Classifications

• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
• • 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
• • 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

Definitions

• the present invention relates to a composition for forming a resist underlayer film, a method for producing a semiconductor substrate, and a polymer for forming a resist underlayer film.
• a multi-layer resist process in which a resist pattern is formed by exposing and developing a resist film that is laminated on a substrate via a resist underlayer film such as an organic underlayer film or a silicon-containing film.
• a resist underlayer film such as an organic underlayer film or a silicon-containing film.
• the resist underlayer film is etched using this resist pattern as a mask, and the substrate is further etched using the resulting resist underlayer film pattern as a mask, thereby forming a desired pattern on the semiconductor substrate.
• the resist underlayer film is required to have resistance to the solvent in the resist composition, and pattern rectangularity that suppresses pattern tailing at the bottom of the resist film and ensures the rectangularity of the resist pattern.
• the present invention was made based on the above circumstances, and its purpose is to provide a composition for forming a resist underlayer film capable of forming a resist underlayer film having excellent solvent resistance and pattern rectangularity, a method for manufacturing a semiconductor substrate, and a polymer for forming a resist underlayer film.
• the present invention comprises: A polymer (hereinafter also referred to as “polymer (A)”) having a repeating unit represented by the following formula (1) (hereinafter also referred to as “repeating unit (1)”) or a repeating unit represented by the following formula (2) (hereinafter also referred to as “repeating unit (2)”),
• the present invention relates to a composition for forming a resist underlayer film, comprising:
• Ar 1 is a divalent group having an aromatic ring with 6 to 20 ring members.
• R A is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.
• Ar 1 is a divalent group having an aromatic ring having 6 to 20 ring members.
• the present invention provides a method for producing a pharmaceutical composition comprising the steps of: A step of directly or indirectly applying a composition for forming a resist underlayer film to a substrate; a step of applying a composition for forming a resist film to the resist underlayer film formed by the above-mentioned step of applying a composition for forming a resist underlayer film; a step of exposing the resist film formed by the resist film-forming composition application step to radiation; and developing at least the exposed resist film.
• composition for forming a resist underlayer film A polymer having a repeating unit represented by the following formula (1) or a repeating unit represented by the following formula (2), A method for manufacturing a semiconductor substrate, comprising:
• Ar 1 is a divalent group having an aromatic ring having 6 to 20 ring members.
• R A is a divalent organic group.
• Ar 1 is a divalent group having an aromatic ring having 6 to 20 ring members.
• R 1 and R 3 are each independently a substituted or unsubstituted trivalent hydrocarbon group having 1 to 20 carbon atoms.
• R 2 and R 4 are each independently a hydroxy group or a monovalent organic group.
• L 1 and L 2 are each independently a single bond or a divalent linking group.
• R B is a divalent organic group.
• the present invention provides a method for producing a pharmaceutical composition comprising the steps of:
• the present invention relates to a polymer for forming a resist underlayer film, which is obtained by reacting a compound represented by the following formula ( ⁇ ) with a compound represented by the following formula ( ⁇ 1) or a compound represented by the following formula ( ⁇ 2):
• Ar 1 is a divalent group having an aromatic ring having 6 to 20 ring members.
• R A is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.
• R 1a and R 3a are each independently a monovalent group having an epoxy structure or an oxetane structure.
• R 1B is a divalent organic group having 1 to 20 carbon atoms.
• number of ring members refers to the number of atoms constituting the ring.
• a biphenyl ring has 12 ring members
• a naphthalene ring has 10 ring members
• a fluorene ring has 13 ring members.
• organic group refers to a group having at least one carbon atom.
• the composition for forming a resist underlayer film can form a film that is excellent in solvent resistance and pattern rectangularity.
• the method for manufacturing a semiconductor substrate uses a composition for forming a resist underlayer film that can form a resist underlayer film that is excellent in solvent resistance and pattern rectangularity, so that a semiconductor substrate can be manufactured efficiently.
• the polymer for forming a resist underlayer film is suitable for use in a composition for forming a resist underlayer film. Therefore, they can be suitably used in the manufacture of semiconductor devices, etc.
• composition for forming a resist underlayer film the method for producing a semiconductor substrate, and the polymer for forming a resist underlayer film according to each embodiment of the present invention will be described in detail. Combinations of preferred aspects in the embodiments are also preferred.
• composition for forming a resist underlayer film contains a polymer (A) and a solvent (B).
• the composition may contain any optional components within a range that does not impair the effects of the present invention.
• compositions for forming a resist film include a positive or negative chemically amplified resist composition containing a radiation-sensitive acid generator, a positive resist composition containing an alkali-soluble resin and a quinone diazide-based photosensitizer, a negative resist composition containing an alkali-soluble resin and a crosslinker, and a metal-containing resist composition containing metals such as tin, zirconium, and hafnium.
• the underlayer film formed by the composition contains a polymer [A] containing many aromatic rings in the main chain, so that in the development process after exposure to extreme ultraviolet rays, the organic resist film and the metal-containing resist film have sufficient developer solubility in the interface region on the underlayer film side, and the rectangularity of the resist pattern can be ensured by suppressing the tailing of the pattern at the bottom of the resist film.
