Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • 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
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
• • 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
  • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
• • 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
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
• • 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
• • 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

Definitions

• the present invention relates to a resist composition and a resist pattern forming method.
• Japanese Unexamined Patent Publication No. 56-019044 Japanese Unexamined Patent Publication No. 56-088134 Japanese Patent Application Publication No. 2000-321791 Japanese Patent Application Publication No. 2004-279694
• resist compositions have been required to have a wide tolerance to the amount of exposure in the exposure process, in other words, to have a wide exposure margin. Furthermore, it is naturally required that the resist pattern has few defects and is clear. However, the resist compositions that have been studied so far have room for improvement in terms of both expanding the exposure margin and clarifying the resulting resist pattern.
• an object of the present invention is to provide a resist composition and a resist pattern forming method that can form a clear resist pattern with a wide exposure margin and few defects.
• the present inventor conducted extensive studies with the aim of solving the above problems. As a result, by incorporating a crosslinking agent that reacts with ionizing radiation or non-ionizing radiation with a wavelength of 300 nm or less into the resist composition, the resist film can have a wide exposure margin and a clear resist pattern with few defects.
• the present invention was completed based on the new discovery that it is possible to form .
• the resist composition of the present invention contains a crosslinking agent that reacts with ionizing radiation or non-ionizing radiation with a wavelength of 300 nm or less. , a solvent, and a polymer. According to a resist composition containing such a specific crosslinking agent, the formed resist film has a wide exposure margin, and the obtained resist pattern has few defects and is clear.
• the polymer is of a main chain truncated type. If the polymer is of the main chain cleavage type, better exposure margin expansion effects and pattern clarifying effects can be obtained.
• the polymer The following general formula (I): (In formula (I), R 1 is a halogen atom or an alkyl group substituted with a halogen atom, R 2 is an organic group having 0 to 11 hydrogen atoms or fluorine atoms, R 3 and R 4 is a hydrogen atom, a halogen atom, an unsubstituted alkyl group, or an alkyl group substituted with a halogen atom, and may be the same or different from each other.
• R 1 is a halogen atom or an alkyl group substituted with a halogen atom
• R 2 is an organic group having 0 to 11 hydrogen atoms or fluorine atoms
• R 3 and R 4 is a hydrogen atom, a halogen atom, an unsubstituted alkyl group, or an alkyl group substituted with a halogen atom, and may be the same or different from each other.
• R 5 , R 6 , R 8 , and R 9 are a hydrogen atom, a halogen atom, an unsubstituted alkyl group, or an alkyl group substituted with a halogen atom, and may be the same or different from each other)
• R7 is a hydrogen atom, an unsubstituted alkyl group, or an alkyl group substituted with a halogen atom
• a copolymer having a monomer unit (B) represented by the following is preferable. In this way, if the resist composition contains a copolymer having a predetermined monomer unit, it becomes possible to improve the resolution of the resulting resist pattern.
• the crosslinking agent has an unsaturated bond.
• the crosslinking agent has 1 or more and 10 or less of the unsaturated bonds.
• the unsaturated bond that the crosslinking agent has is an unsaturated bond contained in a vinyl group, a (meth)acrylate group, or an allyl group. It is preferable that there is.
• a crosslinking agent having a functional group containing such a specific unsaturated bond even better exposure margin expansion effects and pattern clarifying effects can be obtained.
• (meth)acrylate means acrylate or methacrylate.
• the resist composition according to any one of [1] to [6] above contains the crosslinking agent in a proportion of 1 part by mass or more and 60 parts by mass or less, based on 100 parts by mass of the polymer. is preferred. If the amount of the crosslinking agent is within this range, better exposure margin expansion effects and pattern clarifying effects can be obtained, and the resulting resist pattern can have higher resolution.
• the present invention aims to advantageously solve the above problems, and the resist pattern forming method of the present invention reacts with ionizing radiation or non-ionizing radiation with a wavelength of 300 nm or less.
• the exposure margin in the exposure step is wide and the resulting resist pattern has few defects and is clear.
• the polymer is a main chain cleavage type, and in the exposure step, the crosslinking reaction and the main chain cleavage reaction of the polymer proceed in parallel. It is preferable to do so.
• the exposure margin in the exposure step is wider, and the resulting resist pattern has fewer and clearer defects.
• the present invention it is possible to provide a resist composition and a resist pattern forming method that can form a clear resist pattern with a wide exposure margin and few defects.
• the resist composition and resist pattern forming method of the present invention are not particularly limited, and are suitable for, for example, forming resist patterns in the manufacturing process of printed circuit boards such as build-up boards, semiconductors, photomasks, molds, etc. Can be used. Note that the resist composition of the present invention can be suitably used in the resist pattern forming method of the present invention.
• the resist composition of the present invention is characterized by containing a crosslinking agent that reacts with ionizing radiation or non-ionizing radiation with a wavelength of 300 nm or less, a solvent, and a polymer. According to a resist composition containing such a specific crosslinking agent, the formed resist film has a wide exposure margin, and the obtained resist pattern has few defects and is clear. Although the reason is not clear, it is presumed to be as follows.
• a crosslinking agent that has the property of proceeding with a crosslinking reaction triggered by ionizing radiation or non-ionizing radiation with a wavelength of 300 nm or less, that is, radiation that can be used as exposure light in the exposure process, does not undergo the crosslinking reaction before the exposure process.
• a crosslinking reaction is initiated by being given a trigger called exposure light in the exposure step.
• formation of a latent image pattern progresses by irradiating the resist film with exposure light. Specifically, when forming a latent image pattern, a difference is formed in the solubility of a polymer constituting the resist film in a solvent between an exposed area and a non-exposed area of the resist film.
• the resist film contains the above-mentioned predetermined crosslinking agent in addition to the polymer, a reaction between the crosslinking agents and a reaction between the crosslinking agent and the polymer constituting the poorly soluble portion A will cause the resist film to become poorly soluble.
• Part A may become less soluble. This can favorably promote the formation of a difference in solubility between the "hardly soluble portion A" and the "easily soluble portion B" even when the exposure amount in the exposure step is relatively small.
• EUV lithography areas affected by reflected light flare caused by an EUV exposure apparatus and leakage light caused by a mask pattern can become areas that receive "low-dose" irradiation.
• a predetermined crosslinking agent inhibits the increase in the molecular weight of the polymer in the "easily soluble portion B", thereby making it possible to form a clear resist pattern even at a high dose.
• the polymer is a chemically amplified polymer in which a catalytic reaction is induced in the subsequent post-exposure bake step by the acid of an acid generator generated by exposure light, the presence of a crosslinking agent is required.
• the difference in solubility between the slightly soluble part A and the easily soluble part B can be expanded, and a clear resist pattern can be formed.
