Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
  • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
  • C08G73/0644—Poly(1,3,5)triazines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes

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 method for forming a pattern.
• microfabrication by lithography using a resist composition has been performed.
• the microfabrication is a processing method in which a thin film of a photoresist composition is formed on a semiconductor substrate such as a silicon wafer, and the thin film is irradiated with active light such as ultraviolet light through a mask pattern on which a device pattern is drawn, developed, and the substrate is etched using the obtained photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the photoresist pattern.
• Patent Document 1 discloses a composition for forming an underlayer film for lithography that contains a naphthalene ring having a halogen atom.
• Patent Document 2 discloses a halogenated anti-reflective film.
• Patent Document 3 discloses a composition for forming a resist underlayer film.
• the properties required for the resist underlayer film include, for example, the absence of intermixing with the resist film formed on the upper layer (being insoluble in a resist solvent) and the ability to form a fine resist pattern with high sensitivity.
• the present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a composition for forming a resist underlayer film capable of forming a resist underlayer film capable of forming a fine resist pattern with high sensitivity, and a method for producing a resist underlayer film, a laminate, a semiconductor element, and a pattern forming method using the composition for forming a resist underlayer film.
• a composition for forming a resist underlayer film comprising a polymer (A), a compound (B) having a hydrophobic substituent, and a solvent (C).
• a polymer (A) is at least one of an isocyanuric acid polymer, a polyester polymer, an acrylic polymer, and a polyether.
• the polymer (A) is a polymer having a hydroxy group in a unit structure.
• the crosslinking agent (D) is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.
• a semiconductor substrate; [9], and A laminate comprising: [11] 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 [8]; forming a resist film on the resist underlayer film;
• a method for manufacturing a semiconductor device comprising: [12] 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 [8]; forming a resist film on the resist underlayer film; a step of 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 capable of forming a resist underlayer film capable of forming a fine resist pattern with high sensitivity, as well as a method for producing a resist underlayer film, a laminate, and a semiconductor element, and a method for forming a pattern, using the composition for forming a resist underlayer film.
• composition for forming resist underlayer film contains a polymer (A), a compound (B), and a solvent (C).
• the composition for forming a resist underlayer film may contain a crosslinking agent (D), a curing catalyst (E), and the like.
• the polymer (A) is not particularly limited.
• the polymer (A) is, for example, an organic polymer.
• the polymer (A) is, for example, an isocyanuric acid polymer.
• the isocyanuric acid polymer refers to a polymer having the following isocyanuric acid skeleton. (In the formula, * represents a bond.) One of the bonds represented by * may be bonded to a hydrogen atom.
• the polymer (A) is, for example, a polyester polymer.
• a polyester polymer refers to a polymer having at least an ester bond in the main chain.
• the ester bond in the polyester polymer is formed, for example, by a reaction between a -CO-X group (X represents a hydroxy group, a halogen atom, or an alkoxy group having 1 to 4 carbon atoms) and a hydroxy group or an epoxy group.
• X represents a hydroxy group, a halogen atom, or an alkoxy group having 1 to 4 carbon atoms
• the polymer is an isocyanuric acid-based polymer and also a polyester-based polymer.
• the polymer (A) is, for example, an acrylic polymer.
• the acrylic polymer is, for example, a polymer formed by polymerizing the polymerizable unsaturated bonds of a compound having a group having a polymerizable unsaturated bond.
• the acrylic polymer may be a homopolymer or a copolymer.
• Examples of the group having a polymerizable unsaturated bond include a (meth)acryloyl group, a vinylaryl group (for example, a styryl group), a vinyloxy group, and an allyl group.
• the polymer (A) is, for example, a polyether, which is, for example, a reaction product between a compound having two phenolic hydroxy groups and a compound having two epoxy groups.
• polyethers include the polymers described in WO2022/071468. Such polymers are, for example, polymers derived from a compound (B) represented by the following formula (11).
• Y1 represents a single bond, an oxygen atom, a sulfur atom, an alkylene group having 1 to 10 carbon atoms which may be substituted with a halogen atom or an aryl group having 6 to 40 carbon atoms, or a sulfonyl group; T1 and T2 represent an alkyl group having 1 to 10 carbon atoms; and n1 and n2 each independently represent an integer of 0 to 4.