• the underlayer film formed by the composition contains a polymer [A] also having a urethane bond or an ether bond, so that the solvent resistance of the resist composition can be ensured.
• the lower limit of the content of the metal or metal compound in the components other than the solvent in the metal-containing resist composition is preferably 50% by mass, more preferably 70% by mass, even more preferably 80% by mass, and particularly preferably 85% by mass.
• the upper limit of the content is, for example, 100% by mass or 95% by mass.
• the polymer [A] has the repeating unit (1) or repeating unit (2).
• the polymer [A] can contain one or more types of the repeating unit (1) or the repeating unit (2).
• the composition may contain a combination of the polymer [A] having the repeating unit (1) and the polymer [A] having the repeating unit (2).
• the polymer [A] may have a repeating unit other than the repeating unit (1) and the repeating unit (2).
• the composition may contain one or more types of the polymer [A].
• the polymer preferably has at least one halogen atom per repeating unit, and more preferably has two, three or four halogen atoms.
• halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Among them, fluorine atoms and iodine atoms are preferred as halogen atoms, and iodine atoms are more preferred.
• This can increase the efficiency of secondary electron generation due to absorption of extreme ultraviolet rays, and can cause a sufficient solubility difference in the interface region on the lower layer film side of the organic resist film during exposure to extreme ultraviolet rays, or can promote the insolubilization of the metal-containing resist film. As a result, the pattern tailing at the bottom of the resist film can be suppressed, and the rectangularity of the resist pattern can be ensured.
• the repeating unit (1) is represented by the following formula (1).
• Ar 1 is a divalent group having an aromatic ring with 6 to 20 ring members.
• R A is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.
• examples of the aromatic ring having 6 to 20 ring members in Ar 1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, an indene ring, a pyrene ring, and a fluorene ring, aromatic heterocycles such as a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring, and combinations thereof.
• the aromatic ring in Ar 1 is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring, a fluorene ring, or a combination thereof.
• preferred examples of the divalent group having an aromatic ring having 6 to 20 ring members represented by Ar 1 include a group in which two hydrogen atoms have been removed from the aromatic ring having 6 to 20 ring members in Ar 1 (hereinafter also referred to as "group (i)”), and a group in which the group (i) is combined with a divalent linking group not containing an aromatic ring (hereinafter also referred to as “group (ii)”) (hereinafter also referred to as "group (iii)").
• Examples of the group (ii) include a divalent linear or branched chain hydrocarbon group having 1 to 20 carbon atoms; a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms; a divalent heteroatom-containing linking group; a group having the above-mentioned divalent heteroatom-containing linking group between carbon atoms of a chain or alicyclic hydrocarbon group; or a group formed by combining two or more of these groups.
• Examples of the divalent linear or branched hydrocarbon group having 1 to 20 carbon atoms include alkanediyl groups having 1 to 20 carbon atoms, such as methanediyl group, ethanediyl group, propanediyl group, butanediyl group, and hexanediyl group; alkenediyl groups having 2 to 20 carbon atoms, such as ethenediyl group and propenediyl group; and alkynediyl groups having 2 to 20 carbon atoms, such as ethynediyl group and propynediyl group. Among these, alkanediyl groups having 1 to 5 carbon atoms are preferred.
• Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic cycloalkanediyl groups such as cyclopentanediyl groups and cyclohexanediyl groups; and polycyclic cycloalkanediyl groups such as norbornanediyl groups and adamantanediyl groups. Among these, cycloalkanediyl groups having 5 to 12 carbon atoms are preferred.
• Examples of the divalent heteroatom-containing linking group include -CO-, -CS-, -NR'-, -O-, -S-, -SO 2 - and combinations of these, etc.
• R' is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
• Ar 1 is preferably a divalent group having an aromatic ring having 6 to 20 ring members substituted with at least one halogen atom.
• the number of halogen atoms in Ar 1 is preferably 2, 3 or 4.
• Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Among them, iodine atoms are preferable as halogen atoms. This can increase the efficiency of secondary electron generation due to absorption of extreme ultraviolet rays, and can improve the rectangularity of the resist pattern by suppressing the tailing of the pattern at the bottom of the resist film.
• the multiple halogen atoms may be present on the same aromatic ring or on different aromatic rings.
• Examples of the substituent that the divalent group represented by Ar1 may have include, in addition to the above-mentioned halogen atoms, monovalent chain hydrocarbon groups having 1 to 10 carbon atoms, alkoxy groups such as a methoxy group, an ethoxy group, and a propoxy group, alkoxycarbonyl groups such as a methoxycarbonyl group and an ethoxycarbonyl group, alkoxycarbonyloxy groups such as a methoxycarbonyloxy group and an ethoxycarbonyloxy group, acyl groups such as a formyl group, an acetyl group, a propionyl group, and a butyryl group, a hydroxy group, a cyano group, a nitro group, an amino group, a sulfanyl group, and a carboxy group.
