WO2012046543A1 - Procédé de formation d'un motif de réserve et composition de résine sensible aux rayonnements - Google Patents

Procédé de formation d'un motif de réserve et composition de résine sensible aux rayonnements Download PDF

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Publication number
WO2012046543A1
WO2012046543A1 PCT/JP2011/070770 JP2011070770W WO2012046543A1 WO 2012046543 A1 WO2012046543 A1 WO 2012046543A1 JP 2011070770 W JP2011070770 W JP 2011070770W WO 2012046543 A1 WO2012046543 A1 WO 2012046543A1
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group
polymer
radiation
acid
anion
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Japanese (ja)
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亘史 伊藤
宏和 榊原
雅史 堀
泰一 古川
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JSR Corp
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JSR Corp
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    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/325—Non-aqueous compositions

Definitions

  • the present invention relates to a resist pattern forming method and a radiation sensitive resin composition.
  • immersion exposure it is said that even when a light source having the same exposure wavelength is used, the same high resolution as that when a light source having a shorter wavelength is used can be achieved. Therefore, immersion exposure is attracting attention as a technique for achieving high resolution while reducing an increase in cost in the manufacture of semiconductor elements that require a large capital investment.
  • the resist film changes in quality due to elution of substances contained in the resist into the immersion medium and the performance is degraded, and the refractive index of the immersion medium is locally affected by the eluted substances.
  • There may be inconveniences that adversely affect the lithographic properties due to the change and contamination of the lens surface by the eluted substances see WO 04/068242 pamphlet.
  • a double exposure technique or a double patterning technique is known.
  • the present invention has been made on the basis of the above circumstances, and the object thereof is a method for forming a resist pattern that has less occurrence of missing contact holes when a developer containing an organic solvent is used and has excellent lithography properties, and It is to provide a radiation sensitive resin composition.
  • the invention made to solve the above problems is (1) a resist film forming step of applying a radiation sensitive resin composition on a substrate; (2) an exposure step, and (3) a resist pattern forming method including a step of developing using a developer containing 80% by mass or more of an organic solvent,
  • the radiation sensitive resin composition is [A] Base polymer having an acid dissociable group (hereinafter sometimes referred to as “[A] polymer”)
  • the [B] acid generator contained in the radiation sensitive resin composition has an alicyclic group, and the atomic ratio (F / C) of fluorine atom to carbon atom is 0.1 or more and 0.5.
  • the [C] polymer having a higher fluorine atom content than the [A] polymer is unevenly distributed on the resist film surface at the time of applying the resist, thereby imparting water repellency to the resist and soaking the liquid.
  • a resist film more suitable for exposure can be formed. Therefore, in the resist pattern forming method in which development is performed using a developer containing 80% by mass or more of an organic solvent, the occurrence of missing contact holes is suppressed and the lithography properties are excellent by combining the composition having the specific structure. Resist pattern formation is possible.
  • the acid dissociable group of the polymer preferably has a monocyclic or polycyclic alicyclic hydrocarbon group. Thereby, it is excellent in acid dissociation property and sufficient sensitivity can be obtained.
  • R 1 is a monovalent organic group containing a monocyclic or polycyclic alicyclic group.
  • N is 1 or 2.
  • R f1 and R f2 are each independently. A hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 4 carbon atoms, except when both R f1 and R f2 are hydrogen atoms, and each of R f1 and R f2 has a plurality of In this case, the plurality of R f1 and R f2 may be the same or different.
  • the [B] acid generator Since the anion of the acid generator has the above-mentioned specific structure, the [B] acid generator is more uniformly dispersed in the resist film, and effectively suppresses uneven generation of acid in the exposed area. Can do.
  • the anion having an alicyclic group of the acid generator is preferably at least one anion selected from the group consisting of anions represented by the following formulas (2) to (5).
  • the dispersibility of the [B] acid generator in the resist film is further improved, and the suppression of the occurrence of missing contact holes can be further enhanced.
  • the organic solvent contained in the developer is at least one solvent selected from the group consisting of alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, and hydrocarbon solvents. Is preferred.
  • a specific organic solvent an appropriate combination with a predetermined resist composition can be realized, and a resist pattern with more excellent lithography characteristics can be obtained.