• Conceivable For example, if the polymer is a main chain cleavage type in which the polymer chain is cleaved by exposure light as a trigger and becomes a low molecular weight substance that becomes easily soluble, the low molecular weight bodies generated by the cleavage of the main chain recombine with each other. It is thought that by increasing the molecular weight, it is possible to inhibit the solubility from becoming difficult to dissolve.
• Crosslinking agent a crosslinking agent that reacts with ionizing radiation or non-ionizing radiation with a wavelength of 300 nm or less is used. More specifically, as a crosslinking agent, a film made of a crosslinking agent is irradiated with a predetermined radiation to bring it into a crosslinked state, and then immersed for 1 minute in a solvent that can dissolve the crosslinking agent. It is possible to use a material whose thickness decreases from the previous value by less than 50%.
• the crosslinking agent is also used to remove solvents when forming a resist film. It is preferable that the crosslinking reaction does not proceed during the drying process (usually accompanied by heating).
• the number of unsaturated bonds contained in the molecular structure of the crosslinking agent is preferably one or more, and two or more. It is more preferable that it is, it is preferable that it is 10 or less, and it is more preferable that it is 8 or less.
• the unsaturated bond contained in the crosslinking agent is an unsaturated bond contained in a vinyl group, (meth)acrylate group, or allyl group.
• a crosslinking agent having a functional group containing such a specific unsaturated bond it is possible to obtain an even better exposure margin expansion effect and pattern clarifying effect, and it is also possible to increase the resolution of the resulting resist pattern. can.
• the crosslinking agent may have only one of a vinyl group, a (meth)acrylate group, and an allyl group, or may have a plurality of them.
• the number of these functional groups that the crosslinking agent can contain is preferably one or more, more preferably two or more, preferably 10 or less, and more preferably 8 or less. preferable.
• the crosslinking agent that can be used is not particularly limited, and the following compounds can be mentioned. Examples include compounds having a vinyl group, compounds having an allyl group, acrylate compounds, methacrylate compounds, and isocyanurate compounds.
• Examples of the compounds having a vinyl group and compounds having an allyl group include alkene compounds such as ethylene, propene, 1-butene, 2-butene, iso-butene, 1-pentene, 1-hexene, and 1-octene; acrylonitrile , methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -cyanoethyl acrylonitrile, and other cyano group-containing unsaturated hydrocarbon compounds; vinyl ethyl ether, vinyl butyl ether, vinyl phenyl ether, vinyl 2-chloroethyl ether, 3,4-dihydro-2H - Monovinyl ether compounds such as pyran, 2,3-dihydrofuran, 1,4-dioxene, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, isopropenyl methyl ether; divinyl ether, ethylene glycol divinyl ether, diethylene glycol
• polyfunctional vinyl ether compounds having an aromatic ring skeleton vinyl ester compounds such as vinyl acetate, vinyl butyrate, isopropenyl acetate, vinyl caprate, and vinyl benzoate; unsaturated alcohols such as allyl alcohol and cinnamic alcohol; 1,3-butadiene , isoprene, 1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, 2,5-dimethyl-2,4-hexadiene and Conjugated diene compounds such as chloroprene; styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4,6-trimethylstyrene, 4-butylstyrene, 4-phenylstyrene, 4-fluorostyrene, 2, 3,4,5,6-pentafluorostyren
• acrylate compound examples include monofunctional acrylate compounds, bifunctional acrylate compounds, and trifunctional or higher functional acrylate compounds.
• Examples of monofunctional acrylate compounds include acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, iso- Alkyl acrylates such as pentyl acrylate, tert-pentyl acrylate, neopentyl acrylate, hexyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, benzyl acrylate, alkyl phenol (butyl phenol, octyl phenol, nonyl phenol or dodecyl phenol, etc.), ethylene oxide adduct acrylate , isobornyl acrylate, cyclohexyl acrylate, tricyclodecane monomethylo
• Bifunctional acrylate compounds include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, Polypropylene glycol diacrylate, butylene glycol diacrylate, pentyl glycol diacrylate, neopentyl glycol diacrylate, hydroxypivalyl hydroxypivalate diacrylate, hydroxypivalyl hydroxypivalate dicaprolactonate diacrylate, 1,6-hexane diol diacrylate Acrylate, 1,2-hexanediol diacrylate, 1,5-hexanediol diacrylate, 2,5-hexanediol diacrylate, 1,7-heptanediol diacrylate, 1,8-octanediol diacrylate, 1,2 -O
• polyfunctional acrylate compounds include glycerin triacrylate, trimethylolpropane triacrylate, trimethylolpropane tricaprolactonate triacrylate, trimethylolethane triacrylate, trimethylolhexane triacrylate, trimethylol octane triacrylate, pentaerythritol triacrylate, Pentaerythritol Tetraacrylate, Pentaerythritol Tetracaprolactonate Tetraacrylate, Diglycerin Tetraacrylate, Ditrimethylolpropane Tetraacrylate, Ditrimethylolpropane Tetracaprolactonate Tetraacrylate, Ditrimethylolethane Tetraacrylate, Ditrimethylolbutane Tetraacrylate, Ditri Methylolhexanetetraacrylate, ditrimethyloloctanetetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa
• methacrylate compound examples include monofunctional methacrylate compounds, bifunctional methacrylate compounds, and trifunctional or higher functional methacrylate compounds.
• Examples of monofunctional methacrylate compounds include methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, iso- Alkyl methacrylates such as pentyl methacrylate, tert-pentyl methacrylate, neopentyl methacrylate, hexyl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, benzyl methacrylate, alkyl phenol (butyl phenol, octyl phenol, nonyl phenol or dodecyl phenol, etc.), ethylene oxide adduct methacrylate , isobornyl meth
• Bifunctional methacrylate compounds include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, Polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, pentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, hydroxypivalyl hydroxypivalate dimethacrylate, hydroxypivalyl hydroxypivalate dicaprolactonate dimethacrylate, 1,6 hexanediol dimethacrylate , 1,2-hexanediol dimethacrylate, 1,5-hexanediol dimethacrylate, 2,5-hexanediol dimethacrylate,
• polyfunctional methacrylate compounds include glycerin trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tricaprolactonate trimethacrylate, trimethylolethane trimethacrylate, trimethylolhexane trimethacrylate, trimethylol octane trimethacrylate, pentaerythritol trimethacrylate, Pentaerythritol Tetramethacrylate, Pentaerythritol Tetracaprolactonate Tetramethacrylate, Diglycerin Tetramethacrylate, Ditrimethylolpropane Tetramethacrylate, Ditrimethylolpropane Tetracaprolactonate Tetramethacrylate, Ditrimethylolethane Tetramethacrylate, Ditrimethylolbutane Tetramethacrylate, Ditri Methylolhexanetetramethacrylate, ditrimethyloloctanetetra
• isocyanurate compounds that can be used as crosslinking agents include tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate, Polyfunctional (meth)acryloyl group-containing isocyanurates such as oxyethyl) isocyanurate; and polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate.
