer satisfying 1 ⁇ n9 ⁇ 3, n10 is an integer satisfying 2 ⁇ n10 ⁇ 5, n11 is an integer satisfying 0 ⁇ n11 ⁇ 3, n12 is an integer satisfying 0 ⁇ n12 ⁇ 3, and 3 ⁇ ( n9 + n10 + n11 + n12 ) ⁇ 6.
  • n13 is an integer satisfying 1 ⁇ n13 ⁇ 3, n14 is an integer satisfying 1 ⁇ n14 ⁇ 4, n15 is an integer satisfying 0 ⁇ n15 ⁇ 3, n16 is an integer satisfying 0 ⁇ n16 ⁇ 3, and 2 ⁇ ( n13 + n14 + n15 + n16 ) ⁇ 5.
  • m2 represents an integer of 2 to 10.
  • the m2-valent organic group for Q2 includes, for example, an m2-valent organic group having 1 to 4 carbon atoms.
  • Examples of the compound represented by formula (G-1) or formula (G-2) include the following compounds:
  • Examples of the compound represented by formula (G-3) or formula (G-4) include the following compounds:
  • the above compound is available as a product of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd.
  • An example of the product is TMOM-BP, a product name of Asahi Organic Chemicals Co., Ltd.
  • glycoluril compounds are preferred, specifically tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, tetramethylol glycoluril compounds in which one to four methylol groups are methoxymethylated or mixtures thereof, and tetramethylol glycoluril compounds in which one to four methylol groups are acyloxymethylated or mixtures thereof, with tetramethoxymethyl glycoluril being more preferred.
  • the molecular weight of the crosslinking agent (C) is not particularly limited, but is preferably 1,000 or less.
  • the content of crosslinking agent (C) in the composition for forming a resist underlayer film is not particularly limited, but is, for example, 1% to 70% by mass, and preferably 5% to 60% by mass, relative to the resin (A).
  • the curing catalyst (D) contained as an optional component in the composition for forming a resist underlayer film may be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator.
  • the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonate salt), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, 4-hydroxybenzen
  • photoacid generators examples include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.
  • onium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenyls
  • sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.
  • disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.
  • the curing catalyst (D) can be used alone or in combination of two or more types.
  • the content of the curing catalyst (D) relative to the crosslinking agent (C) is, for example, 0.1% to 50% by mass, and preferably 1% to 30% by mass.
  • a surfactant may be further added to the composition for forming a resist underlayer film in order to prevent pinholes, striations, etc., and to further improve coating properties for preventing surface irregularities.
  • surfactants include linear or branched alkylbenzenesulfonic acids (e.g., dodecylbenzenesulfonic acid, etc.), polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and polyoxyethylene sorbitan monolaurate.
  • alkylbenzenesulfonic acids e.g., dodecylbenzenesulfonic acid,
  • nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as Eftop EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, and R-30 (trade names, manufactured by DIC Corporation), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by AGC Inc.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the amount of these surfactants added is usually 2.0% by mass or
  • the composition for forming a resist underlayer film may contain a polymerization inhibitor (radical trapping agent) as needed.
  • a polymerization inhibitor Radical trapping agent
  • examples of the polymerization inhibitor include 2,6-diisobutylphenol, 3,5-di-tert-butylphenol, 3,5-di-tert-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and 4-methoxy-1-naphthol.
  • the content of the polymerization inhibitor in the composition for forming a resist underlayer film is not particularly limited, but is preferably 1 mass % or less based on the solid content.
  • the solid content of the composition for forming a resist underlayer film of the present invention i.e., the components excluding the solvent, is, for example, 0.01% by mass to 10% by mass.
  • the composition for forming a resist underlayer film is preferably used in an EUV (extreme ultraviolet) exposure process.
  • the composition for forming a resist underlayer film is preferably used to form an underlayer film of a metal-containing resist.
  • the resist underlayer film of the present invention is a cured product of the above-mentioned composition for forming a resist underlayer film.
  • the resist underlayer film can be produced, for example, by applying the above-described composition for forming a resist underlayer film onto a semiconductor substrate and baking it.
  • Semiconductor substrates onto which the resist underlayer film-forming composition can be applied include, for example, silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.
  • the inorganic film can be formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (spin-on-glass: SOG).