• alkoxycarbonyl groups such as a methoxycarbonyl group and an ethoxycarbonyl group
• examples of the substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms represented by R A include divalent linear or branched chain hydrocarbon groups having 1 to 20 carbon atoms; divalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, or combinations thereof.
• the divalent linear or branched chain hydrocarbon group having 1 to 20 carbon atoms in R A As the divalent linear or branched chain hydrocarbon group having 1 to 20 carbon atoms in R A , the above-mentioned divalent linear or branched hydrocarbon group having 1 to 20 carbon atoms in group (ii) can be suitably used.
• the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms for R 3 A can be suitably used.
• divalent aromatic hydrocarbon group having 6 to 20 carbon atoms for R 3 A a group corresponding to the aromatic hydrocarbon among the above groups (i) can be suitably adopted.
• R A preferably contains a substituted or unsubstituted divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
• a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms in R A a cycloalkanediyl group having 5 to 12 carbon atoms is preferable, and a cyclopentanediyl group or a cyclohexanediyl group is more preferable.
• a benzenediyl group is preferable.
• R A has a substituent
• the above-mentioned substituents which Ar 1 may have can be suitably adopted as the substituent.
• repeating unit (1) include repeating units represented by the following formulas (1-1) to (1-18).
• the other repeating unit includes a repeating unit represented by the following formula (3) (hereinafter, also referred to as “repeating unit (3)").
• R C is a divalent organic group having 1 to 20 carbon atoms and no aromatic ring.
• the divalent organic group having 1 to 20 carbon atoms and no aromatic ring represented by R C the group (ii) in Ar 1 in the above formula (1) can be suitably adopted.
• R C a divalent linear or branched chain hydrocarbon group having 1 to 20 carbon atoms or a combination thereof with a divalent heteroatom-containing linking group is preferable.
• repeating unit (3) include repeating units represented by the following formulas (3-1) to (3-6).
• the method for producing the polymer [A] having the repeating unit (1) is not particularly limited.
• the polymer [A] can be obtained by reacting (polyaddition) a compound represented by the following formula ( ⁇ ) (hereinafter also referred to as "compound ( ⁇ )”) with a compound represented by the following formula ( ⁇ 1) (hereinafter also referred to as “compound ( ⁇ 1)”): (In formula ( ⁇ ) and formula ( ⁇ 1), Ar 1 and R A are the same as those in formula (1) above.)
• the lower limit of the molar ratio (( ⁇ )/( ⁇ 1)) of the number of moles of compound ( ⁇ ) to the number of moles of compound ( ⁇ 1) is preferably 0.1, more preferably 0.5.
• the upper limit of the molar ratio (( ⁇ )/( ⁇ 1)) is preferably 0.9, more preferably 0.5.
• the compound ( ⁇ ), the compound ( ⁇ 1), and a compound represented by the following formula ( ⁇ ) may be subjected to a polyaddition reaction.
• compound ( ⁇ ) a compound represented by the following formula ( ⁇ ) (hereinafter also referred to as “compound ( ⁇ )”) may be subjected to a polyaddition reaction.
• R C has the same meaning as in formula (3) above.
• the content of compound ( ⁇ ) should be such that the ratio of the total number of moles of compound ( ⁇ ) and compound ( ⁇ ) to the number of moles of compound ( ⁇ 1) ( ⁇ ( ⁇ )+( ⁇ ) ⁇ /( ⁇ 1)) falls within the above range of molar ratio (( ⁇ )/( ⁇ 1)).
• the solvent [B] described below can be used as the reaction solvent.
• the lower limit of the reaction temperature is preferably 40°C, more preferably 60°C.
• the upper limit of the reaction temperature is preferably 140°C, more preferably 100°C.
• the lower limit of the reaction time is preferably 1 hour, more preferably 4 hours.
• the upper limit of the reaction time is preferably 24 hours, more preferably 12 hours.
• the polymer (A) has the repeating unit (2) described above.
• the repeating unit (2) is represented by the following formula (2).
• Ar 1 is a divalent group having an aromatic ring having 6 to 20 ring members.
• R 1 and R 3 are each independently a substituted or unsubstituted trivalent hydrocarbon group having 1 to 20 carbon atoms.
• R 2 and R 4 are each independently a hydroxy group or a monovalent organic group.
• L 1 and L 2 are each independently a single bond or a divalent linking group.
• R B is a divalent organic group having 1 to 20 carbon atoms.
• R 1 and R 3 are each preferably a substituted or unsubstituted trivalent linear hydrocarbon group having 1 to 20 carbon atoms or a substituted or unsubstituted trivalent alicyclic hydrocarbon group having 3 to 20 carbon atoms.
• R 1 and R 3 are each preferably an alkanetriyl group having 3 to 8 carbon atoms or a cycloalkanetriyl group having 5 to 10 carbon atoms, and more preferably a propanetriyl group, a butanetriyl group, or a cyclohexanetriyl group.