• the polymer is, for example, a reaction product of a compound (B) and a compound (C) capable of reacting with compound (B).
• the polymer (A) is, for example, a polymer having a hydroxy group in its unit structure.
• the hydroxy group is, for example, a hydroxy group bonded to a secondary carbon atom.
• the polymer (A) may be, for example, a polymer having a unit structure represented by the following formula (P):
• the polymer having a unit structure represented by the following formula (P) may be, for example, a polymer described in WO2022/196662 (a polymer having a unit structure represented by formula (P)).
• a 1 , A 2 , A 3 , A 4 , A 5 and A 6 each independently represent a hydrogen atom, a methyl group or an ethyl group.
• Q 1 and Q 2 each independently represent a divalent organic group containing a heterocyclic structure or an aromatic ring structure having 6 to 40 carbon atoms.
• T2 and T3 each independently represent a single bond, an ester bond or an ether bond.
• L2 and L3 each independently represent a single bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, or an optionally substituted alkenylene group having 2 to 10 carbon atoms.
• Q1 includes, for example, a structure represented by the following formula (P-1).
• X1 represents the following formula (P-1-1), the following formula (P-1-2) or the following formula (P-1-3).
• Z 1 and Z 2 each independently represent a single bond or the following formula (P-1-4).
• R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, and the phenyl group may be substituted with at least one monovalent group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms.
• R 1 and R 2 may be bonded to each other to form a ring having 3 to 6 carbon atoms.
• * represents a bond.
• *1 represents a bond bonded to a carbon atom.
• *2 represents a bond bonded to a nitrogen atom.
• R 3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, and the phenyl group may be substituted with at least one monovalent group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group,
• *1 represents a bond bonded to a carbon atom.
• *2 represents a bond bonded to a nitrogen atom.
• m1 is an integer of 0 to 4
• m2 is 0 or 1
• m3 is 0 or 1
• m4 is an integer of 0 to 2.
• *3 represents a bond bonded to the nitrogen atom in formula (P-1).
• *4 represents a bond.
• examples of a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the alkyl group is not limited to being linear, but may be branched or cyclic.
• linear or branched alkyl groups include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and an n-hexyl group.
• Examples of cyclic alkyl groups (cycloalkyl groups) include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
• examples of an alkoxy group include a methoxy group, an ethoxy group, an n-pentyloxy group, and an isopropoxy group.
• examples of the alkylthio group include a methylthio group, an ethylthio group, an n-pentylthio group, an isopropylthio group and the like.
• examples of the alkenyl group include an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-ethenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 2-methyl-1-propenyl group, and a 2-methyl-2-propenyl group.
• examples of the alkynyl group include the above-mentioned "alkenyl groups" in which the double bond is replaced with a triple bond.
• examples of the alkenyloxy group include a vinyloxy group, a 1-propenyloxy group, a 2-n-propenyloxy group (allyloxy group), a 1-n-butenyloxy group, and a prenyloxy group.
• examples of the alkynyloxy group include a 2-propynyloxy group, a 1-methyl-2-propynyloxy group, a 2-methyl-2-propynyloxy group, a 2-butynyloxy group, and a 3-butynyloxy group.
• examples of the acyl group include an acetyl group and a propionyl group.
• examples of the aryloxy group include a phenoxy group, naphthyloxy group, and the like.
• examples of the arylcarbonyl group include a phenylcarbonyl group.
• examples of the aralkyl group include a benzyl group and a phenethyl group.
• examples of the alkylene group include a methylene group, an ethylene group, a 1,3-propylene group, a 2,2-propylene group, a 1-methylethylene group, a 1,4-butylene group, a 1-ethylethylene group, a 1-methylpropylene group, a 2-methylpropylene group, a 1,5-pentylene group, a 1-methylbutylene group, a 2-methylbutylene group, a 1,1-dimethylpropylene group, a 1,2-dimethylpropylene group, a 1-ethylpropylene group, a 2-ethylpropylene group, a 1,6-hexylene group, a 1,4-cyclohexylene group, a 1,8-octylene group, a 2-ethyloctylene group, a 1,9-nonylene group, and a 1,10-decylene group.
• Examples of the structure represented by formula (P-1) include the following structures. (* represents a bond.)