• crosslinking agents that can be suitably used, the following can be mentioned. They are a mixture of isocyanuric acid ethylene oxide-modified diacrylate and isocyanuric acid ethylene oxide-modified triacrylate (manufactured by Toagosei Co., Ltd., product name: "Aronix (registered trademark) M-315"), trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd., product name: "Aronix (registered trademark) M-315"), Co., Ltd., product name: "Aronix (registered trademark) M-309”), a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., product name: "Aronix (registered trademark) M- 403''), polyethylene glycol diacrylate (manufactured by
• the blending amount of the crosslinking agent is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, based on 100 parts by mass of the polymer described below. It is particularly preferably at least 5 parts by mass, most preferably at least 5 parts by mass, preferably at most 60 parts by mass, more preferably at most 50 parts by mass, even more preferably at most 40 parts by mass, It is particularly preferably 35 parts by mass or less, and most preferably 30 parts by mass or less. If the amount of the crosslinking agent is within the above range, better exposure margin expansion effects and pattern clarifying effects can be obtained. Furthermore, if the amount of the crosslinking agent is within the above range, the resulting resist pattern can have high resolution.
• the amount of the crosslinking agent can be further optimized depending on the functional number of the crosslinking agent.
• the amount of the crosslinking agent blended is preferably 6 parts by mass or more and 60 parts by mass or less, based on 100 parts by mass of the polymer.
• the amount of the crosslinking agent blended is preferably 5 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the polymer.
• the amount of the crosslinking agent blended is preferably 4 parts by mass or more and 40 parts by mass or less, based on 100 parts by mass of the polymer.
• the amount of the crosslinking agent blended is preferably 3 parts by mass or more and 30 parts by mass or less, based on 100 parts by mass of the polymer. If the blending amount of the crosslinking agent having a predetermined functional number is within the above range, better exposure margin expansion effects and pattern clarifying effects can be obtained. Furthermore, if the amount of the crosslinking agent having a predetermined functional number is within the above range, the resulting resist pattern can have high resolution.
• the polymer used in the resist pattern forming method of the present invention is not particularly limited.
• the polymer may be of the main chain truncated type or may be of the chemically amplified type.
• the main chain cleavage type polymer can be used alone or in combination of multiple types.
• the chemically amplified polymer can be used alone or in combination.
• the polymer is successfully used as a main chain cleavage type positive resist in which the main chain is cleaved and the molecular weight is reduced by irradiation with exposure light such as ionizing radiation such as an electron beam or non-ionizing radiation with a wavelength of 300 nm or less.
• exposure light such as ionizing radiation such as an electron beam or non-ionizing radiation with a wavelength of 300 nm or less.
• it is a polymer that can.
• polymers are not particularly limited, and are, for example, those described in Japanese Patent Publication No. 8-3636, Japanese Patent Application Publication No. 2020-134683, International Publication No. 2019/150966, and International Publication No. 2020/066806. You can use whatever you have.
• R 1 is a halogen atom or an alkyl group substituted with a halogen atom
• R 2 is an organic group having 0 to 11 hydrogen atoms or fluorine atoms
• R 3 and R 4 is a hydrogen atom, a halogen atom, an unsubstituted alkyl group, or an alkyl group substituted with a halogen atom, and may be the same or different from each other.
• R 5 , R 6 , R 8 , and R 9 are a hydrogen atom, a halogen atom, an unsubstituted alkyl group, or an alkyl group substituted with a halogen atom, and may be the same or different from each other)
• R7 is a hydrogen atom, an unsubstituted alkyl group, or an alkyl group substituted with a halogen atom
• B monomer unit represented by:
• the above-mentioned copolymer may contain any monomer units other than the monomer unit (A) and the monomer unit (B), but in all the monomer units constituting the copolymer,
• the proportion occupied by the monomer unit (A) and the monomer unit (B) is preferably 90 mol% or more in total, more preferably substantially 100 mol%, and 100 mol% (i.e. It is more preferable that the copolymer contains only the monomer unit (A) and the monomer unit (B).
• the above-mentioned copolymers include, for example, random polymers, block polymers, alternating polymers (ABAB%), etc., as long as they have a monomer unit (A) and a monomer unit (B). Any of these may be used, but it is preferably a copolymer containing 90% by mass or more (the upper limit is 100% by mass) of the alternating polymer.
• the above-mentioned copolymer contains predetermined monomer units (A) and monomer units (B), when exposed to light, the main chain is cut and the molecular weight is reduced. .
• the monomer unit (A) has the following general formula (III): (In formula (III), R 1 to R 4 are the same as those in formula (I).) It is a structural unit derived from monomer (a).
• the proportion of the monomer unit (A) in all the monomer units constituting the copolymer is not particularly limited, and can be, for example, 30 mol% or more and 70 mol% or less.
• the halogen atoms that can constitute R 1 , R 3 , and R 4 in formula (I) and formula (III) are not particularly limited, and include chlorine atom, fluorine atom, bromine atom, and iodine atom. can be mentioned.
• the alkyl group substituted with a halogen atom that can constitute R 1 , R 3 , and R 4 in formula (I) and formula (III) is not particularly limited, and the hydrogen atom in the alkyl group is not particularly limited. Examples include a group having a structure in which part or all of is substituted with the above halogen atom.
• the unsubstituted alkyl group that can constitute R 3 and R 4 in formula (I) and formula (III) is not particularly limited, and includes an unsubstituted alkyl group having 1 to 10 carbon atoms. Can be mentioned. Among these, the unsubstituted alkyl group that can constitute R 3 and R 4 is preferably a methyl group or an ethyl group.
• R 1 in formula (I) and formula (III) is a chlorine atom.
• a fluorine atom or an alkyl group substituted with a fluorine atom and having 1 to 5 carbon atoms more preferably a chlorine atom, a fluorine atom or a perfluoromethyl group, and a chlorine atom or a fluorine atom is more preferred, and a chlorine atom is particularly preferred.
• the monomer (a) in which R 1 in formula (III) is a chlorine atom has excellent polymerizability
• the monomer unit (A) in which R 1 in formula (I) is a chlorine atom The copolymer having the above is also excellent in that it is easy to prepare.
• R 3 and R 4 in formula (I) and formula (III) are Each is preferably a hydrogen atom or an unsubstituted alkyl group, more preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms, and still more preferably a hydrogen atom.
• R 2 in formula (I) and formula (III) is preferably a hydrogen atom or an organic group having 0 or more fluorine atoms.