• Examples of the monovalent organic group represented by R2 and R4 include a monovalent hydrocarbon group having 1 to 20 carbon atoms, a group having a divalent heteroatom-containing linking group between the carbon atoms of this hydrocarbon group, a group in which some or all of the hydrogen atoms of the above-mentioned hydrocarbon group have been substituted with substituents, or a combination of these, etc.
• the organic group is a group having at least one carbon atom.
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms for R2 and R4 include a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof.
• Examples of monovalent chain hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and neopentyl; alkenyl groups such as ethenyl, propenyl, and butenyl; and alkynyl groups such as ethynyl, propynyl, and butynyl.
• Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopentyl and cyclohexyl groups; cycloalkenyl groups such as cyclopropenyl, cyclopentenyl and cyclohexenyl groups; bridged ring saturated hydrocarbon groups such as norbornyl, adamantyl and tricyclodecyl groups; and bridged ring unsaturated hydrocarbon groups such as norbornenyl and tricyclodecenyl groups.
• Examples of monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl, tolyl, naphthyl, anthracenyl, and pyrenyl groups.
• the divalent heteroatom-containing linking group in R2 and R4 the divalent heteroatom-containing group shown as the group (ii) in Ar1 in the above formula (1) can be suitably adopted.
• R 2 and R 4 each independently have a group containing at least one group selected from the group consisting of a hydroxy group, a group represented by the following formula (2-1), and a group represented by the following formula (2-2).
• R 7 is each independently a divalent organic group having 1 to 20 carbon atoms or a single bond. * represents a bond to an atom constituting R 2 or R 4.
• R7 is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably a methanediyl group, an ethanediyl group, a propanediyl group, a benzenediyl group, or a combination thereof.
• the divalent linking group represented by L 1 and L 2 the group (i), group (ii) and group (iii) in Ar 1 of the above formula (1) can be suitably adopted.
• L 1 and L 2 a single bond or -O- is preferable.
• R B As the divalent organic group having 1 to 20 carbon atoms represented by R B , the groups (i), (ii) and (iii) in Ar 1 of the above formula (1) can be suitably adopted.
• R B a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon ring having 6 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a divalent linear or branched chain hydrocarbon group having 1 to 20 carbon atoms, or a combination of these with a divalent heteroatom-containing linking group is preferred, and an arenediyl group having 6 to 12 carbon atoms, a cycloalkanediyl group having 5 to 12 carbon atoms, a linear or branched alkanediyl group having 1 to 10 carbon atoms, or a combination of these with a divalent heteroatom-containing linking group is more preferred.
• repeating unit (2) include repeating units represented by the following formulas (2-1) to (2-15).
• the other repeating units include the repeating unit (3) above.
• the method for producing the polymer [A] having the repeating unit (2) is not particularly limited.
• the polymer [A] can be obtained by reacting (polyaddition) a compound represented by the following formula ( ⁇ ) (i.e., the above-mentioned compound ( ⁇ )) with a compound represented by the following formula ( ⁇ 2) (hereinafter, also referred to as “compound ( ⁇ 2)”).
• ⁇ a compound represented by the following formula ( ⁇ 2)
• Ar 1 and R B are the same as defined in formula (2) above.
• R 1a and R 3a each independently represent a monovalent group having an epoxy structure or an oxetane structure.
• the monovalent groups having an epoxy structure or an oxetane structure represented by R 1a and R 3a are not particularly limited as long as the structures of the R 1 -L 1 -R 2 moiety and the R 3 -L 2 -R 4 moiety in the above formula (2) are obtained when the epoxy structure or the oxetane structure is opened by an addition reaction between the hydroxy group of the compound ( ⁇ ) and the epoxy structure or the oxetane structure of the compound ( ⁇ 2 ) .
• a glycidyl group, a glycidylmethyl group, an oxetanylmethyl group, an oxetanylethyl group, a 3,4-epoxycyclohexylmethyl group, a 3,4-epoxycyclohexylethyl group, and groups substituted with these groups and the like are preferable.
• the substituent the above-mentioned substituents which Ar 1 in the above formula (1) may have can be suitably adopted.
• the lower limit of the molar ratio (( ⁇ )/( ⁇ 2)) of the number of moles of compound ( ⁇ ) to the number of moles of compound ( ⁇ 2) is preferably 0.1, more preferably 0.5.
• the upper limit of the molar ratio (( ⁇ )/( ⁇ 2)) is preferably 0.9, more preferably 0.5.
• the compound ( ⁇ ), the compound ( ⁇ 2), and the compound ( ⁇ ) may be subjected to a polyaddition reaction.
• the method for introducing a group containing at least one group selected from the group represented by the formula (2-1) and the group represented by the formula (2-2) is not particularly limited, and a method of reacting a hydroxy group generated when the epoxy structure or oxetane structure is ring-opened with a halide containing at least one group selected from the group represented by the formula (2-1) and the group represented by the formula (2-2) can be preferably used.