  • the radiation sensitive resin composition of the present invention [A] a base polymer having an acid dissociable group, [B] Generation of a radiation-sensitive acid containing a cation and an anion having an alicyclic group, wherein the ratio of the number of atoms (F / C) of fluorine and carbon in the anion is 0.1 or more and 0.5 or less And [C] a fluorine atom, and a polymer having a fluorine atom content higher than that of the polymer [A].
  • production of a missing contact hole can be effectively suppressed in the resist pattern formation method using the developing solution containing an organic solvent.
  • the present invention is suitable for immersion exposure, and provides a resist pattern forming method and a radiation-sensitive resin composition that are excellent in lithography characteristics with less occurrence of missing contact holes when a developer containing an organic solvent is used. can do.
  • a resist film forming step of applying a radiation-sensitive resin composition on a substrate (2) an exposure step, and (3) development using a developer containing 80% by mass or more of an organic solvent.
  • a resist pattern forming method including a step, wherein the radiation sensitive resin composition includes [A] a base polymer having an acid dissociable group, [B] a cation and an anion having an alicyclic group, A radiation-sensitive acid generator having an atomic number ratio (F / C) of an anion fluorine atom to carbon atom of 0.1 to 0.5, and [C] a fluorine atom, and a [A] polymer It is characterized by containing a polymer having a higher fluorine atom content.
  • each process is explained in full detail.
  • the composition used in the present invention is applied onto a substrate to form a resist film.
  • a substrate for example, a conventionally known substrate such as a silicon wafer or a wafer coated with aluminum can be used.
  • an organic or inorganic antireflection film disclosed in Japanese Patent Publication No. 6-12452 and Japanese Patent Application Laid-Open No. 59-93448 may be formed on the substrate.
  • the thickness of the resist film to be formed is usually 0.01 ⁇ m to 1 ⁇ m, preferably 0.01 ⁇ m to 0.5 ⁇ m.
  • the solvent in the coating film may be volatilized by pre-baking (PB).
  • PB pre-baking
  • the heating conditions for PB are appropriately selected depending on the composition of the composition, but are usually about 30 to 200 ° C, preferably 50 to 150 ° C.
  • a protective film disclosed in, for example, Japanese Patent Laid-Open No. 5-188598 can be provided on the resist layer.
  • an immersion protective film disclosed in, for example, Japanese Patent Application Laid-Open No. 2005-352384 can be provided on the resist layer.
  • Step (2) exposure is performed by reducing and projecting onto a desired region of the resist film formed in step (1) through a mask having a specific pattern and, if necessary, an immersion liquid.
  • the hole pattern can be obtained by performing reduction projection exposure on a substrate coated with a resist through a desired dot pattern mask and developing.
  • the trench pattern can be formed by performing reduced projection exposure on a desired region through an isoline pattern mask. The exposure may be performed twice or more depending on a desired pattern and a mask pattern. When performing exposure twice or more, it is preferable to perform exposure continuously.
  • a first reduced projection exposure is performed on a desired area via a line and space pattern mask, and then the second is so that the line intersects the exposed portion where the first exposure has been performed.
  • a circular contact hole pattern can be formed in the unexposed part surrounded by the exposed part by making the first exposed part and the second exposed part orthogonal to each other.
  • the immersion liquid used for exposure include water and a fluorine-based inert liquid.
  • the immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient that is as small as possible so as to minimize distortion of the optical image projected onto the film.
  • excimer laser light wavelength 193 nm
  • the water used is preferably distilled water.
  • the radiation used for exposure is appropriately selected according to the type of [B] acid generator, and examples thereof include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. Among these, far ultraviolet rays represented by ArF excimer laser and KrF excimer laser (wavelength 248 nm) are preferable, and ArF excimer laser is more preferable.
  • the exposure conditions such as the exposure amount are appropriately selected according to the composition of the composition, the type of additive, and the like.
  • the exposure process may have a plurality of times, and the plurality of exposures may use the same light source or different light sources, but the ArF excimer laser is used for the first exposure. It is preferable to use light.
  • PEB post-exposure baking
  • Step (3) In this step, after the exposure in the step (2), development is performed using a negative developer containing 80% by mass or more of an organic solvent to form a resist pattern.
  • the negative developer is a developer that selectively dissolves and removes the low-exposed portion and the unexposed portion.