• R 2 in formula (I) and formula (III) is preferably an organic group having 11 or less fluorine atoms. Note that when R 2 is an organic group, the number of carbon atoms in R 2 is usually 1 or more and 12 or less.
• R 2 in formula (I) and formula (III) is an alkyl group that may have a substituent, an alkoxyalkyl group that may have a substituent, or an alkyl group that may have a substituent.
• the above-mentioned substituent is not particularly limited, and includes halogen atoms such as a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
• R 2 in formula (I) and formula (III) is an alkyl group, an alkoxyalkyl group, an alkoxyalkenyl group, a fluoroalkyl group, a fluoroalkoxyalkyl group, a fluoroalkoxyalkenyl group, or a group represented by L-Ar. It is more preferable that there be.
• the alkyl group constituting R 2 is preferably a methyl group, ethyl group, propyl group, or butyl group.
• the alkoxyalkyl group constituting R 2 is preferably a methoxymethyl group, an ethoxymethyl group, or an ethoxyethyl group.
• the alkoxyalkenyl group constituting R 2 is preferably a methoxyvinyl group or an ethoxyvinyl group.
• fluoroalkyl group constituting R 2 examples include a monofluoromethyl group (having 1 fluorine atom and 1 carbon atom), a monofluoroethyl group (having 1 fluorine atom and 2 carbon atoms), and 2,2-difluoro Ethyl group (number of fluorine atoms is 2, number of carbon atoms is 2), 2,2,2-trifluoromethyl group (number of fluorine atoms is 3, number of carbon atoms is 1), 2,2,2-trifluoroethyl group (number of fluorine atoms is 3, number of carbon atoms is 2), 2,2,3,3,3-pentafluoropropyl group (number of fluorine atoms is 5, number of carbon atoms is 3), 3,3,4,4, 4-pentafluorobutyl group (number of fluorine atoms is 5, number of carbon atoms is 4), 2-(perfluorobutyl)ethyl group (number of fluor
• fluoroalkoxyalkyl group constituting R 2 examples include a pentafluoromethoxymethyl group (having 5 fluorine atoms and 2 carbon atoms), a pentafluoroethoxymethyl group (having 5 fluorine atoms and 3 carbon atoms), ) or a pentafluoroethoxyethyl group (the number of fluorine atoms is 5 and the number of carbon atoms is 4).
• the fluoroalkoxyalkenyl group constituting R 2 is preferably, for example, a pentafluoroethoxyvinyl group (having 5 fluorine atoms and 4 carbon atoms).
• the divalent linking group that can constitute L in the group represented by the formula L-Ar is not particularly limited, and includes, for example, an alkylene group that may have a substituent, and an alkylene group that may have a substituent. Examples include an alkenylene group which may be an ester.
• the alkylene group which may have a substituent is not particularly limited, and examples include chain alkylene groups such as methylene group, ethylene group, propylene group, n-butylene group, and isobutylene group. , and cyclic alkylene groups such as 1,4-cyclohexylene group.
• the alkylene group is preferably a linear alkylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, a propylene group, an n-butylene group, or an isobutylene group; More preferred are linear alkylene groups having 1 to 6 carbon atoms, such as the following, and even more preferred are linear alkylene groups having 1 to 3 carbon atoms, such as methylene, ethylene, propylene, and the like.
• alkenylene group which may have a substituent is not particularly limited, and examples include chain alkenylene groups such as ethenylene group, 2-propenylene group, 2-butenylene group, and 3-butenylene group. and cyclic alkenylene groups such as cyclohexenylene groups.
• alkenylene group linear alkenylene groups having 2 to 6 carbon atoms are preferable, such as ethenylene group, 2-propenylene group, 2-butenylene group, and 3-butenylene group.
• the divalent linking group is preferably an alkylene group that may have a substituent, and a carbon group that may have a substituent.
• a linear alkylene group having 1 to 6 carbon atoms is more preferable, a linear alkylene group having 1 to 6 carbon atoms which may have a substituent is even more preferable, and a linear alkylene group having 1 to 6 carbon atoms which may have a substituent is more preferable.
• the linear alkylene group of 3 is particularly preferred.
• the divalent linking group that can constitute L has one or more electron-withdrawing groups.
• the divalent linking group is an alkylene group having an electron-withdrawing group as a substituent or an alkenylene group having an electron-withdrawing group as a substituent
• the electron-withdrawing group is represented by formula (I) or formula (III). It is preferable that the bond is bonded to the carbon bonded to O adjacent to the carbonyl carbon in the carbonyl carbon.
• the electron-withdrawing group that can improve the sensitivity to exposure light is not particularly limited, and includes, for example, at least one selected from the group consisting of a fluorine atom, a fluoroalkyl group, a cyano group, and a nitro group. It will be done.
• the fluoroalkyl group is not particularly limited, and includes, for example, a fluoroalkyl group having 1 to 5 carbon atoms. Among these, the fluoroalkyl group is preferably a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a trifluoromethyl group.
• L is preferably a methylene group, a cyanomethylene group, a trifluoromethylmethylene group, or a bis(trifluoromethyl)methylene group; More preferred is a methylene group.
• examples of Ar in the group represented by the formula L-Ar include an aromatic hydrocarbon ring group that may have a substituent and an aromatic heterocyclic group that may have a substituent.
• the aromatic hydrocarbon ring group is not particularly limited, and includes, for example, a benzene ring group, a biphenyl ring group, a naphthalene ring group, an azulene ring group, an anthracene ring group, a phenanthrene ring group, a pyrene ring group, and a chrysene ring group.
• the aromatic heterocyclic group is not particularly limited, and examples thereof include a furan ring group, a thiophene ring group, a pyridine ring group, a pyridazine ring group, a pyrimidine ring group, a pyrazine ring group, a triazine ring group, and an oxadiazole ring group.
• cyclic group triazole cyclic group, imidazole cyclic group, pyrazole cyclic group, thiazole cyclic group, indole cyclic group, benzimidazole cyclic group, benzothiazole cyclic group, benzoxazole cyclic group, quinoxaline cyclic group, quinazoline cyclic group, phthalazine cyclic group, Examples include a benzofuran ring group, a dibenzofuran ring group, a benzothiophene ring group, a dibenzothiophene ring group, and a carbazole ring group.
• the substituent that Ar may have is not particularly limited, and examples thereof include an alkyl group, a fluorine atom, and a fluoroalkyl group.
• the alkyl group as a substituent that Ar may have include chain alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, and isobutyl group.
• examples of the fluoroalkyl group that Ar may have as a substituent include fluoroalkyl groups having 1 to 5 carbon atoms, such as a trifluoromethyl group, a trifluoroethyl group, and a pentafluoropropyl group.