• the content of compound ( ⁇ ) should be such that the ratio of the total number of moles of compound ( ⁇ ) and compound ( ⁇ ) to the number of moles of compound ( ⁇ 2) ( ⁇ ( ⁇ )+( ⁇ ) ⁇ /( ⁇ 2)) falls within the above range of molar ratio (( ⁇ )/( ⁇ 2)).
• reaction solvent, reaction temperature, and reaction temperature may be suitably selected from the production conditions for polymer [A] in the first embodiment.
• the solvent (B) is not particularly limited as long as it can dissolve or disperse the polymer (A) and any optional components contained as necessary.
• Solvents include, for example, hydrocarbon solvents, ester solvents, alcohol solvents, ketone solvents, ether solvents, nitrogen-containing solvents, etc. [B] Solvents can be used alone or in combination of two or more.
• hydrocarbon solvents examples include aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene.
• ester solvents include carbonate solvents such as diethyl carbonate, acetate monoester solvents such as methyl acetate and ethyl acetate, lactone solvents such as ⁇ -butyrolactone, polyhydric alcohol partial ether carboxylate solvents such as diethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, and lactate ester solvents such as methyl lactate and ethyl lactate.
• carbonate solvents such as diethyl carbonate
• acetate monoester solvents such as methyl acetate and ethyl acetate
• lactone solvents such as ⁇ -butyrolactone
• polyhydric alcohol partial ether carboxylate solvents such as diethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate
• lactate ester solvents such as methyl lactate and ethyl lactate.
• alcohol-based solvents examples include monoalcohol-based solvents such as methanol, ethanol, n-propanol, 4-methyl-2-pentanol, and 2,2-dimethyl-1-propanol, and polyhydric alcohol-based solvents such as ethylene glycol and 1,2-propylene glycol.
• Ketone solvents include, for example, chain ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone, and cyclic ketone solvents such as cyclohexanone.
• ether solvents include chain ether solvents such as n-butyl ether, polyhydric alcohol ether solvents such as cyclic ether solvents such as tetrahydrofuran, and polyhydric alcohol partial ether solvents such as diethylene glycol monomethyl ether and propylene glycol monomethyl ether.
• nitrogen-containing solvents examples include chain nitrogen-containing solvents such as N,N-dimethylacetamide, and cyclic nitrogen-containing solvents such as N-methylpyrrolidone.
• ketone solvents As the solvent, ketone solvents, ether solvents, or ester solvents are preferred, cyclic ketone solvents, polyhydric alcohol partial ether solvents, or polyhydric alcohol partial ether carboxylate solvents are more preferred, and cyclohexanone, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are even more preferred.
• the resist underlayer film forming composition may contain optional components within a range that does not impair the effects of the present invention.
• the optional components include a crosslinking agent, an acid generator, a dehydrating agent, an acid diffusion control agent, a surfactant, etc.
• the optional components may be used alone or in combination of two or more.
• the content of the optional components in the total mass of the polymer [A] and the optional components is preferably 30 mass% or less, and more preferably 20 mass% or less.
• composition for forming a resist underlayer film can be prepared by mixing the polymer [A], the solvent [B], and, if necessary, any optional components in a predetermined ratio, and filtering the resulting mixture preferably through a membrane filter or the like having a pore size of 0.5 ⁇ m or less.
• the method for manufacturing a semiconductor substrate includes a step of directly or indirectly applying a composition for forming a resist underlayer film to a substrate (hereinafter also referred to as a “coating step (I)”), a step of applying a composition for forming a resist film to the resist underlayer film formed by the above-mentioned coating step of the composition for forming a resist film (hereinafter also referred to as a “coating step (II)”), a step of exposing the resist film formed by the above-mentioned coating step of the composition for forming a resist film to radiation (hereinafter also referred to as an "exposure step”), and a step of developing at least the exposed resist film (hereinafter also referred to as a "development step”).
• a resist underlayer film having excellent solvent resistance and pattern rectangularity can be formed by using a specific composition for forming a resist underlayer film in the coating step (I), and thus a semiconductor substrate having a good pattern shape can be manufactured.
• the method for manufacturing a semiconductor substrate preferably further includes a step of heating the resist underlayer film formed by the resist underlayer film forming composition application step at 200°C or higher (hereinafter also referred to as the "heating step") prior to the application step (II).
• the method for manufacturing the semiconductor substrate may further include, as necessary, a step of forming a silicon-containing film directly or indirectly on the substrate prior to the coating step (I) (hereinafter also referred to as the "silicon-containing film forming step").
• the method includes the heating step, which is a preferred step, and the silicon-containing film formation step, which is an optional step.
• Silicon-containing film formation process In this step, which is carried out prior to the above coating step (I), a silicon-containing film is formed directly or indirectly on a substrate.
• the substrate may be, for example, a metal or semimetal substrate such as a silicon substrate, an aluminum substrate, a nickel substrate, a chromium substrate, a molybdenum substrate, a tungsten substrate, a copper substrate, a tantalum substrate, or a titanium substrate, and among these, a silicon substrate is preferred.
• the substrate may be a substrate on which a silicon nitride film, an alumina film, a silicon dioxide film, a tantalum nitride film, a titanium nitride film, or the like is formed.