  • the organic solvent used as the negative developer is at least one selected from the group consisting of alcohol solvents, ether solvents, ketone organic solvents, amide solvents, ester organic solvents, and hydrocarbon solvents. Is preferred.
  • alcohol solvent examples include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol , Sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec -und
  • ether solvent examples include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether and the like.
  • ketone solvents include acetone, 2-butanone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl amyl ketone, ethyl-n-butyl ketone, and methyl-n-.
  • ketone solvents such as hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, etc. .
  • amide solvents include N, N′-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, Examples thereof include N-methylpropionamide and N-methylpyrrolidone.
  • ester solvents include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, ⁇ -butyrolactone, ⁇ -valerolactone, n-propyl acetate, iso-propyl acetate, acetic acid-butyl, isopropyl acetate, amyl acetate, iso acetate -Butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-acetate -Nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether
  • hydrocarbon solvents examples include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, cyclohexane , Aliphatic hydrocarbon solvents such as methylcyclohexane; Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene, n-amylnaphthalene Group hydrocarbon solvents and the like.
  • methyl amyl ketone, butyl acetate, isopropyl acetate and amyl acetate are preferred.
  • These organic solvents may be used alone or in combination of two or more.
  • the content of the organic solvent in the developer is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass or more.
  • the organic solvent contained in the developer within the above range, the unexposed portion can be effectively dissolved and removed, and a resist pattern having excellent development characteristics and lithography characteristics can be formed.
  • components other than the organic solvent include water and silicone oil.
  • a surfactant can be added to the developer as necessary.
  • a surfactant for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used.
  • a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle method) ), A method of spraying the developer on the substrate surface (spray method), a method of continuously applying the developer while scanning the developer coating nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
  • the resist film may be washed with a rinse solution after the development in the step (3).
  • an organic solvent can be used also as the rinse liquid in the rinse process, and the generated scum can be efficiently washed.
  • the rinsing liquid hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and the like are preferable. Of these, alcohol solvents and ester solvents are preferable, and monovalent alcohol solvents having 6 to 8 carbon atoms are more preferable.
  • Examples of the monohydric alcohol having 6 to 8 carbon atoms include linear, branched or cyclic monohydric alcohols such as 1-hexanol, 1-heptanol, 1-octanol, and 4-methyl-2-pen. Examples include butanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. Of these, 1-hexanol, 2-hexanol, 2-heptanol, and 4-methyl-2-pentanol are preferable.
  • Each component of the rinse liquid may be used alone or in combination of two or more.
  • the water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.
  • the surfactant mentioned later can be added to the rinse liquid.
  • a cleaning method for example, a method of continuously applying a rinse liquid onto a substrate rotating at a constant speed (rotary coating method), a method of immersing the substrate in a tank filled with the rinse liquid for a predetermined time (dip method) ), A method (spray method) of spraying a rinse liquid on the substrate surface, and the like.
  • the radiation sensitive resin composition used in the present invention contains a [A] polymer, a [B] acid generator, and a [C] polymer.
  • the polymer [A] has an acid dissociable group, and the polarity of the polymer [A] is increased by the dissociation of the acid dissociable group by the action of the acid generated from the [B] acid generator.
  • the acid generator includes a cation and an anion having an alicyclic group, and the atomic number ratio (F / C) of the fluorine atom to the carbon atom of the anion is 0.1 or more and 0.5 or less.
  • the [C] polymer contains fluorine atoms, has a higher fluorine atom content than the [A] polymer, and is unevenly distributed on the resist film surface, so that it can impart water repellency and is suitable for immersion exposure. Contributes to film formation.
  • the said composition may contain arbitrary components in the range which does not impair the effect of this invention. Hereinafter, each component will be described in detail.
  • the polymer is a base polymer containing a structural unit having an acid-dissociable group and increasing in polarity when the acid-dissociable group is dissociated by the action of an acid.
  • the base polymer refers to a polymer that is a main component among the polymers constituting the resist pattern formed from the radiation-sensitive resin composition, and preferably the total polymer constituting the resist pattern. A polymer occupying 50% by mass or more.
  • the “acid-dissociable group” is a group that substitutes a hydrogen atom in a polar functional group such as a carboxyl group, and means a group that is dissociated by the action of an acid generated from an acid generator [B] upon exposure.