• Examples of the aromatic ring having 6 to 40 carbon atoms in Q1 and Q2 include aromatic rings derived from benzene, naphthalene, anthracene, acenaphthene, fluorene, triphenylene, phenalene, phenanthrene, indene, indane, indacene, pyrene, chrysene, perylene, naphthacene, pentacene, coronene, heptacene, benzo[a]anthracene, dibenzophenanthrene, and dibenzo[a,j]anthracene.
• benzene, naphthalene, and anthracene are preferred.
• Examples of the divalent organic group containing an aromatic ring structure having 6 to 40 carbon atoms for Q1 and Q2 include divalent aromatic groups having 6 to 40 carbon atoms which may have a substituent.
• Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.
• Examples of -T 2 -L 2 -Q 2 -L 3 -T 3 - in formula (P) include the following divalent organic groups. (* represents a bond.)
• the polymer (A) may be, for example, a polymer described in WO2009/008446, WO2011/074494, WO2013/018802, etc., which are described below.
• R 1 represents a methoxy group, an alkyl group having 1 to 13 carbon atoms or a halogen atom
• n represents an integer from 0 to 4
• R 2 represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms or a halogen atom
• X represents an ether bond or an ester bond
• a 1 , A 2 , A 3 , A 4 , A 5 and A 6 each independently represent a hydrogen atom, a methyl group or an ethyl group
• Q represents a divalent organic group between two carbon atoms.
• X represents an ester bond or an ether bond
• a 1 , A 2 , A 3 , A 4 , A 5 , and A 6 each represent a hydrogen atom, a methyl group, or an ethyl group
• Q represents the following formula (2) or formula (3).
• Q1 represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group, and the phenylene group, naphthylene group, and anthrylene group may each be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms; n1 and n2 each represent the number 0 or 1; and X1 represents the following formula (4), (5), or (6).)
• R 1 and R 2 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a benzylene group
• a polymer having the structure of the following formula (1a) described in WO2013/018802 (In formula (1a), A 1 , A 2 , A 3 , A 4 , A 5 , and A 6 each represent a hydrogen atom, a methyl group, or an ethyl group; X 1 represents the following formula (2), (3), (4), or (0); and Q represents the following formula (5) or (6).)
• R 1 and R 2 each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 3 to 6 carbon atoms, the benzyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to
• Q 1 represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group
• the alkylene group, the phenylene group, the naphthylene group, and the anthrylene group may each be substituted with an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxy group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxyl group, or a group consisting of a combination thereof; n 1 and n 2 each represent the number 0 or 1; and X 2 represents formula (2), formula (3), formula (4), or formula (0).
• the polymer (A) may be a copolymer having a repeating structural unit represented by the following formula (1-1) and a repeating structural unit represented by the following formula (1-2).
• R 1 and R 2 each independently represent a divalent organic group containing a linear, branched or cyclic functional group having 2 to 20 carbon atoms
• the organic group may have at least one sulfur atom, nitrogen atom or oxygen atom
• i and j each independently represent 0 or 1
• polymer (A) With regard to polymer (A), the contents of the polymers described in WO2022/196662, WO2009/008446, WO2011/074494, WO2013/018802, WO2020/026834, and WO2022/071468 are all incorporated herein by reference to the same extent as if expressly set forth herein.
• the polymer (A) may have a structure represented by the following formula (E):
• the structure represented by formula (E) is located, for example, at an end (one end or both ends) of the polymer (A).
• Y represents a monovalent group.
• n11 represents 0 or 1.
• Examples of the monovalent group for Y in formula (E) include monovalent organic groups having 1 to 30 carbon atoms.
• Examples of Y in formula (E) include a monovalent residue in which one hydrogen atom has been removed from an aliphatic ring which may be substituted with a substituent, and a monovalent aromatic group which may be substituted with a substituent.
• Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.
• Examples of the aromatic group in the monovalent aromatic group which may be substituted with a substituent include aromatic hydrocarbon groups, such as a phenyl group, a naphthyl group, and an anthracenyl group.
• Examples of the compound represented by formula (EA) include the following compounds.
• the molecular weight of the polymer (A) is not particularly limited.
• the lower limit of the weight average molecular weight of the polymer (A) is, for example, 500, 1,000, 2,000, or 3,000.