• the silicon-containing film can be formed by coating a silicon-containing film-forming composition, chemical vapor deposition (CVD), atomic layer deposition (ALD), or the like.
• methods for forming a silicon-containing film by coating a silicon-containing film-forming composition include a method in which the silicon-containing film-forming composition is directly or indirectly coated on a substrate, and the coated film is then cured by exposure and/or heating.
• Examples of commercially available silicon-containing film-forming compositions include "NFC SOG01", “NFC SOG04", and "NFC SOG080” (all from JSR Corporation).
• Silicon oxide films, silicon nitride films, silicon oxynitride films, and amorphous silicon films can be formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).
• Radiation used for the above-mentioned exposure includes, for example, electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, X-rays, and gamma rays, as well as particle beams such as electron beams, molecular beams, and ion beams.
• the lower limit of the temperature when heating the coating film is preferably 90°C, more preferably 150°C, and even more preferably 200°C.
• the upper limit of the above temperature is preferably 550°C, more preferably 450°C, and even more preferably 300°C.
• the lower limit of the average thickness of the silicon-containing film is preferably 1 nm, more preferably 10 nm, and even more preferably 15 nm.
• the upper limit is preferably 20,000 nm, more preferably 1,000 nm, and even more preferably 100 nm.
• the average thickness of the silicon-containing film can be measured in the same manner as the average thickness of the resist underlayer film.
• Examples of forming a silicon-containing film indirectly on a substrate include forming a silicon-containing film on a low dielectric insulating film or an organic underlayer film formed on a substrate.
• the composition for forming resist underlayer film is coated on the silicon-containing film formed on the substrate.
• the coating method of the composition for forming resist underlayer film is not particularly limited, and can be carried out by suitable methods such as spin coating, casting coating, roll coating, etc.This forms a coating film, and the solvent [B] volatilizes, etc., to form a resist underlayer film.
• the lower limit of the average thickness of the resist underlayer film formed is preferably 0.5 nm, more preferably 1 nm, and even more preferably 2 nm.
• the upper limit of the average thickness is preferably 50 nm, more preferably 20 nm, even more preferably 10 nm, and particularly preferably 7 nm.
• the method for measuring the average thickness is as described in the Examples.
• the silicon-containing film forming step can be omitted.
• the coating film may be heated in an air atmosphere or in a nitrogen atmosphere.
• the lower limit of the heating temperature may be 180°C, but 200°C is preferred, 210°C is more preferred, and 220°C is even more preferred.
• the upper limit of the heating temperature is preferably 400°C, 350°C is more preferred, and 280°C is even more preferred.
• the lower limit of the heating time is preferably 15 seconds, and 30 seconds is more preferred.
• the upper limit of the heating time is preferably 800 seconds, 400 seconds is more preferred, and 200 seconds is even more preferred.
• a composition for forming a resist film is applied to the resist underlayer film formed in the above-mentioned step of applying the composition for forming a resist film.
• the method for applying the composition for forming a resist film is not particularly limited, and examples thereof include a rotational coating method.
• a resist composition is applied so that the resist film to be formed has a predetermined thickness, and then the resist film is formed by pre-baking (hereinafter also referred to as "PB") to volatilize the solvent in the applied film.
• PB pre-baking
• the PB temperature and PB time can be appropriately determined depending on the type of resist film forming composition used, etc.
• the lower limit of the PB temperature is preferably 30°C, and more preferably 50°C.
• the upper limit of the PB temperature is preferably 200°C, and more preferably 150°C.
• the lower limit of the PB time is preferably 10 seconds, and more preferably 30 seconds.
• the upper limit of the PB time is preferably 600 seconds, and more preferably 300 seconds.
• the resist film-forming composition used in this process is preferably a composition that is exposed to extreme ultraviolet rays, and examples of such compositions include positive or negative chemically amplified resist compositions that contain a radiation-sensitive acid generator, and metal-containing resist compositions that contain metals such as tin, zirconium, and hafnium.
• the resist film formed in the resist film-forming composition application step is exposed to radiation, which causes a difference in solubility in a developer between exposed and unexposed areas of the resist film.
• the radiation used for exposure can be appropriately selected depending on the type of the resist film-forming composition used.
• visible light, ultraviolet light, far ultraviolet light, electromagnetic waves such as X-rays and gamma rays, electron beams, molecular beams, particle beams such as ion beams, etc. can be mentioned.
• KrF excimer laser light (wavelength 248 nm), ArF excimer laser light (wavelength 193 nm), F2 excimer laser light (wavelength 157 nm), Kr2 excimer laser light (wavelength 147 nm), ArKr excimer laser light (wavelength 134 nm) or extreme ultraviolet light (wavelength 13.5 nm, etc., also referred to as "EUV”) is more preferred, and ArF excimer laser light or EUV is even more preferred.
• the exposure conditions can be appropriately determined depending on the type of the resist film-forming composition used, etc.
• PEB post-exposure baking
• the PEB temperature and PEB time can be appropriately determined depending on the type of resist film-forming composition used, etc.