• Ar is preferably an aromatic hydrocarbon ring group that may have a substituent, and more preferably an unsubstituted aromatic hydrocarbon ring group.
• a benzene ring group (phenyl group) is more preferred.
• the monomer (a) represented by the above-mentioned formula (III) that can form the monomer unit (A) represented by the above-mentioned formula (I) is not particularly limited;
• ⁇ -chloroacrylic acid alkyl esters such as methyl ⁇ -chloroacrylate, ethyl ⁇ -chloroacrylate, propyl ⁇ -chloroacrylate, butyl ⁇ -chloroacrylate; methyl ⁇ -fluoroacrylate, ⁇ -fluoroacrylate ⁇ -fluoroacrylic acid alkyl esters such as ethyl acid, ⁇ -propyl fluoroacrylate, butyl ⁇ -fluoroacrylate; ⁇ -chloroacrylic acid methoxymethyl ester, ⁇ -chloroacrylic acid ethoxymethyl ester, ⁇ -ethoxy chloroacrylate ⁇ -chloroacrylic acid alkoxyalkyl esters such as ethyl ester; ⁇ -flu
• the monomer unit (A) is a monomer unit such as ⁇ -methyl chloroacrylate.
• the monomer unit (B) has the following general formula (IV): (In formula (IV), R 5 to R 9 and p and q are the same as in formula (II).) A structural unit derived from monomer (b) represented by formula (IV).
• the proportion of the monomer unit (B) in all the monomer units constituting the polymer is not particularly limited, and can be, for example, 30 mol% or more and 70 mol% or less.
• the halogen atom or the alkyl group substituted with a halogen atom that may constitute R 5 to R 9 in formula (II) and formula (IV) is not particularly limited, and examples include a chlorine atom, a fluorine atom, , a halogen atom such as a bromine atom or an iodine atom, and a group having a structure in which part or all of the hydrogen atoms in an alkyl group are replaced with the above halogen atoms.
• the unsubstituted alkyl group that can constitute R 5 to R 9 in formula (II) and formula (IV) is not particularly limited, and includes an unsubstituted alkyl group having 1 to 5 carbon atoms. Can be mentioned. Among these, the unsubstituted alkyl group that can constitute R 5 to R 9 is preferably a methyl group or an ethyl group.
• R 5 in formula (II) and formula (IV) is a hydrogen atom or an unsubstituted is preferably an alkyl group, more preferably an unsubstituted alkyl group having 1 or more and 5 or less carbon atoms, and even more preferably a methyl group.
• all of the plurality of R 6 and/or R 7 in formula (II) and formula (IV) are hydrogen atoms or unsubstituted alkyl groups. It is preferably a hydrogen atom or an unsubstituted alkyl group having 1 or more and 5 or less carbon atoms, and even more preferably a hydrogen atom.
• p in formula (II) and formula (IV) is 5, q is 0, and all of the five R 6 are hydrogen atoms.
• R 6 's are hydrogen atoms or unsubstituted alkyl groups having 1 to 5 carbon atoms
• all 5 R 6 's are hydrogen atoms or unsubstituted alkyl groups having 1 to 5 carbon atoms. More preferably, it is a hydrogen atom.
• R 8 and R 9 in formula (II) and formula (IV) are respectively , is preferably a hydrogen atom or an unsubstituted alkyl group, more preferably a hydrogen atom or an unsubstituted alkyl group having 1 or more and 5 or less carbon atoms, and still more preferably a hydrogen atom.
• the monomer (b) represented by the above-mentioned formula (IV) that can form the monomer unit (B) represented by the above-mentioned formula (II) is not particularly limited. Examples include ⁇ -methylstyrene (AMS) and derivatives thereof such as (b-1) to (b-11) below.
• AMS ⁇ -methylstyrene
• the weight average molecular weight (Mw) of the copolymer is preferably 10,000 or more, more preferably 30,000 or more, even more preferably 40,000 or more, and preferably 500,000 or less, 300,000 or less. It is more preferable that When the weight average molecular weight (Mw) of the polymer is in the range from the lower limit to the upper limit, better exposure margin expansion effects and pattern clarifying effects can be obtained. Note that the weight average molecular weight of the copolymer can be determined as a standard polystyrene equivalent value, for example, by gel permeation chromatography. The weight average molecular weight of the copolymer can be measured, for example, by the method described in JP-A-2020-134683.
• the number average molecular weight (Mn) of the copolymer is preferably 6,000 or more, more preferably 18,000 or more, even more preferably 24,000 or more, preferably 300,000 or less, and 250,000 or less. is more preferable, and even more preferably 200,000 or less.
• Mn number average molecular weight
• the number average molecular weight (Mn) of the copolymer can be measured by the same method as the weight average molecular weight (Mw) described above.
• the molecular weight distribution (Mw/Mn) of the copolymer is preferably 1.1 or more, more preferably 1.2 or more, preferably 2.3 or less, and 2.0 or less. It is more preferable that If the molecular weight distribution (Mw/Mn) of the copolymer is 1.1 or more, the ease of manufacturing the copolymer can be improved. On the other hand, if the molecular weight distribution (Mw/Mn) of the copolymer is 2.3 or less, the clarity of the resulting resist pattern can be improved.
• the polymer can be prepared, for example, by polymerizing a monomer composition containing monomers and then optionally purifying the resulting polymer. Polymerization of a monomer composition containing a monomer and purification of the obtained polymer can be performed, for example, by the method described in JP 2020-134683A.
• the solvent is not particularly limited as long as it can dissolve the above-mentioned copolymer, and any known solvent can be used. Among these, from the viewpoint of improving the coatability of the resist composition, it is preferable to use anisole, propylene glycol monomethyl ether acetate (PGMEA), cyclopentanone, cyclohexanone, hexyl acetate, or isoamyl acetate as the solvent. In addition, one type of solvent may be used alone or a plurality of types may be used in combination.
• the resist composition of the present invention may optionally further contain known additives that can be incorporated into the resist composition.
• the blending amount of the additive is not particularly limited, and an appropriate amount can be added depending on the purpose.
• the resist composition of the present invention is not particularly limited, and can be produced by mixing the above-mentioned predetermined crosslinking agent, a solvent, a polymer, and optional additives.
• the mixing method is not particularly limited, and any known mixing method may be employed. Note that, if necessary, the mixture obtained by mixing the above-mentioned formulations can be filtered using a filter medium such as a filter.
• the resist pattern forming method of the present invention involves coating a substrate with a resist composition containing a crosslinking agent that reacts with ionizing radiation or non-ionizing radiation with a wavelength of 300 nm or less, a solvent, and a polymer.