• the upper limit of the weight average molecular weight of the polymer (A) is, for example, 30,000, 20,000, or 10,000.
• the content of the polymer (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 50% by mass to 99% by mass, more preferably 60% by mass to 95% by mass, and particularly preferably 65% by mass to 90% by mass, based on the film-constituting components.
• the film-constituting components refer to components other than the solvent contained in the composition.
• the compound (B) is a compound having a hydrophobic substituent. By adding the compound (B) to the composition for forming a resist underlayer film, the hydrophobicity of the resist underlayer film formed from the composition for forming a resist underlayer film can be increased.
• the compound (B) has a structure different from that of the polymer (A).
• the hydrophobic substituent that the compound (B) has is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, an optionally substituted aryl group or an optionally substituted alkyl group having 1 to 10 carbon atoms is preferable.
• Examples of the substituent in the optionally substituted aryl group include a hydroxy group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogenated alkoxy group having 1 to 10 carbon atoms, and an R x OC( ⁇ O)- group (R x represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having a total of 2 to 6 carbon atoms).
• Examples of the aryl group in the optionally substituted aryl group include a phenyl group and a naphthyl group.
• Examples of the substituent in the optionally substituted alkyl group having 1 to 10 carbon atoms include a hydroxy group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkoxy group having 1 to 10 carbon atoms, and a carboxy group.
• a hydroxy group and a carboxy group are hydrophilic groups, when a hydrophobic substituent is hydrophobic as a whole, the hydrophobic substituent may have a hydrophilic group.
• the compound (B) preferably has at least one group represented by the following formula (X) as a hydrophobic substituent.
• R 1 represents a monovalent group other than a hydrogen atom.
• n represents an integer of 0 to 5.
• R 1 is two or more, the two or more R 1 may be the same or different.
• R 1 in formula (X) examples include a hydroxy group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogenated alkoxy group having 1 to 10 carbon atoms, and an R x OC( ⁇ O)- group (R x represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having a total of 2 to 6 carbon atoms).
• Compound (B) has, for example, a group represented by formula (Q-1) below or a group represented by formula (Q-2) below.
• * represents a bond.
• X1 represents a single bond, an oxygen atom, or an alkylene group having 1 to 6 carbon atoms.
• compound (B) is preferably a compound represented by the following formula (Y).
• X1 represents a group having a valence of m.
• R 11 represents a hydrophobic substituent.
• L 1 represents a single bond or a divalent group.
• m represents an integer of 1 to 4. When there are two or more R 11 s, the two or more R 11 s may be the same or different. When L 1 is two or more, the two or more L 1 may be the same or different.
• hydrophobic substituent for R 11 in formula (Y) an optionally substituted aryl group or an optionally substituted alkyl group having 1 to 10 carbon atoms is preferred.
• the hydrophobic substituent is preferably a group represented by formula (X).
• L 1 in formula (Y) examples include a divalent group represented by the following formula (L).
• a 1 , A 2 , and A 3 each independently represent a hydrogen atom, a methyl group, or an ethyl group.
• p represents an integer of 0 or 1.
• *1 represents a bond bonded to R 11 in formula (Y).
• *2 represents a bond bonded to X1 in formula (Y).
• X1 in formula (Y) has, for example, a ring structure.
• the ring structure include an aromatic ring, an aliphatic ring, and a non-aromatic heterocyclic ring.
• the aromatic ring include a benzene ring and a naphthalene ring.
• the aliphatic ring include a cyclohexane ring.
• the non-aromatic heterocyclic ring include the ring structure represented by formula (Q-1) above.
• Examples of X 1 in formula (Y) include the following groups: In the following groups, * represents a bond.
• compound (B) is preferably at least one of a compound represented by formula (Y1) below and a compound represented by formula (Y2) below.
• R 21 to R 23 each independently represent a hydrophobic substituent.
• R 31 to R 34 each independently represent a hydrophobic substituent.
• X 1 represents a single bond, an oxygen atom, or an alkylene group having 1 to 6 carbon atoms.
• Examples of the compound (B) include the following compounds.
• the compound represented by formula (Y) can be obtained, for example, by reacting a compound represented by the following formula (Y-1) with at least one of a compound represented by the following formula (Y-2-1) and a compound represented by the following formula (Y-2-2).
