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
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
  • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
  • C08G8/14—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with halogenated phenols
• • 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
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
• • 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
  • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
• • 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
  • G03F7/094—Multilayer resist systems, e.g. planarising layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
  • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
• • 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 has been performed by lithography using a resist composition.
• 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), the ability to form a resist pattern with high sensitivity, and a fast etching rate.
• 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, which is capable of forming a resist pattern with high sensitivity and forming a resist underlayer film having a high etching rate, and a method for producing a resist underlayer film, a laminate, and a semiconductor element, and a method for forming a pattern, each of which uses the composition for forming a resist underlayer film.
• a composition for forming a resist underlayer film comprising: (A) a novolak resin having a phenolic hydroxy group and a halogen atom directly bonded to an aromatic hydrocarbon ring; and (B) a solvent.
• A represents an aromatic hydrocarbon ring having a phenolic hydroxy group (the aromatic hydrocarbon ring may have a substituent).
• a in the formula (1) is represented by the following formula (1-1): (In formula (1-1), m1 represents an integer of 1 to 4. n1 represents an integer of 0 to 3. n1+m1 is 4 or less. R 1 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. When n1 is 2 or more, two or more R 1 s may be the same or different.
• R2 represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
• n2 is 2 or more, two or more R 2 s may be the same or different.
• m2 is 2 or more, two or more X's may be the same or different. * represents a bond.
• [6] The composition for forming a resist underlayer film according to any one of [1] to [5], wherein the halogen atom directly bonded to the aromatic hydrocarbon ring is a bromine atom.
• the resist underlayer film according to [9] having a film thickness of 2 nm or more and 20 nm or less.
• a semiconductor substrate; [9] or [10], and A laminate 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 method for manufacturing a semiconductor device, comprising: [13] 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 that can form a resist pattern with high sensitivity and can form a resist underlayer film with a fast etching rate, as well as a method for producing a resist underlayer film, a laminate, and a semiconductor device, and a method for forming a pattern, using the composition for forming a resist underlayer film.
• composition for forming resist underlayer film contains a novolak resin (A) and a solvent (B).
• the composition for forming a resist underlayer film may contain a crosslinking agent (C), a curing catalyst (D), and the like.
• the novolak resin (A) has a phenolic hydroxy group and a halogen atom directly bonded to an aromatic hydrocarbon ring.
• the novolac resin (A) has both a phenolic hydroxy group and a halogen atom directly bonded to the aromatic hydrocarbon ring, which allows the formation of a resist pattern with high sensitivity and a resist underlayer film with a fast etching rate, compared to a case in which the novolac resin does not have a halogen atom directly bonded to the aromatic hydrocarbon ring.
• halogen atom directly bonded to the aromatic hydrocarbon ring examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of suitably obtaining the effects of the present invention, a bromine atom and an iodine atom are preferred, and a bromine atom is more preferred.
• the number of halogen atoms directly bonded to one aromatic hydrocarbon ring may be one or may be two or more. When the number of halogen atoms directly bonded to one aromatic hydrocarbon ring is two or more, the two or more halogen atoms may be the same or different.
• the phenolic hydroxy group in the present invention is also called an aromatic hydroxy group, and the aromatic ring to which the hydroxy group is directly bonded is not limited to a benzene ring, but may be an aromatic hydrocarbon ring such as a naphthalene ring or an anthracene ring, or may be an aromatic heterocycle.
• the novolak resin (A) preferably has a repeating unit represented by the following formula (1).
• A represents an aromatic hydrocarbon ring having a phenolic hydroxy group (the aromatic hydrocarbon ring may have a substituent).
• B represents an aromatic hydrocarbon group to which at least one of a bromine atom and an iodine atom is directly bonded (the aromatic hydrocarbon group may have a substituent).
• a in the formula (1) is an aromatic hydrocarbon ring having a phenolic hydroxy group.