• a resist film forming step in which a coating layer is obtained and the solvent is removed from the coating layer to form a resist film, and the resist film formed in the resist film forming step is exposed to ionizing radiation or , an exposure step (exposure step) of forming a latent image pattern while promoting a crosslinking reaction by the crosslinking agent by exposing non-ionizing radiation having a wavelength of 300 nm or less as exposure light.
• the resist pattern forming method of the present invention includes a step of developing the latent image pattern obtained in the exposure step (development step), a step of heating the resist film between the exposure step and the development step (post-exposure baking step). ) and/or may further include a step of washing and removing the developer (rinsing step) after the developing step.
• resist film formation process In the resist film forming step, a predetermined resist composition is coated on a workpiece such as a substrate to be processed using a resist pattern to obtain a coated layer (coating step), and then a coated layer is obtained (coating step). The solvent is removed from the coated layer to form a resist film (drying step).
• the workpieces to be coated with a predetermined resist composition in the coating process are not particularly limited, and include semiconductor substrates used in the production of semiconductor devices, etc.; insulating layers used in the production of printed circuit boards, etc. A substrate having a copper foil provided on an insulating layer; and mask blanks having a light shielding layer formed on the substrate can be used. Furthermore, the method for applying the predetermined resist composition is not particularly limited, and any known method can be employed. As the predetermined resist composition to be coated on the workpiece, the above-described positive resist composition of the present invention can be suitably used.
• the method for removing the solvent from the coating layer is not particularly limited, and a drying method generally used for forming a resist film can be used, but the resist composition may be heated (prebaked) to form a resist film.
• a film is formed.
• the temperature at which the coating layer is dried is preferably 100°C or higher, and 110°C or higher, from the viewpoint of adhesion between the resist film formed through the drying process and the workpiece. It is more preferable that the temperature be 250° C. or lower, and more preferably 200° C. or lower from the viewpoint of reducing thermal effects on the workpiece and the resist film.
• the time for drying the coating layer (drying time) is set at 10% from the viewpoint of sufficiently improving the adhesion between the resist film formed by performing the drying process at a lower temperature range and the workpiece. It is preferably longer than 2 seconds, more preferably 30 seconds or more, even more preferably 1 minute or more, and from the viewpoint of reducing changes in the molecular weight of the polymer in the resist film before and after the drying step, 60 minutes or less.
• the duration is preferably 30 minutes or less, and more preferably 30 minutes or less.
• a desired pattern is drawn by irradiating exposure light, which is ionizing radiation or non-ionizing radiation with a wavelength of 300 nm or less, to a predetermined location of the resist film formed in the resist film forming step.
• exposure light which is ionizing radiation or non-ionizing radiation with a wavelength of 300 nm or less
• a poorly soluble portion A and an easily soluble portion B are created in the resist film to form a latent image pattern.
• a latent image pattern is formed while the crosslinking reaction by the crosslinking agent is progressing.
• the crosslinking reaction and the polymer main chain cleavage reaction proceed in parallel in the exposure step. In this case, it is more advantageous in terms of expanding the exposure margin and obtaining clarity of the resist pattern.
• ionizing radiation is radiation that has sufficient energy to ionize atoms or molecules.
• non-ionizing radiation is radiation that does not have sufficient energy to ionize atoms or molecules.
• ionizing radiation examples include electron beams, extreme ultraviolet rays, gamma rays, X-rays, alpha rays, heavy particle beams, proton beams, beta rays, and ion beams.
• electron beams or extreme ultraviolet rays are preferable, and electron beams are more preferable.
• the wavelength of the extreme ultraviolet rays is not particularly limited, and can be, for example, 1 nm or more and 30 nm or less, and preferably 13.5 nm.
• KrF excimer laser beam 248 nm
• ArF excimer laser beam 193 nm
• the irradiation amount in the exposure step is not particularly limited, but is usually 10 mJ/cm 2 or more and 3000 mJ/cm 2 or less, and when using an electron beam (EB), it is usually 0.1 ⁇ C/cm 2 or more and 1000 ⁇ C/cm 2 It is as follows. Further, for example, as an exposure device that performs the exposure step, a known exposure device such as an electron beam lithography device or a laser lithography device can be used.
• a post-exposure baking step of heating the resist film is optionally performed after the exposure step.
• the heating temperature is not particularly limited, but from the viewpoint of sufficiently suppressing the occurrence of unevenness in the resist pattern, it is preferably 80°C or higher, more preferably 100°C or higher, and the resist film is not decomposed by heat. From the viewpoint of suppressing the generation of gas caused by this, the temperature is preferably 160°C or lower, and more preferably 140°C or lower.
• the time for heating the resist film in the post-exposure baking process is not particularly limited, but from the viewpoint of sufficiently suppressing the occurrence of unevenness in the resist pattern, it is preferably 30 seconds or more, and 1 minute. It is more preferable that the time is above, and from the viewpoint of production efficiency, the time is preferably 20 minutes or less, and more preferably 10 minutes or less.
• the method of heating the resist film in the post-exposure baking step is not particularly limited, and examples include a method of heating the resist film with a hot plate, a method of heating the resist film in an oven, and a method of blowing hot air onto the resist film. .
• the latent image pattern of the resist film that has undergone the exposure process or the post-exposure baking process is developed to form a developed film on the workpiece.
• the resist film can be developed by, for example, bringing the resist film into contact with a developer.
• the method of bringing the resist film into contact with the developer is not particularly limited, and known methods such as immersing the resist film in the developer or applying the developer to the resist film can be used.
• the developer can be appropriately selected depending on the properties of the copolymer described above.
• As the developer it is preferable to select a developer that does not dissolve the resist film before the exposure process, but can dissolve the easily soluble portion B of the resist film that has undergone the exposure process or the post-exposure bake process.
• the developer is not particularly limited, and any known developer can be used. Moreover, one type of developer may be used alone, or two or more types may be used as a mixture in any ratio.
• a step of removing the developer can be performed after the developing step.
• the developer can be removed using, for example, a rinse solution.
• the rinsing liquid is not particularly limited as long as it does not dissolve the resist pattern, and water or a solution containing a general organic solvent can be used. When selecting a rinsing liquid, it is preferable to select a rinsing liquid that easily mixes with the developer.
• ⁇ Attributes of crosslinking agent> The determination of whether a crosslinking agent satisfies the attribute of "reacting with ionizing radiation or non-ionizing radiation with a wavelength of 300 nm or less" was carried out according to the following method.
• a crosslinking agent solution (concentration: 10% by mass, solvent: isoamyl acetate) was applied onto a silicon wafer, the solvent was evaporated, and a test piece was prepared that did not flow even when left standing. The thickness of this test piece was measured and defined as T1 .