• X1 represents a group having a valence of m.
• a 1 , A 2 and A 3 each independently represent a hydrogen atom, a methyl group or an ethyl group.
• m represents an integer of 1 to 4.
• R 11 represents a hydrophobic substituent.
• p represents an integer of 0 or 1.
• the hydrophobic substituent for R 11 in formula (Y-2-1) is preferably an optionally substituted aryl group or an optionally substituted alkyl group having 1 to 10 carbon atoms.
• the hydrophobic substituent is preferably a group represented by formula (X).
• R 12 represents a monovalent group other than a hydrogen atom.
• n represents an integer of 0 to 4.
• the two or more R 12 may be the same or different.
• R 12 in formula (Y-2-2) examples include a hydroxy group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogenated alkoxy group having 1 to 10 carbon atoms, and an R x OC( ⁇ O)- group (R x represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having a total of 2 to 6 carbon atoms).
• Examples of the compound represented by formula (Y-1) include the following compounds.
• Examples of the compound represented by formula (Y-2-1) and the compound represented by formula (Y-2-2) include the following compounds.
• At least one carboxy group in the compound represented by formula (Y-2-1) may be capped with a solvent when reacting the compound represented by formula (Y-1) with the compound represented by the following formula (Y-2-1).
• a solvent when reacting the compound represented by formula (Y-1) with the compound represented by the following formula (Y-2-1).
• An example of the solvent used for capping is alkylene glycol monoalkyl ether.
• the molecular weight of compound (B) is not particularly limited, but is preferably, for example, 500 to 3,000.
• the molecular weight of compound (B) is preferably smaller than the weight average molecular weight of polymer (A).
• the content of compound (B) in the composition for forming a resist underlayer film is not particularly limited, but from the viewpoint of optimally obtaining the effects of the present invention, it is preferably 1% by mass to 40% by mass, more preferably 2% by mass to 30% by mass, and particularly preferably 5% by mass to 20% by mass, relative to polymer (A).
• the content of the compound (B) in the composition for forming a resist underlayer film is not particularly limited, but is preferably 3% by mass to 100% by mass, more preferably 5% by mass to 75% by mass, and particularly preferably 10% by mass to 50% by mass, relative to the crosslinking agent (D).
• the solvent (C) is not particularly limited, and may be water or an organic solvent.
• the organic solvent include alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.
• the alkylene group of the alkylene glycol monoalkyl ether is, for example, an alkylene group having 2 to 4 carbon atoms.
• the alkyl group of the alkylene glycol monoalkyl ether is, for example, an alkyl group having 1 to 4 carbon atoms.
• the alkylene glycol monoalkyl ether may have, for example, 3 to 8 carbon atoms.
• Examples of the alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.
• the alkylene group of the monocarboxylic acid ester of an alkylene glycol monoalkyl ether may, for example, be an alkylene group having 2 to 4 carbon atoms.
• Examples of the alkyl group of the monocarboxylic acid ester of an alkylene glycol monoalkyl ether include alkyl groups having 1 to 4 carbon atoms.
• Examples of the monocarboxylic acid of the monocarboxylic acid ester of an alkylene glycol monoalkyl ether include saturated monocarboxylic acids having 2 to 4 carbon atoms.
• saturated monocarboxylic acids having 2 to 4 carbon atoms include acetic acid, propionic acid, and butyric acid.
• the monocarboxylic acid ester of an alkylene glycol monoalkyl ether may have, for example, 5 to 10 carbon atoms.
• Examples of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol propyl ether acetate.
• organic solvents include, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentan
• alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers are preferred.
• solvents (C) can be used alone or in combination of two or more.
• the mass ratio of the organic solvent in solvent (C) is not particularly limited, but is preferably 50% by mass to 100% by mass.
• the content of the solvent (C) in the composition for forming the 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 (D) is not particularly limited.
• the crosslinking agent (D) has a structure different from the polymer (A) and the compound (B).
• 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.
• Examples of the crosslinking agent (D) 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, for example, bonded to 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.
• crosslinking agent (D) melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, and compounds having a phenolic hydroxyl group are preferred. These can be used alone or in combination of two or more.