• a in formula (1) is a divalent group. Therefore, an aromatic hydrocarbon ring having a phenolic hydroxy group can be said to be a divalent group obtained by removing two hydrogen atoms from an aromatic hydrocarbon ring having a phenolic hydroxy group.
• the aromatic hydrocarbon ring in A in formula (1) is not particularly limited and may be, for example, a benzene ring, a naphthalene ring, an anthracene ring, or a pyrene ring. From the viewpoint of optimally obtaining the effects of the present invention, a benzene ring is preferred.
• the number of phenolic hydroxy groups in the aromatic hydrocarbon ring in A in formula (1) may be one or two or more, but from the viewpoint of optimally obtaining the effects of the present invention, two or more is preferred, and two to four is more preferred.
• the aromatic hydrocarbon ring in A in formula (1) may have a substituent.
• the substituent is not particularly limited, but examples thereof include a halogen atom, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. There is no particular limit to the number of substituents that the aromatic hydrocarbon ring has.
• a in formula (1) is preferably represented by the following formula (1-1).
• m1 represents an integer of 1 to 4.
• n1 represents an integer of 0 to 3.
• n1+m1 is 4 or less.
• R 1 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. When n1 is 2 or more, two or more R 1 s may be the same or different. * represents a bond.
• m1 is preferably 2 or 3.
• a in formula (1) is preferably derived from optionally substituted phloroglucinol (1,3,5-trihydroxybenzene).
• a in the formula (1) derived from optionally substituted phloroglucinol is preferably represented by the following formula (1-1-1).
• R 1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. * represents a bond.
• alkyl group having 1 to 6 carbon atoms an alkyl group having 1 to 4 carbon atoms is preferable, and an alkyl group having 1 to 2 carbon atoms is more preferable.
• examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-d
• alkoxy group having 1 to 6 carbon atoms an alkoxy group having 1 to 4 carbon atoms is preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable.
• examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-
• B in the formula (1) is an aromatic hydrocarbon group to which at least one of a bromine atom and an iodine atom is directly bonded.
• B is a monovalent group. Therefore, an aromatic hydrocarbon group to which at least one of a bromine atom and an iodine atom is directly bonded can be said to be a monovalent group in which one hydrogen atom has been removed from an aromatic hydrocarbon ring to which at least one of a bromine atom and an iodine atom is directly bonded.
• the aromatic hydrocarbon ring in the aromatic hydrocarbon group of B in formula (1) is not particularly limited and examples include a benzene ring, a naphthalene ring, an anthracene ring, and a pyrene ring. From the viewpoint of optimally obtaining the effects of the present invention, a benzene ring is preferred.
• the number of at least one of the bromine atom and the iodine atom in the aromatic hydrocarbon ring in the aromatic hydrocarbon group of B in formula (1) may be one or two or more, but is preferably two or more, and more preferably two to five.
• the aromatic hydrocarbon ring in the aromatic hydrocarbon group in B in formula (1) may have a substituent.
• the substituent is not particularly limited, but examples thereof include a hydroxyl group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. There is no particular limit to the number of substituents.
• B in formula (1) is preferably represented by the following formula (1-2).
• m2 represents an integer of 1 to 5.
• n2 represents an integer of 0 to 4.
• n2+m2 is less than or equal to 5.
• X represents a bromine atom or an iodine atom.
• R2 represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
• n2 is 2 or more, two or more R 2 s may be the same or different.
• m2 is 2 or more, two or more X's may be the same or different.
• * represents a bond.
• m2 is preferably 2.
• the repeating unit represented by formula (1) is preferably a repeating unit represented by the following formula (1X):
• the repeating unit represented by formula (1X) may be one type or two or more types.
• m1 represents an integer of 1 to 4.
• n1 represents an integer of 0 to 3.
• n1+m1 is 4 or less.
• R 1 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
• n1 is 2 or more, two or more R 1 s may be the same or different.
• m2 represents an integer of 1 to 5.
• n2 represents an integer of 0 to 4.
• n2+m2 is 5 or less.
• X represents a bromine atom or an iodine atom.
• R2 represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
• n2 is 2 or more, two or more R 2 s may be the same or different.
• m2 is 2 or more, two or more X's may be the same or different.
• repeating unit represented by formula (1) examples include the following repeating units.
• the novolak resin (A) can be synthesized, for example, by the following method.
• B represents an aromatic hydrocarbon group to which a halogen atom is directly bonded (the aromatic hydrocarbon group may have a substituent).