• this test piece After irradiating this test piece with a 50 keV electron beam at 400 uC/cm 2 , it was immersed for 1 minute at room temperature (23°C) in the same type of solvent used to prepare the crosslinking agent solution. Dry. The thickness T 2 of the dried test piece is measured, and if the value of T 2 /T 1 ⁇ 100 is 50% or more, it is determined that the crosslinking agent has reacted with ionizing radiation or non-ionizing radiation with a wavelength of 300 nm or less. ” was determined.
• ⁇ Exposure margin> The range of electron beam irradiation that allowed formation of a resist pattern with a half pitch (hp) of 25 nm was evaluated in accordance with the following criteria in "resolution of resist pattern" described below.
• B Range of electron beam irradiation amount is 30 ⁇ C/cm 2 or more and less than 50 ⁇ C/cm Less than 2
• Electron beam irradiation range is less than 30 ⁇ C/cm 2
• ⁇ Resolution of resist pattern> Regarding the line and space patterns with half pitch (hp) of 18 nm, 20 nm, 22 nm, 25 nm, and 30 nm formed in Examples and Comparative Examples, the pattern quality was not concerned, and a certain electron beam irradiation amount (irradiated 10 to 600 ⁇ C/cm 2 ), it was visually confirmed whether the resist pattern was formed as a whole. Then, the resolution of the resist pattern was evaluated according to the following criteria. AA: Patterns with half pitch (hp) of 18 nm, 20 nm, 22 nm, 25 nm, and 30 nm have been formed.
• A Patterns with half pitches (hp) of 20 nm, 22 nm, 25 nm, and 30 nm have been formed.
• B Patterns with half pitches (hp) of 22 nm, 25 nm, and 30 nm have been formed.
• C Patterns with half pitch (hp) of 25 nm and 30 nm have been formed. Or the pattern has not been formed.
• the temperature was returned to room temperature and the inside of the glass container was exposed to the atmosphere, and then 10 g of tetrahydrofuran (THF) was added to the obtained solution.
• THF tetrahydrofuran
• a solution containing 10 g of THF was dropped into 100 g of methanol to precipitate a polymer, and then the solution containing the precipitated polymer was filtered through a Kiriyama funnel to obtain a white coagulated product (polymer).
• the obtained polymer was dissolved in 10 g of THF, the obtained solution was added dropwise to 100 g of methanol (MeOH), the precipitated solid content was separated by filtration, and the obtained solid content was further dissolved in 10 g of THF.
• the resulting solution was added dropwise to 100 g of methanol (MeOH) (that is, reprecipitation purification was performed twice by dropping the THF solution into methanol), and a white solidified product ( ⁇ -methylstyrene units and ⁇ -chloro A copolymer containing methyl acrylate units) was precipitated. Thereafter, the solution containing the precipitated copolymer was filtered using a Kiriyama funnel to obtain a white copolymer A.
• the weight average molecular weight (Mw) of the obtained polymer was 55,000, the number average molecular weight (Mn) was 29,000, and the molecular weight distribution (Mw/Mn) was 1.90.
• Copolymer B contained 50 mol% each of ⁇ -methylstyrene units and ⁇ -chloroacrylate-1-phenyl-1-trifluoromethyl-2,2,2-trifluoroethyl units.
• the weight average molecular weight (Mw) of the obtained polymer was 62,344, the number average molecular weight (Mn) was 39,845, and the molecular weight distribution (Mw/Mn) was 1.565.
• composition 1 100 parts by mass of copolymer A synthesized in Synthesis Example 1, a mixture of isocyanuric acid ethylene oxide modified diacrylate and isocyanuric acid ethylene oxide modified triacrylate as a crosslinking agent (manufactured by Toagosei Co., Ltd., product name: "Aronix (registered) Trademark) M-315'', a mixture of bifunctional compounds and trifunctional compounds, 5 parts by mass of crosslinking agent A) (denoted as crosslinking agent A in Tables 1 and 2), and 5143 parts by mass of anisole as a solvent were mixed, resulting in a mixed solution.
• crosslinking agent A manufactured by Toagosei Co., Ltd., product name: "Aronix (registered) Trademark
• Composition 1 was filtered through a membrane filter with a pore size of 20 nm to prepare Composition 1.
• ⁇ Formation of resist pattern> -Resist film formation process- Using a spin coater (manufactured by Mikasa, MS-A150), the positive resist composition prepared in Synthesis Example 1 was coated onto a 4-inch silicon wafer to a thickness of 30 nm to form a coating layer. (Coating process). In order to remove the solvent from the formed coating layer, the coating layer was heated and dried (prebaked) for 3 minutes on a hot plate at a temperature of 180° C. to form a positive resist film on the silicon wafer (drying step).
• the resist film was exposed using an electron beam lithography system (manufactured by Elionix Co., Ltd., ELS-S50) at an acceleration voltage of 50 kV and an electron beam irradiation amount of 10 to 600 ⁇ C/cm 2 to form a half pitch (hp) of 18 nm.
• ELS-S50 electron beam lithography system
• hp half pitch
• Example 2 Composition 2 (Example 2) and Composition 3 (Example 3) were prepared in the same manner as in Example 1, except that the amount of crosslinking agent was changed to 15 parts (Example 2) or 25 parts (Example 3).
• Example 3) were prepared, resist patterns were formed in the same manner as in Example 1, and various evaluations similar to those in Example 1 were performed. The results are shown in Table 1.
• Example 4 Using Composition 2, the same resist film forming step to exposure step as in Example 1 was carried out, and then, before the development step, a post-exposure baking step was performed in which the resist film was heated on a hot plate at a temperature of 120° C. for 1 minute. Ta. Thereafter, the same development process as in Example 1 was carried out, and various evaluations similar to those in Example 1 were carried out. The results are shown in Table 1.
• composition 4 Preparation of positive resist composition (composition 4)> 100 parts by mass of copolymer B prepared in Synthesis Example 2, a mixture of isocyanuric acid ethylene oxide modified diacrylate and isocyanuric acid ethylene oxide modified triacrylate as a crosslinking agent (manufactured by Toagosei Co., Ltd., product name: "Aronix M-") 315'', a mixture of bifunctional compounds and trifunctional compounds (denoted as crosslinking agent A in Tables 1 and 2), and 5143 parts by mass of isoamyl acetate as a solvent, and the resulting mixed solution was Composition 4 was prepared by filtration with a membrane filter.
• Example 7 Composition 5 (Example 6) and Composition 6 (Example 6) were prepared in the same manner as in Example 5, except that the amount of crosslinking agent was changed to 15 parts (Example 6) or 25 parts (Example 7).
• Example 7) were prepared, resist patterns were formed in the same manner as in Example 1, and various evaluations similar to those in Example 1 were performed. The results are shown in Table 1.