• melamine compounds include hexamethylol melamine, hexamethoxymethyl melamine, compounds in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated or mixtures thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, compounds in which 1 to 6 methylol groups of hexamethylol melamine are acyloxymethylated or mixtures thereof, etc.
• guanamine compounds include tetramethylol guanamine, tetramethoxymethyl guanamine, compounds in which one to four methylol groups of tetramethylol guanamine are methoxymethylated or mixtures thereof, tetramethoxyethyl guanamine, tetraacyloxyguanamine, compounds in which one to four methylol groups of tetramethylol guanamine are acyloxymethylated or mixtures thereof, etc.
• glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which one to four methylol groups of tetramethylol glycoluril are methoxymethylated or mixtures thereof, and compounds in which one to four methylol groups of tetramethylol glycoluril are acyloxymethylated or mixtures thereof.
• the glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E).
• the four R 1s each independently represent a methyl group or an ethyl group
• R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.
• glycoluril derivative represented by formula (1E) examples include compounds represented by the following formulas (1E-1) to (1E-6).
• the glycoluril derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).
• R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represent an alkyl group having 1 to 4 carbon atoms.
• R 1 represents a methyl group or an ethyl group.
• glycoluril derivative represented by formula (2E) examples include compounds represented by the following formulae (2E-1) to (2E-4).
• Examples of the compound represented by formula (3d) include compounds represented by the following formulae (3d-1) and (3d-2).
• urea compounds include tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea compounds in which one to four methylol groups are methoxymethylated or mixtures thereof, tetramethoxyethyl urea, etc.
• 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 from 2 to 10.
• Examples of the compound having a phenolic hydroxy group include the 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 from 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 Yukizai Kogyo Co., Ltd. and Honshu Chemical Industry Co., Ltd.
• An example of the product is TMOM-BP, a product name of Asahi Yukizai Kogyo Co., Ltd.
• glycoluril compounds are preferred, specifically tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, a compound in which one to four methylol groups of tetramethylol glycoluril are methoxymethylated or a mixture thereof, and a compound in which one to four methylol groups of tetramethylol glycoluril are acyloxymethylated or a mixture thereof, with tetramethoxymethyl glycoluril being more preferred.
• the molecular weight of the crosslinking agent (D) is not particularly limited, but is preferably 500 or less.
• the content of the crosslinking agent (D) in the composition for forming the resist underlayer film is not particularly limited, but is, for example, 1% by mass to 50% by mass, and preferably 5% by mass to 40% by mass, relative to the polymer (A).
• the curing catalyst (E) 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-hydroxybenzenesulf
• 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 nonafluoronormal butanesulfonate, diphenyliodonium perfluoronormal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium triflu
• 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 content of the curing catalyst (E) relative to the crosslinking agent (D) is, for example, 0.1% by mass to 50% by mass, and preferably 1% by mass 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, and the like, and to further improve the coatability against surface unevenness.
• surfactant examples include 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; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, and the like; nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan
• the amount of these surfactants to be added is usually 2.0% by mass or less, and preferably 1.0% by mass or less, based on the total solid content of the composition for forming a resist underlayer film.
• These surfactants may be added alone or in combination of two or more kinds.
• 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 water contact angle of the resist underlayer film formed from the composition for forming a resist underlayer film is, for example, 40° to 80°, 45° to 75°, or 50° to 70°.
• the resist underlayer film is, for example, a resist underlayer film having a thickness of 5 nm when a composition for forming a resist underlayer film is applied onto a silicon wafer and baked at 205° C. for 60 seconds.
• the water contact angle can be measured by the drop method using, for example, a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.).
• the resist underlayer 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-mentioned composition for forming a resist underlayer film onto a semiconductor substrate and baking the applied composition.
• Semiconductor substrates onto which the resist underlayer film forming composition is 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 is 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.
• the inorganic film include polysilicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium nitride oxide film, tungsten film, gallium nitride film, and gallium arsenide film.
• the resist underlayer film forming composition of the present invention is applied onto such a semiconductor substrate by a suitable 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.
• the baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes.
• the baking temperature is 120°C to 350°C
• the baking time is 0.5 minutes to 30 minutes
• the baking temperature is 150°C to 300°C
• the baking time is 0.8 minutes to 10 minutes.