• the phenolic compound A includes, for example, a compound represented by the following formula (A-1).
• the structure represented by formula (1-1) is introduced into the novolak resin (A).
• m1 represents an integer of 1 to 4.
• n1 represents an integer of 0 to 3.
• n1+m1 is 4 or less.
• R 1 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. When n1 is 2 or more, two or more R 1's may be the same or different.
• Examples of compounds represented by formula (A-1) include catechol, resorcinol, hydroquinone, 2,6-dimethylhydroquinone, pyrogallol, hydroxyquinol, and phloroglucinol.
• aldehyde compound B is a compound represented by the following formula (B-1).
• the structure represented by formula (1-2) is introduced into the novolak resin (A).
• m2 represents an integer of 1 to 5.
• n2 represents an integer of 0 to 4.
• n2+m2 is less than or equal to 5.
• X represents a bromine atom or an iodine atom.
• R2 represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
• two or more R 2 s may be the same or different.
• m2 is 2 or more, two or more X's may be the same or different.
• Examples of compounds represented by formula (B-1) include 3,5-dibromobenzaldehyde and 3,5-dibromo-4-hydroxybenzaldehyde.
• aldehyde compound B In the condensation reaction of phenolic compound A and aldehyde compound B, aldehyde compound B can be reacted with 1 mole of phenolic compound A in a ratio of, for example, 0.1 to 10 moles, preferably 0.8 to 2.2 moles, and more preferably 1.0 mole.
• an acid catalyst may be used, for example, a mineral acid such as sulfuric acid, phosphoric acid, or perchloric acid; an organic sulfonic acid such as p-toluenesulfonic acid or p-toluenesulfonic acid monohydrate; or a carboxylic acid such as formic acid or oxalic acid.
• the amount of the acid catalyst used in the above condensation reaction is selected according to the type of acid used. Usually, the amount of the acid catalyst used is 0.001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.1 to 100 parts by mass, per 100 parts by mass of the total of the phenolic compound A and the aldehyde compound B.
• the above condensation reaction can be carried out without using a solvent when either the starting compounds or the acid catalyst used are liquid, but is usually carried out using a solvent.
• a solvent is not particularly limited as long as it does not inhibit the reaction, but typical examples include ether compounds, monoalkyl ether compounds, and ether ester compounds.
• the ether compound include cyclic ether compounds such as tetrahydrofuran and dioxane.
• the monoalkyl ether compound include propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, and dipropylene glycol monomethyl ether.
• ether ester compound examples include methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, and propylene glycol monopropyl ether propionate.
• PMEA propylene glycol monomethyl ether acetate
• PMEA propylene glycol monoethyl ether acetate
• propylene glycol monopropyl ether acetate propylene glycol monomethyl ether propionate
• propylene glycol monoethyl ether propionate propylene glycol monopropyl ether propionate
• the reaction temperature during condensation is usually between 40°C and 200°C.
• the reaction time varies depending on the reaction temperature, but is usually between about 30 minutes and 50 hours.
• the molecular weight of the novolak resin (A) is not particularly limited.
• the lower limit of the weight average molecular weight of the novolak resin (A) is, for example, 500, 1,000, 2,000, or 3,000.
• the upper limit of the weight average molecular weight of the novolak resin (A) is, for example, 30,000, 20,000, or 10,000.
• the content of the novolak resin (A) in the composition for forming a resist underlayer film is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 40% by mass to 99% by mass, more preferably 45% by mass to 95% by mass, and particularly preferably 50% 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 solvent (B) 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 (B) can be used alone or in combination of two or more.
• the mass ratio of the organic solvent in solvent (B) is not particularly limited, but is preferably 50% by mass to 100% by mass.
• the content of the solvent (B) 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 (C) is not particularly limited.
• the crosslinking agent (C) has a structure different from that of the novolak resin (A).
• an aminoplast crosslinking agent or a phenoplast crosslinking agent is preferred.
• Aminoplast crosslinking agents are addition condensation products of a compound having an amino group, such as melamine or guanamine, and formaldehyde.
• the phenoplast crosslinking agent is an addition condensation product of a compound having a phenolic hydroxy group and formaldehyde.
• Examples of the crosslinking agent (C) include compounds having two or more of the following structures.
• R 101 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond.
• the bond is, 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 (C) 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 formulas (1E-1) to (1E-6) below.