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • reactive sputtering ion plating
  • vacuum deposition vacuum deposition
  • spin coating spin-on-glass: SOG
  • inorganic films include polysilicon films, silicon oxide films, silicon nitride films, BPSG (Boro-Phospho Silicate Glass) films, titanium nitride films, titanium nitride oxide films, tungsten films, gallium nitride films, and gallium arsenide films.
  • the resist underlayer film-forming composition of the present invention is applied to such a semiconductor substrate using an appropriate application method such as a spinner or coater.
  • the resist underlayer film is then formed by baking using a heating means such as a hot plate.
  • Baking conditions are appropriately selected from a bake temperature of 100°C to 400°C and a bake time of 0.3 to 60 minutes.
  • a bake temperature of 120°C to 350°C and a bake time of 0.5 to 30 minutes are preferred, and a bake temperature of 150°C to 300°C and a bake time of 0.8 to 10 minutes are more preferred.
  • the thickness of the resist underlayer film can be, for example, 0.001 ⁇ m (1 nm) to 10 ⁇ m, 0.002 ⁇ m (2 nm) to 1 ⁇ m, 0.005 ⁇ m (5 nm) to 0.5 ⁇ m (500 nm), 0.001 ⁇ m (1 nm) to 0.05 ⁇ m (50 nm), 0.002 ⁇ m (2 nm) to 0.05 ⁇ m (50 nm), 0.003 ⁇ m (3 nm) to 0.05 ⁇ m (50 nm), 0.004 ⁇ m (4 nm) to 0.05 ⁇ m (50 nm), 0.005 ⁇ m ( 0.003 ⁇ m (3 nm) to 0.02 ⁇ m (20 nm), 0.005 ⁇ m (5 nm) to 0.02 ⁇ m (20 nm), 0.003 ⁇ m (3 nm) to 0.01 ⁇ m (10 nm), 0.005 ⁇ m (5 nm) to 0.01 ⁇ m (10
  • the method for measuring the film thickness of the resist underlayer film is as follows. - Measurement equipment name: Ellipso film thickness measurement equipment RE-3100 (SCREEN Co., Ltd.) - SWE (single wavelength ellipsometer) mode - Arithmetic average of 8 points (for example, measuring 8 points at 1 cm intervals in the X direction of the wafer)
  • the laminate of the present invention comprises a semiconductor substrate and the resist underlayer film of the present invention.
  • the semiconductor substrate may be, for example, the semiconductor substrate described above.
  • the resist underlayer film is disposed on, for example, a semiconductor substrate.
  • the method for manufacturing a semiconductor device of the present invention includes at least the following steps. - forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film of the present invention; and - forming a resist film on the resist underlayer film.
  • the pattern forming method of the present invention includes at least the following steps.
  • the resist film formed on the resist underlayer film by a known method is not particularly limited as long as it responds to light or electron beam (EB) used for irradiation.
  • EB electron beam
  • a resist that responds to EB is also referred to as a photoresist.
  • photoresists include positive photoresists made of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists made of a binder having a group that decomposes in the presence of acid to increase the alkaline dissolution rate and a photoacid generator, chemically amplified photoresists made of a low molecular weight compound that decomposes in the presence of acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and chemically amplified photoresists made of a binder having a group that decomposes in the presence of acid to increase the alkaline dissolution rate of the photoresist, a low molecular weight compound that decomposes in the presence of acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator, and resists containing metal elements
  • Examples include V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley Chemical Co., Ltd., PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. Further, for example, the photoresists described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).
  • resist compositions include the following compositions:
  • An actinic ray-sensitive or radiation-sensitive resin composition comprising: resin A having a repeating unit having an acid-decomposable group in which a polar group is protected with a protecting group that is cleaved by the action of acid; and a compound represented by the following general formula (121):
  • m represents an integer of 1 to 6.
  • R 1 and R 2 each independently represent a fluorine atom or a perfluoroalkyl group.
  • L 1 represents —O—, —S—, —COO—, —SO 2 — or —SO 3 —.
  • L2 represents an alkylene group which may have a substituent or a single bond.
  • W1 represents a cyclic organic group which may have a substituent.
  • M + represents a cation.
  • a metal-containing film-forming composition for extreme ultraviolet or electron beam lithography comprising a compound having a metal-oxygen covalent bond and a solvent, wherein the metal element constituting the compound belongs to Periods 3 to 7 of Groups 3 to 15 of the periodic table.
  • a radiation-sensitive resin composition comprising a polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) containing an acid-dissociable group, and an acid generator.
  • Ar represents a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms.
  • R1 represents a hydroxy group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms.