• the water contact angle of the resist underlayer film is, for example, 40° to 80°, 45° to 75°, or 50° to 70°.
• the water contact angle can be measured by the drop method using, for example, a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.).
• the thickness of the resist underlayer film may 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 (5 nm) to 0.05 ⁇ m (5 0 nm), 0.003 ⁇ m (3 nm) to 0.03 ⁇ m (30 nm), 0.003 ⁇ m (3 nm) to 0.02 ⁇ m (20 nm), 0.005 ⁇ m (5 nm) to 0.02 ⁇ m (20 nm),
• the method for measuring the film thickness of the resist underlayer film is as follows.
• 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, for example, on 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.
• a step of etching the resist underlayer film using the resist pattern as a mask includes at least the following steps.
• a resist layer is formed on the resist underlayer film.
• the thickness of the resist layer is preferably 200 nm or less, more preferably 150 nm or less, even more preferably 100 nm or less, and particularly preferably 80 nm or less.
• the thickness of the resist layer is preferably 10 nm or more, more preferably 20 nm or more, and particularly preferably 30 nm or more.
• the resist 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 called 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 with acid to increase the alkaline dissolution rate and a photoacid generator, chemically amplified photoresists made of a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, chemically amplified photoresists made of a binder having a group that decomposes with acid to increase the alkaline dissolution rate of the photoresist, a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator, and resists containing metal elements.
• V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. may be mentioned.
• 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 an 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, the metal element constituting the compound belonging 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 is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms.
• R 1 is a hydroxy group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms.
• n is an integer from 0 to 11. When n is 2 or more, multiple R 1s are the same or different.
• R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• R 3 is a monovalent group having 1 to 20 carbon atoms containing the above-mentioned acid dissociable group.
• Z is a single bond, an oxygen atom, or a sulfur atom.
• R 4 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• R 2 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom
• X 1 represents a single bond, -CO-O-* or -CO-NR 4 -*
• * represents a bond to -Ar
• R 4 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 hydroxyl group and a carboxyl 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 is each independently a hydrogen atom or a methyl group.
• R 1 and R 2 are each independently a tertiary alkyl group having 4 to 6 carbon atoms.
• R 3 is each independently a fluorine atom or a methyl group.
• m is an integer of 0 to 4.
• X 1 is a single bond, a phenylene group or a naphthylene group, or a linking group having 1 to 12 carbon atoms 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 is a hydrogen atom or a methyl group.
• X 1 is a single bond or an ester group.
• X 2 is a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, a part 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 is a single bond, an ether group, an ester group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, a part 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 of them is a fluorine atom or a trifluoromethyl group.
• Rf 1 and Rf 2 may combine to form a carbonyl group.
• R 1 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 of 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 is a hydrogen atom or a methyl group.
• R 1 is a hydrogen atom or an acid labile group.
• R 2 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine.
• X 1 is 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 is -O-, -O-CH 2 - or -NH-.
• m is an integer of 1 to 4.
• u is an integer of 0 to 3, with the proviso that m+u is an integer of 1 to 4.
• a resist composition which generates an acid upon exposure and changes its solubility in a developer by 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) having a structural unit (f1) containing a base dissociable group, and a structural unit (f2) containing a group represented by the following general formula (f2-r-1):
• Rf 21 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a hydroxyalkyl group, or a cyano group.
• n′′ is 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).
• R is each 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.
• R 2 is each independently an organic group having a fluorine atom.
• coatings examples include the following:
• a coating comprising a metal oxo-hydroxo network with organic ligands via metal carbon bonds and/or metal carboxylate bonds.
• RzSnO (2-(z/2)-(x/2)) (OH) x , where 0 ⁇ z ⁇ 2 and 0 ⁇ (
• a coating solution comprising an organic solvent and a first organometallic compound having the formula RSnO (3/2-x/2) (OH) x , where 0 ⁇ x ⁇ 3, wherein the solution contains from about 0.0025M to about 1.5M tin, and R is an alkyl or cycloalkyl group having 3 to 31 carbon atoms, the alkyl or cycloalkyl group being bonded to the tin at a secondary or tertiary carbon atom.
• An aqueous inorganic pattern forming precursor solution comprising water, a mixture of metal suboxide cations, polyatomic inorganic anions, and a radiation sensitive ligand comprising a peroxide group.