• the lower limit of the PEB temperature is preferably 50°C, and more preferably 70°C.
• the upper limit of the PEB temperature is preferably 200°C, and more preferably 150°C.
• the lower limit of the PEB time is preferably 10 seconds, and more preferably 30 seconds.
• the upper limit of the PEB time is preferably 600 seconds, and more preferably 300 seconds.
• the exposed resist film is developed. At this time, a part of the resist underlayer film may be further developed.
• the developer used in this development include an alkaline aqueous solution (alkaline developer), an organic solvent-containing liquid (organic solvent developer), and the like.
• the basic liquid for alkaline development is not particularly limited, and any known basic liquid can be used.
• Examples of basic liquids for alkaline development include aqueous alkaline solutions in which at least one of the following alkaline compounds is dissolved: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc.
• TMAH tetramethylammonium hydroxide
• TMAH tetramethylammonium hydrox
• examples of the organic solvent developer include those exemplified as the solvent [B] above.
• organic solvent developer ester-based solvents, ether-based solvents, alcohol-based solvents, ketone-based solvents and/or hydrocarbon-based solvents are preferred, ketone-based solvents are more preferred, and 2-heptanone is particularly preferred.
• washing and/or drying may be performed after the development.
• etching is performed using the resist pattern (and resist underlayer film pattern) as a mask.
• the number of times of etching may be one or more, that is, etching may be performed sequentially using the pattern obtained by etching as a mask. From the viewpoint of obtaining a pattern with a better shape, multiple times are preferable.
• etching is performed sequentially in the order of the silicon-containing film and the substrate.
• the etching method include dry etching and wet etching. From the viewpoint of obtaining a better shape of the pattern of the substrate, dry etching is preferable. For this dry etching, for example, gas plasma such as oxygen plasma is used.
• Dry etching can be performed, for example, using a known dry etching device.
• the etching gas used in dry etching can be appropriately selected according to the mask pattern, the elemental composition of the film to be etched, etc., and includes, for example, fluorine-based gases such as CHF3 , CF4 , C2F6 , C3F8 , SF6 , etc., chlorine-based gases such as Cl2 , BCl3 , oxygen-based gases such as O2 , O3 , H2O , H2, NH3 , CO , CO2 , CH4 , C2H2 , C2H4 , C2H6 , C3H4 , C3H6 , C3H8 , HF, HI, HBr, HCl , NO, BCl3 , etc.
• fluorine-based gases such as CHF3 , CF4 , C2F6 , C3F8 , SF6 , etc.
• reducing gases such as He, N2 , Ar , etc.
• inert gases such as He, N2 , Ar , etc.
• gases can also be used in mixture.
• a fluorine-based gas is usually used.
• the silicon-containing film can be removed by carrying out a removal process.
• the polymer for forming a resist underlayer film can be obtained by reacting a compound represented by the following formula ( ⁇ ) with a compound represented by the following formula ( ⁇ 1) or a compound represented by the following formula ( ⁇ 2).
• Ar 1 is a divalent group having an aromatic ring having 6 to 20 ring members.
• R 1 A is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.
• R 1a and R 3a are each independently a monovalent group having an epoxy structure or an oxetane structure.
• R 1B is a divalent organic group having 1 to 20 carbon atoms.
• the polymer [A] in the composition for forming a resist underlayer film described above and its manufacturing method can be suitably used.
• Mw Weight average molecular weight
• the average thickness of the film was determined by measuring the film thickness at any nine positions at 5 cm intervals including the center of the resist underlayer film formed on the silicon wafer using a spectroscopic ellipsometer (J.A. WOOLLAM's "M2000D") and calculating the average value of the film thicknesses.
• Polymer [A] was synthesized according to the procedure shown below.
• the numbers attached to each repeating unit indicate the content (mol %) of that repeating unit.
• the content of that repeating unit is 100 mol %.
• the composition ratio was confirmed by 13 C-NMR.
• Example 1-1 25 parts by mass of (A-1) as the polymer [A] was dissolved in 7,900 parts by mass of (B-1) and 2,000 parts by mass of (B-2) as the solvent [B]. The resulting solution was filtered through a polytetrafluoroethylene (PTFE) membrane filter having a pore size of 0.45 ⁇ m to prepare a composition (J-1).
• PTFE polytetrafluoroethylene
• Example 1-22 and Comparative Example 1-1 Compositions (J-2) to (J-22) and (CJ-1) were prepared in the same manner as in Example 1, except that the types and amounts of each component shown in Table 2 below were used.
• the composition prepared above was applied onto a 12-inch silicon wafer by a spin coating method using a spin coater (Tokyo Electron Co., Ltd.'s "CLEAN TRACK ACT12"). Next, in an air atmosphere, the wafer was heated at 250°C for 60 seconds, and then cooled at 23°C for 60 seconds to form a resist underlayer film having an average thickness of 5 nm, thereby obtaining a substrate with a resist underlayer film formed on the substrate. The substrate with the resist underlayer film obtained above was immersed in cyclohexanone (23°C) for 1 minute. The average film thickness before and after immersion was measured.