  • Specific acid dissociable groups possessed by the polymer include groups represented by the following general formula (7).
  • R 2 is a hydrogen atom, a methyl group or a trifluoromethyl group .
  • R p represents an acid dissociable group.
  • the acid dissociable group represented by R p is preferably a group represented by the following formula (7).
  • R p1 , R p2 and R p3 are each an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a monovalent group having 4 to 20 carbon atoms.
  • R p2 and R p3 may be bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms together with the carbon atom to which they are bonded.
  • Examples of the alkyl group having 1 to 4 carbon atoms represented by R p1 , R p2 and R p3 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group and the like.
  • Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R p1 , R p2 and R p3 include polycyclic alicyclic rings having a bridged skeleton such as an adamantane skeleton and a norbornane skeleton. A formula group; And monocyclic alicyclic groups having a cycloalkane skeleton such as cyclopentane and cyclohexane. These groups may be substituted with one or more of linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, for example.
  • Examples of the monovalent heterocyclic group having 4 to 20 carbon atoms represented by R p1 , R p2 and R p3 include groups represented by the following formulae.
  • n represents an integer of 0 to 3
  • X represents an oxygen atom or a methylene group.
  • R p1 is an alkyl group having 1 to 4 carbon atoms
  • R p2 and R p3 are bonded to each other and have an adamantane skeleton or a cycloalkane skeleton together with the carbon atoms to which they are bonded. It is preferable to form a divalent group.
  • Examples of the structural unit (I) include structural units represented by the following formulas (6-1) to (6-4).
  • R 2 is .R p1, R p2 and R p3 as defined in the above formula (6) has the same meaning as the above formula (7) .
  • n p is (It is an integer from 1 to 4.)
  • Examples of the structural unit represented by the above formula (6) or (6-1) to (6-4) include a structural unit represented by the following formula.
  • the content of the structural unit (I) is preferably such that the total amount of the structural unit (I) with respect to all the structural units constituting the [A] polymer exceeds 10 mol%, More preferably, it is 60 mol%.
  • the [A] polymer may have 1 type, or 2 or more types of structural units (I).
  • the polymer preferably has a structural unit (II) having a lactone structure and / or a cyclic carbonate structure.
  • the lactone structure represents a cyclic group containing one ring (lactone ring) containing an —O—C (O) — structure.
  • the lactone ring is counted as the first ring, and when it is only the lactone ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure.
  • structural unit (II) which has a lactone structure As structural unit (II) which has a lactone structure, the structural unit represented by a following formula is mentioned, for example.
  • R L1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • Examples of the monomer that generates the structural unit (II) containing a lactone structure include compounds represented by the following formula (L-1).
  • R L1 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R L2 is a single bond or a divalent linking group.
  • R L3 is a monovalent organic compound having a lactone structure. Group.
  • Examples of the divalent linking group represented by R L2 include a divalent linear or branched hydrocarbon group having 1 to 20 carbon atoms.
  • Examples of the monovalent organic group having a lactone structure represented by R L3 include groups represented by the following formulas (L3-1) to (L3-6).
  • R Lc1 is an oxygen atom or a methylene group.
  • R Lc2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • N Lc1 is 0 or 1.
  • N Lc2 is an integer of 0 to 3. * represents a bond that binds to R L2 in the above formula (L-1), and is represented by formulas (L3-1) to (L3-6). The group to be substituted may have a substituent.
  • Examples of a preferable monomer that gives the structural unit (II) having the lactone structure include monomers described in paragraph [0043] of International Publication No. 2007/116664.
  • R C1 is a hydrogen atom or a methyl group.
  • the content of the structural unit (II) is preferably such that the total amount of the structural unit (II) with respect to all the structural units constituting the [A] polymer exceeds 10 mol%, More preferably, it is 60 mol%.
  • the polymer may have one or more structural units (II).
  • the polymer may contain other structural units other than the above structural units (I) and / or (II).
  • Examples of the structural unit other than the structural unit (I) and / or (II) include, for example, adamantane-1-yl (meth) acrylate, 3-methyladamantan-1-yl (meth) acrylate, and (meth) acrylic.
  • the polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator.