• Irradiation with light or electron beams is performed, 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.
• baking Post Exposure Bake
• the baking temperature is not particularly limited, but is preferably from 60°C to 150°C, more preferably from 70°C to 120°C, and particularly preferably from 75°C to 110°C.
• the baking time is not particularly limited, but is preferably from 1 second to 10 minutes, more preferably from 10 seconds to 5 minutes, and particularly preferably from 30 seconds to 3 minutes.
• an alkaline developer is used.
• the development temperature is, for example, from 5°C to 50°C.
• the development time may be, for example, from 10 seconds to 300 seconds.
• alkaline developer for example, aqueous solutions of alkalis such as inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and cyclic amines such as pyrrole and piperidine can be used.
• alkalis
• an appropriate amount of alcohols such as isopropyl alcohol and a nonionic surfactant can be added to the aqueous solution of the above-mentioned alkalis.
• preferred developers are aqueous solutions of quaternary ammonium salts, more preferably aqueous solutions of tetramethylammonium hydroxide and aqueous solutions of choline.
• surfactants and the like can be added to these developers.
• a method can also be used in which development is performed with an organic solvent such as butyl acetate instead of an alkaline developer to develop the parts of the photoresist where the alkaline dissolution rate is not improved.
• the resist underlayer film is etched using the formed resist pattern as a mask.
• the etching may be dry etching or wet etching, but is preferably dry etching.
• the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and when the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed.
• the semiconductor substrate is then processed by a known method (e.g., dry etching) to produce a semiconductor element.
• the weight average molecular weights of the polymers shown in the following Synthesis Examples 1 to 10 and Comparative Synthesis Example 1 in this specification are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC).
• GPC gel permeation chromatography
• a GPC device manufactured by Tosoh Corporation was used, and the measurement conditions etc. are as follows.
• Standard sample polystyrene (manufactured by Tosoh Corporation)
• polymer 2 had a weight average molecular weight of 3,800 and a dispersity of 2.5 in terms of standard polystyrene.
• the structure present in polymer 2 is shown in the following formula.
• the structure present in polymer 3 is shown in the following formula.
• the structure present in polymer 4 is shown in the following formula.
• Comparative Synthesis Example 1 100.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemical Industry Co., Ltd.), 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. 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. When GPC analysis was performed, 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.
• compositions for forming resist underlayer film (Examples and Comparative Examples)
• the polymers, crosslinking agents, curing catalysts, and solvents obtained in Synthesis Examples 1 to 10 and Comparative Synthesis Example 1 were mixed in the ratios shown in Tables 1-1 and 1-2 so that the solid content was about 0.19% by mass, and the mixture was filtered through a 0.1 ⁇ m fluororesin filter to prepare compositions for forming resist underlayer films.
• PL-LI Tetramethoxymethylglycoluril
• PGME-PL Imidaz[4,5-d]imidazole-2,5(1H,3H)-dione,tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl]- (structural formula below)
• PyPSA Pyridinium-p-hydroxybenzenesulfonic acid
• R-30N Surfactant (manufactured by DIC Corporation)
• PGMEA propylene glycol monomethyl ether acetate
• PGME propylene glycol monomethyl ether The amount of each added is shown in parts by mass, and the solvent is shown in composition ratio.
• resist patterning evaluation [Resist pattern formation test using an electron beam lithography device]
• Each of the resist underlayer film forming compositions of Examples 1 to 10, Comparative Example 1, and Comparative Example 2 was applied onto 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 film thickness of 5 nm.
• a positive resist solution for EUV was spin-coated onto the resist underlayer film, and heated at 105°C for 60 seconds to form an EUV resist film.
• the resist film was exposed under predetermined conditions using an electron beam lithography device (ELS-G130).
• the film was baked (PEB) at 95°C for 60 seconds, cooled to room temperature on a cooling plate, and paddle development was performed for 30 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., product name NMD-3) as a photoresist developer.
• a resist pattern with a line size of 18 nm to 32 nm was formed.
• a scanning electron microscope manufactured by Hitachi High-Technologies Corporation, CG4100 was used to measure the length of the resist pattern.
• the photoresist pattern thus obtained was subjected to the formation of 28 nm lines and spaces (L/S).

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