  • n represents an integer from 0 to 11. When n is 2 or greater, multiple R1s may be the same or different.
  • R2 represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
  • R3 represents a monovalent group having 1 to 20 carbon atoms and containing the above-mentioned acid-dissociable group.
  • Z represents a single bond, an oxygen atom, or a sulfur atom.
  • R4 represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
  • R2 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom
  • X1 represents a single bond, -CO-O-* or -CO- NR4- *, * represents a bond to -Ar
  • R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have one or more groups selected from the group consisting of a hydroxy group and a carboxy group.
  • resist films examples include:
  • a resist film comprising a base resin containing a repeating unit represented by the following formula (a1) and/or a repeating unit represented by the following formula (a2), and a repeating unit that generates an acid bonded to the polymer main chain upon exposure.
  • R A each independently represents a hydrogen atom or a methyl group.
  • R 1 and R 2 each independently represent a tertiary alkyl group having 4 to 6 carbon atoms.
  • R 3 each independently represents a fluorine atom or a methyl group.
  • m is an integer of 0 to 4.
  • X 1 is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group.
  • X 2 is a single bond, an ester bond, or an amide bond.
  • resist materials examples include:
  • R A represents a hydrogen atom or a methyl group.
  • X 1 represents a single bond or an ester group.
  • X 2 represents a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and some of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group, or a lactone ring-containing group, and at least one hydrogen atom contained in X 2 is substituted with a bromine atom.
  • X 3 represents a single bond, an ether group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and some of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group.
  • Rf 1 to Rf 4 are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and at least one is a fluorine atom or a trifluoromethyl group. and 2 may combine to form a carbonyl group.
  • R 1 to R 5 are each independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, some or all of the hydrogen atoms in these groups may be substituted with a hydroxy group, a carboxy group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group, or a sulfonium salt-containing group, and some of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbon
  • a resist material comprising a base resin containing a polymer containing a repeating unit represented by the following formula (a):
  • R A represents a hydrogen atom or a methyl group.
  • R 1 represents a hydrogen atom or an acid labile group.
  • R 2 represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine.
  • X 1 represents a single bond, a phenylene group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms which may contain an ester group or a lactone ring.
  • X 2 represents —O—, —O—CH 2 —, or —NH—.
  • m represents an integer of 1 to 4.
  • u represents an integer of 0 to 3, with the proviso that m+u represents an integer of 1 to 4.
  • a resist composition that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid
  • the composition contains a base component (A) whose solubility in a developer changes under the action of an acid, and a fluorine additive component (F) that is decomposable in an alkaline developer
  • the fluorine additive component (F) is a resist composition containing a fluorine resin component (F1) that has a structural unit (f1) that includes a base-dissociable group, and a structural unit (f2) that includes a group represented by the following general formula (f2-r-1):
  • each Rf21 independently represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a hydroxyalkyl group, or a cyano group.
  • n" represents an integer of 0 to 2. * represents a bond.
  • the structural unit (f1) includes a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2):
  • each R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
  • X is a divalent linking group having no acid dissociable site.
  • a aryl is a divalent aromatic cyclic group which may have a substituent.
  • X 01 is a single bond or a divalent linking group.
  • Each R 2 is independently an organic group having a fluorine atom.
  • the resist composition may be a metal-containing resist.
  • Metal-containing resists are also called metal oxide resists (MOR), and a representative example is a tin oxide-based resist.
  • MOR metal oxide resists
  • metal oxide resist materials include coating compositions containing metal oxo-hydroxo networks having organic ligands via metal carbon bonds and/or metal carboxylate bonds, as described in JP 2019-113855 A.
  • One example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand.
  • Peroxo-based metal oxo-hydroxo compounds are described in detail in, for example, the patent documents listed in paragraph [0011] of Publication No. 2019-532489. Examples of such patent documents include U.S. Pat. No.
  • a coating comprising a metal oxo-hydroxo network having organic ligands via metal-carbon and/or metal carboxylate bonds.
  • An aqueous inorganic pattern-forming precursor solution comprising a mixture of water, metal suboxide cations, polyatomic inorganic anions, and radiation-sensitive ligands comprising peroxide groups.
  • the light or electron beam irradiation is carried out, for example, through a mask (reticle) for forming a predetermined pattern.
  • a mask for example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) is used.
  • the composition for forming a resist underlayer film of the present invention is preferably applied for EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm) irradiation, and more preferably applied for EUV (extreme ultraviolet) exposure.