  • a radical polymerization initiator for example, a solution containing a monomer and a radical initiator is dropped into a reaction solvent or a solution containing the monomer to cause a polymerization reaction, and a solution containing the monomer and
  • a solution containing a radical initiator is dropped into a solution containing a reaction solvent or a monomer separately to cause a polymerization reaction.
  • radical initiator used in the polymerization examples include azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2 -Cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and the like. These initiators may be used alone or in combination of two or more.
  • Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; Ketones such as acetone, 2-butanone, 4-methyl-2-p
  • the reaction temperature in the polymerization is usually about 40 ° C to 150 ° C, and preferably 50 ° C to 120 ° C.
  • the reaction time is usually about 1 to 48 hours, and preferably 1 to 24 hours.
  • the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and 1,000. ⁇ 30,000 is particularly preferred.
  • Mw of a polymer By making Mw of a polymer into the said range, it has the solubility to a resist solvent sufficient to use as a resist, and dry etching resistance and a resist pattern cross-sectional shape become favorable.
  • the ratio (Mw / Mn) of the Mw of the polymer to the number average molecular weight (Mn) in terms of polystyrene by GPC method is usually 1 to 3, preferably 1 to 2.
  • [B] Acid generator> The acid generator generates an acid upon exposure, and the acid dissociable groups present in the [A] polymer are dissociated by the acid. As a result, the polymer [A] becomes hardly soluble in a developer containing an organic solvent.
  • the content of the [B] acid generator in the composition is a compound as described below (hereinafter sometimes referred to as “[B] acid generator” as appropriate), and the anion or cation is a polymer. It may be in the form incorporated as part or a mixture of both forms.
  • the [B] acid generator used in the present invention contains a cation and an anion having an alicyclic group, and the atomic ratio (F / C) of fluorine atom to carbon atom of this anion is 0.1 or more and 0.00. 5 or less.
  • the anion of the acid generator has an alicyclic group, the [B] acid generator is excellent in compatibility with the resin and suitability as a composition.
  • the atomic ratio (F / C) of fluorine atoms and carbon atoms contained in the anion is 0.1 or more and 0.5 or less, the [B] acid generator is unevenly distributed in the vicinity of the resist film surface. Evenly distributed without any problems.
  • the [B] acid generator is uniformly dispersed in the resist film, so that excessive generation of acid on the resist film surface is suppressed, and the polymer deprotects specifically on the outermost surface of the resist coating film. As a result, the occurrence of missing contact holes can be prevented.
  • Examples of the cation contained in the acid generator include a sulfonium cation, a thiophenium cation, an ammonium cation, a phosphonium cation, an iodonium cation, and a pyridinium cation.
  • a sulfonium cation and a thiophenium cation are preferable, a cation represented by the following formula (B-pc) is more preferable, and a triphenylsulfonium cation is particularly preferable.
  • R pc1 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or an alkoxycarbonyl group having 2 to 11 carbon atoms.
  • R pc2 is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or an alkanesulfonyl group having 1 to 10 carbon atoms
  • R pc3 is independently an alkyl group having 1 to 10 carbon atoms, phenyl
  • the two R pc3 may be bonded to each other to form a divalent group having 2 to 10 carbon atoms, t represents an integer of 0 to 2, and r is Represents an integer of 0 to 10.
  • the anion contained in the acid generator has an alicyclic group, and the atomic ratio (F / C) between the fluorine atom and the carbon atom contained in the anion is 0.1 or more and 0.5 or less, Among these, (F / C) is preferably 0.1 or more and 0.4 or less, and more preferably 0.1 or more and 0.3 or less.
  • the anion of the acid generator is preferably represented by the following formula (1).
  • R 1 is a monovalent organic group containing a monocyclic or polycyclic alicyclic group.
  • N is 1 or 2.
  • R f1 and R f2 are each independently a hydrogen atom.
  • the monovalent organic group containing an alicyclic group represented by R 1 is, for example, a monovalent containing a monocyclic alicyclic group having a cycloalkane skeleton such as cyclopentane or cyclohexane.
  • Hydrocarbon groups of And monovalent hydrocarbon groups including polycyclic alicyclic groups having a bridged skeleton such as an adamantane skeleton and a norbornane skeleton.
  • Examples of the monovalent hydrocarbon group include a chain hydrocarbon group having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, i-propyl group, butyl group, pentyl group, hexyl group, and octyl group.