• Example 8 Using Composition 5, the same resist film forming step to exposure step as in Example 6 was carried out, and then, before the development step, a post-exposure baking step was performed in which the resist film was heated on a hot plate at a temperature of 120° C. for 1 minute. Ta. Thereafter, the same development process as in Example 1 was carried out, and various evaluations similar to those in Example 1 were carried out. The results are shown in Table 1.
• Example 9 The crosslinking agent added to the resist composition is trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd., product name: "Aronix (registered trademark) M-309", trifunctional, expressed as crosslinking agent B in Tables 1 and 2).
• Composition 7 was prepared in the same manner as in Example 1 except that the amount was changed to 15 parts, a resist pattern was formed in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 1.
• the crosslinking agent to be added to the resist composition is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., product name: "Aronix (registered trademark) M-403", pentafunctional, Tables 1 to 2).
• Composition 8 was prepared in the same manner as in Example 1 except that the amount was changed to 10 parts (denoted as crosslinking agent C), a resist pattern was formed, and various evaluations were performed. The results are shown in Table 1.
• Example 11 The crosslinking agent added to the resist composition is polyethylene glycol diacrylate (manufactured by Toagosei Co., Ltd., product name: "Aronix (registered trademark) M-240"), bifunctional, expressed as crosslinking agent D in Tables 1 and 2).
• Composition 9 was prepared in the same manner as in Example 5 except that the amount was changed to 20 parts, a resist pattern was formed, and various evaluations were performed. The results are shown in Table 1.
• Example 12 Except that the crosslinking agent added to the resist composition was changed to 15 parts of triallylisocyanurate (manufactured by Mitsubishi Chemical Corporation, product name: "TAIC", trifunctional, expressed as crosslinking agent H in Tables 1 and 2).
• Composition 10 was prepared in the same manner as in Example 1, a resist pattern was formed, and various evaluations were performed. The results are shown in Table 1.
• Example 13 Except that the crosslinking agent added to the resist composition was changed to 15 parts of triethylene glycol divinyl ether (manufactured by Nippon Carbide Industries Co., Ltd., product name "TEGDVE", bifunctional, expressed as crosslinking agent I in Tables 1 and 2). Composition 11 was prepared in the same manner as in Example 5, a resist pattern was formed, and various evaluations were performed. The results are shown in Table 1.
• Example 14 As the polymer blended into the resist composition, polymethyl methacrylate (denoted as Polymer C in Table 1, weight average molecular weight in terms of polystyrene: 40,000) was used instead of a copolymer. Then, 100 parts by mass of the polymer C, a mixture of isocyanuric acid ethylene oxide modified diacrylate and isocyanuric acid ethylene oxide modified triacrylate as a crosslinking agent (manufactured by Toagosei Co., Ltd., product name: "Aronix (registered trademark) M- 315'', a mixture of bifunctional compounds and trifunctional compounds (denoted as crosslinking agent A in Tables 1 and 2), and 5634 parts by mass of cellosolve acetate as a solvent were mixed, and the resulting mixed solution was mixed with a pore size of 20 nm.
• a crosslinking agent manufactured by Toagosei Co., Ltd., product name: "Aronix (registered trademark) M
• Composition 12 was prepared by filtration with a membrane filter.
• heating drying prebaking
• prebaking heating drying
• Example 15 Except that the crosslinking agent added to the resist composition was changed to 35 parts of triallylisocyanurate (manufactured by Mitsubishi Chemical Corporation, product name: "TAIC", trifunctional, expressed as crosslinking agent H in Tables 1 and 2).
• Composition 13 was prepared in the same manner as in Example 5, a resist pattern was formed, and various evaluations were performed. The results are shown in Table 1.
• Example 16 The crosslinking agent added to the resist composition was changed to 40 parts of phenoxypolyethylene glycol acrylate (manufactured by Shin Nakamura Chemical Co., Ltd., product name: "NK Ester AMP20GY", monofunctional, expressed as crosslinking agent E in Tables 1 and 2). Except for the above, Composition 14 was prepared in the same manner as in Example 5, a resist pattern was formed, and various evaluations were performed. The results are shown in Table 1.
• Example 17 The crosslinking agent added to the resist composition is ethoxylated -o-phenylphenol acrylate (manufactured by Shin Nakamura Chemical Co., Ltd., product name: "NK ester A-LEN-10"), monofunctional, crosslinked according to Tables 1 and 2.
• Composition 15 was prepared in the same manner as in Example 5 except that the amount was changed to 40 parts (denoted as Agent F), a resist pattern was formed, and various evaluations were performed. The results are shown in Table 1.
• the crosslinking agent to be added to the resist composition is 2-acryloyloxyethyl succinate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: "NK Ester A-SA”), monofunctional, and crosslinking agent G in Tables 1 and 2.
• Composition 16 was prepared in the same manner as in Example 5 except that the amount was changed to 40 parts, a resist pattern was formed, and various evaluations were performed. The results are shown in Table 1.
• Composition 17 was prepared in the same manner as in Example 1 except that no crosslinking agent was blended, a resist pattern was formed, and various evaluations were performed. The results are shown in Table 2.
• Composition 18 was prepared in the same manner as in Example 5, except that no crosslinking agent was added, a resist pattern was formed, and various evaluations were performed. The results are shown in Table 2.
• Comparative example 3 Using Composition 17 prepared in the same manner as Comparative Example 1, except that heating drying (prebaking) to remove the solvent from the coating layer in the resist film forming step was performed on a hot plate at a temperature of 180 ° C. for 3 minutes. After carrying out the same resist film forming step to exposure step as in Example 1, a post-exposure baking step was performed in which the resist film was heated for 1 minute on a hot plate at a temperature of 120° C. before the developing step. Thereafter, the same development process as in Example 1 was carried out, and various evaluations similar to those in Example 1 were carried out. The results are shown in Table 2.
• Composition 19 was prepared in the same manner as in Example 14 except that no crosslinking agent was added, a resist pattern was formed, and various evaluations were performed. The results are shown in Table 2.
• Composition 20 similar to Comparative Example 5 was prepared, and 2 parts of 1-benzyl-2-phenylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: "Curezol (registered trademark) 1B2PZ"), which is a curing agent, was further added. Composition 21 was obtained. Using this composition, a coating layer was formed in the same manner as in Example 1, and the coating layer was heated on a hot plate at a temperature of 150°C for 2 hours to not only remove the solvent from the coating layer, but also to remove the solvent from the coating layer. The crosslinking reaction of crosslinking agent J was allowed to proceed. Regarding the resist film thus obtained, a resist pattern was formed in the same manner as in Comparative Example 5, and various evaluations were performed. The results are shown in Table 2.
• the present invention it is possible to provide a resist composition and a resist pattern forming method that can form a clear resist pattern with a wide exposure margin and few defects.

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