• the average thickness of the resist underlayer film before immersion was X0
• the average thickness of the resist underlayer film after immersion was X
• the absolute value of the value obtained by ⁇ (X-X0)/X0 ⁇ x100 was calculated to obtain the film thickness change rate (%).
• the solvent resistance was evaluated as "A” (good) when the film thickness change rate was less than 10%, and as “B” (poor) when it was 10% or more.
• an organic underlayer film forming material (“HM8006” by JSR Corporation) was applied by a spin coating method using a spin coater ("CLEAN TRACK ACT12" by Tokyo Electron Co., Ltd.), and then heated at 250° C. for 60 seconds to form an organic underlayer film having an average thickness of 100 nm.
• a silicon-containing film forming composition (“NFC SOG080” by JSR Corporation) was applied, heated at 220° C. for 60 seconds, and then cooled at 23° C. for 30 seconds to form a silicon-containing film having an average thickness of 20 nm.
• the composition prepared above was applied to form a resist underlayer film.
• the resist underlayer film formed above was heated at 250° C. for 90 seconds, and then cooled at 23° C. for 30 seconds to obtain a resist underlayer film having an average thickness of 5 nm.
• a resist composition (R-1) was applied onto the resist underlayer film formed above, heated at 130° C. for 60 seconds, and then cooled at 23° C. for 30 seconds to form a resist film having an average thickness of 50 nm.
• the resist film was irradiated with extreme ultraviolet rays using an EUV scanner (ASML's "TWINSCAN NXE:3300B" (NA 0.3, sigma 0.9, quadrupole illumination, 1:1 line and space mask with line width of 16 nm on the wafer).
• EUV scanner ASML's "TWINSCAN NXE:3300B” (NA 0.3, sigma 0.9, quadrupole illumination, 1:1 line and space mask with line width of 16 nm on the wafer).
• extreme ultraviolet rays the substrate was heated at 110°C for 60 seconds, and then cooled at 23°C for 60 seconds. Thereafter, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (20°C to 25°C) was used for development by the paddle method, followed by washing with water and drying to obtain an evaluation substrate on which a 1:1 line and space resist pattern with a line width of 16 nm was formed.
• a scanning electron microscope (Hitachi High-Technologies Corporation's "SU8220" was used to measure and observe the resist pattern of the evaluation substrate.
• the pattern rectangularity was evaluated as "A” (good) when the cross-sectional shape of the pattern was rectangular, and as “B” (bad) when the cross-section of the pattern had a skirt.
• Compound (S-1) was an oxide hydroxide product of a hydrolysis product of isopropyltin trichloride (having a structural unit of i-PrSnO (3/2-x/2) (OH) x (0 ⁇ x ⁇ 3)).
• an organic underlayer film forming material (“HM8006” by JSR Corporation) was applied by a spin coating method using a spin coater ("CLEAN TRACK ACT12" by Tokyo Electron Limited), and then heated at 250°C for 60 seconds to form an organic underlayer film having an average thickness of 100 nm.
• the resist underlayer film forming composition prepared above was applied, heated at 220°C for 60 seconds, and then cooled at 23°C for 30 seconds to form a resist underlayer film having an average thickness of 5 nm.
• a resist composition (R-2) for EUV exposure was applied by a spin coating method using the spin coater, and after a predetermined time had elapsed, the resist film was heated at 90°C for 60 seconds, and then cooled at 23°C for 30 seconds to form a resist film having an average thickness of 35 nm.
• the resist film was exposed to light using an EUV scanner (ASML's "TWINSCAN NXE:3300B" (NA 0.3, sigma 0.9, quadrupole illumination, 1:1 line and space mask with a line width of 16 nm on the wafer). After exposure, the substrate was heated at 110°C for 60 seconds, and then cooled at 23°C for 60 seconds.
• the substrate was developed by the paddle method using 2-heptanone (20 to 25°C), and then dried to obtain an evaluation substrate on which a 1:1 line and space resist pattern with a line width of 16 nm was formed.
• a scanning electron microscope (Hitachi High-Tech's "CG-6300") was used to measure and observe the resist pattern of the evaluation substrate.
• the pattern rectangularity was evaluated as "A” (good) when the cross-sectional shape of the pattern was rectangular, and as "B" (bad) when the cross-section of the pattern had a footing.
• the resist underlayer films formed from the compositions of the examples had superior solvent resistance and pattern rectangularity compared to the resist underlayer films formed from the compositions of the comparative examples.
• composition for forming a resist underlayer film of the present invention a film having excellent solvent resistance and pattern rectangularity can be formed.
• a composition for forming a resist underlayer film capable of forming a resist underlayer film having excellent solvent resistance and pattern rectangularity is used, so that a semiconductor substrate can be produced efficiently.
• the polymer for forming a resist underlayer film of the present invention is suitable for the composition for forming a resist underlayer film. Therefore, these can be suitably used in the production of semiconductor devices, etc.

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