  • a group in which at least one hydrogen atom is substituted with the alicyclic group can be exemplified.
  • a group obtained by combining these groups with one or more groups selected from the group consisting of an oxygen atom, a sulfur atom, an ether group, an ester group, a carbonyl group, an imino group, and an amide group.
  • examples of the fluorinated alkyl group having 1 to 4 carbon atoms include fluorinated methyl group, fluorinated ethyl group, fluorinated n-propyl group, fluorinated i-propyl group, and fluorinated n-butyl. Group, fluorinated t-butyl group and the like.
  • Examples of such anions include norbornane derivatives, adamantane derivatives, deoxycholic acid esters, lithocholic acid esters and the like in which the above (F / C) is 0.1 or more and 0.5 or less. It is done.
  • examples of the anion of the above [B] acid generator include those represented by the following formulas (2) to (5) and (8) to (25). Among these, the following formula (2) ) To (5) are more preferred. In the formula, “Me” represents a methyl group.
  • the atomic ratio (F / C) of fluorine atom and carbon atom contained in the anion of the acid generator can be determined by measuring 13 C-NMR, 1 H-NMR, and IR spectrum.
  • the anion does not contain an aromatic group.
  • the ArF laser transmittance in the resist coating is improved, and the ArF laser is uniformly irradiated from the resist film surface to the vicinity of the resist substrate, thereby improving the rectangularity of the resist pattern. To do.
  • Specific examples of the acid generator include Examples of the sulfonium salt include triphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1].
  • Hept-2-yl-1,1-difluoroethanesulfonate 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4- Methanesulfonylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-6- (1-adamantanecarbonyloxy) -hexane-1-sulfonate and Etc.
  • triphenylsulfonium 2-adamantyl-1,1-difluoroethane sulfonates triphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept -2-yl-1,1-difluoroethanesulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-6- (1-adamantanecarbonyloxy) -hexane-1-sulfonate and triphenylsulfonium 2-adamantyl- 1,1-difluoroethanesulfonate is preferred.
  • tetrahydrothiophenium salts include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2- Tetrafluoroethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethane Sulfonate and 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate Can be mentioned.
  • iodonium salts include diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate and bis (4-tert-butylphenyl) iodonium 2-bicyclo [ 2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate and the like.
  • [B] acid generators may be used alone or in combination of two or more.
  • known sulfonimide compounds, halogen-containing compounds, diazoketone compounds and the like can be used in combination as other acid generators.
  • the content of the [B] acid generator contained in the solid content (component excluding the solvent) of the radiation-sensitive resin composition used in the present invention is preferably 5% by mass or more and 10% by mass or less, and more preferably 8% by mass or more. 9 mass% or less is more preferable.
  • the amount used when [B] the acid generator is an acid generator is usually from 0 to 100 parts by mass of the [A] polymer from the viewpoint of ensuring the sensitivity and developability as a resist. 1 to 15 parts by mass is preferable, 3 to 15 parts by mass is more preferable, and 5 to 12 parts by mass is further preferable.
  • the amount of the [B] acid generator used is less than 0.1 parts by mass, the sensitivity and developability tend to be reduced. On the other hand, if it exceeds 15 parts by mass, the transparency to radiation is reduced and desired. It tends to be difficult to obtain a resist pattern.
  • the [C] polymer is a polymer having a higher fluorine atom content than the [A] polymer.
  • the radiation-sensitive resin composition used in the resist pattern forming method contains the [C] polymer, so that when the resist film is formed, the water-repellent characteristics of the [C] polymer in the film The distribution tends to be unevenly distributed near the resist film surface. For this reason, it is preferable that an acid generator, an acid diffusion controller, and the like are prevented from being eluted into the immersion medium during immersion exposure. Further, due to the water-repellent characteristics of the [C] polymer, the advancing contact angle between the resist film and the immersion medium can be controlled within a desired range, and the occurrence of bubble defects can be suppressed.
  • the receding contact angle between the resist film and the immersion medium is increased, and no water droplets remain, and high-speed scanning exposure is possible.
  • the [C] polymer is not particularly limited as long as it has the above properties, but preferably has a fluorinated alkyl group. When the polymer [C] has a fluorinated alkyl group in the structure, the above characteristics are further improved.