  • the irradiation energy of the electron beam and the exposure dose of light are not particularly limited.
  • an alkaline developer or an organic solvent is used.
  • the development temperature is, for example, 5°C to 50°C.
  • the development time is, for example, 10 seconds to 300 seconds.
  • alkaline developers that can be used include aqueous solutions of alkalis such as inorganic alkalis (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia); primary amines (e.g., ethylamine and n-propylamine); secondary amines (e.g., diethylamine and di-n-butylamine); tertiary amines (e.g., triethylamine and methyldiethylamine); alcohol amines (e.g., dimethylethanolamine and triethanolamine); quaternary ammonium salts (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide,
  • Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl a
  • the atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 85°C for 24 hours.
  • the reaction vessel was then allowed to cool to room temperature, and 1.69 g of cis-4-cyclohexene-1,2-dicarboxylic anhydride and 6.76 g of propylene glycol monomethyl ether acetate were added and dissolved in the reaction vessel.
  • the atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out again at 85°C for 24 hours, yielding a solution containing polymer 1.
  • GPC analysis revealed that the weight average molecular weight of the obtained polymer 1 was 13,600 and the dispersity was 3.2 in terms of standard polystyrene.
  • the structure present in polymer 1 is shown in the following formula.
  • polyglycidyl methacrylate Maruzen Petrochemical Co., Ltd., 30 wt% propylene glycol monomethyl ether acetate solution
  • methacrylic acid Tokyo Chemical Industry Co., Ltd.
  • polyglycidyl methacrylate manufactured by Maruzen Petrochemical Co., Ltd., 30 wt % propylene glycol monomethyl ether acetate solution
  • methacrylic acid manufactured by Tokyo Chemical Industry Co., Ltd.
  • polyglycidyl methacrylate Maruzen Petrochemical Co., Ltd., 30 wt % propylene glycol monomethyl ether acetate solution
  • methacrylic acid Tokyo Chemical Industry Co., Ltd.
  • the reaction vessel was then allowed to cool to room temperature, and 0.99 g of maleic anhydride and 3.96 g of propylene glycol monomethyl ether acetate were added and dissolved in the reaction vessel.
  • the atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out again at 60°C for 24 hours, yielding a solution containing polymer 5.
  • GPC analysis revealed that the resulting polymer 5 had a weight average molecular weight of 13,100 and a polydispersity of 2.5, calculated in terms of standard polystyrene.
  • the structure present in polymer 5 is shown in the following formula.
  • polyglycidyl methacrylate manufactured by Maruzen Petrochemical Co., Ltd., 30 wt % propylene glycol monomethyl ether acetate solution
  • methacrylic acid manufactured by Tokyo Chemical Industry Co., Ltd.
  • the atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 85°C for 24 hours.
  • the reaction vessel was then allowed to cool to room temperature, and 1.13 g of itaconic anhydride and 4.53 g of propylene glycol monomethyl ether acetate were added and dissolved in the reaction vessel.
  • the atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out again at 60°C for 24 hours, yielding a solution containing polymer 6.
  • GPC analysis revealed that the resulting polymer 6 had a weight average molecular weight of 18,800 and a polydispersity of 4.3, calculated in terms of standard polystyrene.
  • the structure present in polymer 6 is shown in the following formula.
  • polyglycidyl methacrylate Maruzen Petrochemical Co., Ltd., 30 wt % propylene glycol monomethyl ether acetate solution
  • methacrylic acid Tokyo Chemical Industry Co., Ltd.
  • the reaction vessel was then allowed to cool to room temperature, and 1.13 g of citraconic anhydride and 4.53 g of propylene glycol monomethyl ether acetate were added and dissolved in the reaction vessel.
  • the atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out again at 60°C for 24 hours, yielding a solution containing polymer 7.
  • GPC analysis revealed that the resulting polymer 7 had a weight average molecular weight of 12,800 and a polydispersity of 3.3, calculated in terms of standard polystyrene.
  • the structure present in polymer 7 is shown in the following formula.
  • Comparative Synthesis Example 1 100.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemicals Corporation), 66.4 g of 5,5-diethylbarbituric acid, and 4.1 g of benzyltriethylammonium chloride were added to 682.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved therein. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out at 130°C for 24 hours to obtain a solution containing Comparative Polymer 1. GPC analysis showed that the obtained Comparative Polymer 1 had a weight average molecular weight of 6,800 and a dispersity of 4.8, calculated as standard polystyrene. The structure present in Comparative Polymer 1 is shown in the following formula.