• 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 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 (C) is not particularly limited, but is preferably 500 or less.
• the content of the crosslinking agent (C) in the composition for forming the resist underlayer film is not particularly limited, but is, for example, 1% by mass to 70% by mass, and preferably 5% by mass to 60% by mass, relative to the novolac resin (A).
• the curing catalyst (D) contained as an optional component in the composition for forming a resist underlayer film may be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator.
• the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate (pyridinium p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonate salt), pyridinium trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-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, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfon
• 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 (D) relative to the crosslinking agent (C) 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 resist underlayer film forming composition of the present invention is preferably a resist underlayer film forming composition for EUV (extreme ultraviolet) or electron beam lithography.
• 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 film 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 thickness of the resist underlayer film is preferably 2 nm or more and 20 nm or less in order to optimally obtain the effects of the present invention.
• 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, for example, 3,000 nm or less, 2,000 nm or less, 1,800 nm or less, 1,500 nm or less, or 1,000 nm or less.
• the lower limit is 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, or 10 nm.
• the resist film formed on the resist underlayer film by a known method is not particularly limited as long as it responds to light or electron beam (EB) used for irradiation.
• EB electron beam
• a resist that responds to EB is also 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. 2 may combine to form a carbonyl group.
• R 1 to R 5 are each independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, some or all of the hydrogen atoms 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 carbonate group
• 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 4 and Comparative Synthesis Example 1 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.
• Eluent N,N-dimethylformamide (DMF)
• Standard sample Polystyrene (Tosoh Corporation)
• the polymer obtained in this synthesis example has structural units represented by the following formulas (1a) and (1b).
• the polymer obtained in this synthesis example has structural units represented by the following formulas (1a) and (2b).
• the polymer obtained in this synthesis example has structural units represented by the following formulas (2a) and (2b).
• the polymer solution did not become cloudy even when cooled to room temperature, and the solubility in propylene glycol monomethyl ether was good.
• the polymer in the obtained solution had a weight average molecular weight of 9000 in terms of standard polystyrene.
• the polymer obtained in this synthesis example has structural units represented by the following formulas (1a) and (4b).
• Comparative Synthesis Example 1 5.00 g of phloroglucinol (Tokyo Chemical Industry Co., Ltd.) and 4.21 g of benzaldehyde (Tokyo Chemical Industry Co., Ltd.) were added to 22.5 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After replacing the reaction vessel with nitrogen, the reaction was carried out at 90° C. for 24 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in propylene glycol monomethyl ether. When GPC analysis was performed, the polymer in the obtained solution had a weight average molecular weight of 4000 in terms of standard polystyrene.
• the polymer obtained in this synthesis example has structural units represented by the following formulas (1a) and (3b).
• Table 3 shows the irradiation energy ( ⁇ C/cm 2 ) when the charge amount at which a 23 nm contact hole was formed was taken as the optimum irradiation energy and Comparative Example 1 was taken as 1.00. A reduction in the optimum irradiation energy was confirmed in Examples 1 to 2 and 4, compared to Comparative Example 1.

Landscapes

• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Structural Engineering (AREA)
• Architecture (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Materials For Photolithography (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=92906512

Family Applications (1)

Country Status (6)

Citations (63)

• 2024
  • 2024-03-26 JP JP2025510908A patent/JPWO2024204163A1/ja active Pending
  • 2024-03-26 CN CN202480015367.2A patent/CN120693572A/zh active Pending
  • 2024-03-26 EP EP24780276.2A patent/EP4692942A1/en active Pending
  • 2024-03-26 WO PCT/JP2024/011894 patent/WO2024204163A1/ja not_active Ceased
  • 2024-03-26 KR KR1020257027718A patent/KR20250166879A/ko active Pending
  • 2024-03-28 TW TW113111737A patent/TW202506778A/zh unknown

Patent Citations (66)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events