  • composition for forming resist underlayer film (Examples and Comparative Examples) Acid-modified epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd.), the polymers obtained in Synthesis Examples 1 to 7 and Comparative Synthesis Example 1, a crosslinking agent, a curing catalyst, and a solvent were mixed in the proportions shown in Table 1 or Table 2, and the mixture was filtered through a 0.1 ⁇ m fluororesin filter to prepare solutions of compositions for forming resist underlayer films.
  • Each of the resist underlayer film-forming compositions of Examples 1 to 13 and Comparative Example 1 was applied to a silicon wafer using a spinner.
  • the silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a film with a thickness of 10 nm.
  • a change in film thickness of 5 ⁇ or less was rated as "good," and a change in film thickness of more than 5 ⁇ was rated as "poor.” The results are shown in Table 3.
  • Resist patterning evaluation-1 Resist pattern formation test using EUV exposure equipment
  • the resist underlayer film-forming compositions of Examples 1, 3 to 8, and Comparative Example 1 were each applied to a silicon wafer using a spinner.
  • the silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer film with a thickness of 10 nm.
  • a negative EUV resist solution was spin-coated onto the resist underlayer film and heated at 100°C for 60 seconds to form an EUV resist film.
  • the resist film was exposed under specified conditions using an EUV exposure system (NXE3400B). After exposure, the resist film was baked at 170°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and developed with a negative photoresist developer.
  • the resist film was baked at 250°C for 60 seconds (HB), cooled to room temperature on a cooling plate, and formed a resist pattern with pillar sizes of 17 nm to 23 nm.
  • the resist pattern was measured using a scanning electron microscope (CG6300, manufactured by Hitachi High-Technologies Corporation).
  • the photoresist patterns thus obtained were evaluated for the possibility of forming 21 nm pillars (PL). Formation of 21 nm PL patterns was confirmed in all cases of Examples 1, 3 to 8, and Comparative Example 1.
  • the EUV irradiation dose that formed 21 nm pillars was defined as the optimal irradiation energy, and the irradiation energy (mJ/cm 2 ) at that time is shown in Table 4. It was confirmed that Examples 1, 3 to 8 exhibited good irradiation energy and minimum CD size.
  • the resist film was baked at 250°C for 60 seconds (HB), cooled to room temperature on a cooling plate, and formed a resist pattern with a line size of 11 nm to 17 nm.
  • a scanning electron microscope (CG6300, manufactured by Hitachi High-Technologies Corporation) was used to measure the resist pattern.
  • the photoresist patterns thus obtained were evaluated for the possibility of forming 14 nm lines and spaces (L/S). Formation of 14 nm L/S patterns was confirmed in all cases of Examples 1 to 13 and Comparative Example 1.
  • the EUV irradiation dose that formed 14 nm lines/28 nm pitch was defined as the optimal irradiation energy.
  • the irradiation energy (mJ/cm 2 ) at this time and the minimum CD size at which no collapse was observed within the resist pattern shot are shown in Table 5.
  • Table 5 also shows the maximum CD size at which no bridging (bridging) was observed within the resist pattern shot. Improvements in sensitivity were confirmed in Examples 1 to 13 compared to Comparative Example 1, and Examples 1 to 13 also exhibited favorable minimum and maximum CD sizes.

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Abstract

L'invention concerne une composition pour former un film de sous-couche de réserve, la composition contenant : une résine (A) ayant une liaison multiple polymérisable et un groupe carboxy ; et un solvant (B).
PCT/JP2025/008752 2024-03-12 2025-03-10 Composition pour former un film de sous-couche de réserve Pending WO2025192513A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014091790A (ja) * 2012-11-05 2014-05-19 Toyo Ink Sc Holdings Co Ltd 樹脂組成物
JP2020098334A (ja) * 2018-12-14 2020-06-25 日鉄ケミカル＆マテリアル株式会社 表示装置用基板及びその製造方法、並びにそれらに用いる反射防止層用樹脂組成物溶液

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014091790A (ja) * 2012-11-05 2014-05-19 Toyo Ink Sc Holdings Co Ltd 樹脂組成物
JP2020098334A (ja) * 2018-12-14 2020-06-25 日鉄ケミカル＆マテリアル株式会社 表示装置用基板及びその製造方法、並びにそれらに用いる反射防止層用樹脂組成物溶液

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