  • the [C] polymer in the present invention is formed by polymerizing one or more monomers containing fluorine in the structure.
  • the monomer containing fluorine in the structure include those containing a fluorine atom in the main chain, those containing a fluorine atom in the side chain, and those containing a fluorine atom in the main chain and the side chain.
  • Examples of monomers containing fluorine atoms in the main chain include ⁇ -fluoroacrylate compounds, ⁇ -trifluoromethyl acrylate compounds, ⁇ -fluoroacrylate compounds, ⁇ -trifluoromethyl acrylate compounds, ⁇ , ⁇ -fluoroacrylate compounds. , ⁇ , ⁇ -trifluoromethyl acrylate compounds, compounds in which one or more kinds of vinyl moiety hydrogen are substituted with fluorine or a trifluoromethyl group, and the like.
  • Examples of the monomer containing a fluorine atom in the side chain include those in which the side chain of an alicyclic olefin compound such as norbornene is fluorine or a fluoroalkyl group or a derivative thereof, or a fluoroalkyl of acrylic acid or methacrylic acid. And an ester compound of a group or a derivative thereof, and one or more olefin side chains (parts not including a double bond) are fluorine or a fluoroalkyl group or a derivative thereof.
  • examples of the monomer containing a fluorine atom in the main chain and the side chain include ⁇ -fluoroacrylic acid, ⁇ -fluoroacrylic acid, ⁇ , ⁇ -fluoroacrylic acid, ⁇ -trifluoromethylacrylic acid, ⁇ - An ester compound of a fluoroalkyl group such as trifluoromethylacrylic acid or ⁇ , ⁇ -trifluoromethylacrylic acid or a derivative thereof, or a compound in which one or more types of vinyl moiety hydrogen is substituted with fluorine or a trifluoromethyl group
  • the chain is substituted with a fluorine or fluoroalkyl group or a derivative thereof, the hydrogen bonded to the double bond of one or more alicyclic olefin compounds is substituted with a fluorine atom or a trifluoromethyl group, and the side chain In which is a fluoroalkyl group or a derivative thereof.
  • the alicyclic olefin compound here represents
  • the structural unit for imparting fluorine to the [C] polymer is not particularly limited as described above, but is a structural unit represented by the following formula (21) (hereinafter referred to as “structural unit (1)”). Is preferably used.
  • R 3 represents hydrogen, a methyl group or a trifluoromethyl group.
  • A represents a linking group, R 4 represents a linear or branched alkyl group having 1 to 6 carbon atoms and a monovalent alicyclic carbon atom having 4 to 20 carbon atoms, containing at least one fluorine atom.
  • a in the formula (21) represents a linking group, and examples thereof include a single bond, an oxygen atom, a sulfur atom, a carbonyloxy group, an oxycarbonyl group, an amide group, a sulfonylamide group, and a urethane group.
  • Preferred monomers that give the structural unit (1) include trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, and perfluoroethyl (meth) acrylate.
  • the above [C] polymer may contain only one type of the structural unit (1), or may contain two or more types.
  • the content of the structural unit (1) is usually 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more when the total structural unit in the [C] polymer is 100 mol%. is there. If the content of the structural unit (1) is less than 5 mol%, a receding contact angle of 70 degrees or more may not be achieved, and elution of an acid generator or the like from the resist film may not be suppressed.
  • the polymer includes, for example, a structural unit having an acid-dissociable group for controlling the dissolution rate in a developer, a lactone skeleton, a hydroxyl group, and a carboxyl.
  • a structural unit having an acid-dissociable group for controlling the dissolution rate in a developer
  • a lactone skeleton for controlling the dissolution rate in a developer
  • a lactone skeleton for controlling the dissolution rate in a developer
  • a lactone skeleton for controlling the dissolution rate in a developer
  • a hydroxyl group a hydroxyl group
  • carboxyl a structural unit having a group having an alicyclic compound
  • a structural unit derived from an aromatic compound for suppressing light scattering due to reflection from a substrate are contained. be able to.
  • structural unit (2) those having an acid-dissociable group can be the same as the structural unit (I) of the polymer [A] (hereinafter referred to as “structural unit (2)”). ).
  • Examples of such structural unit (2) include (meth) acrylic acid 2-methyladamantyl-2-yl ester, (meth) acrylic acid 2-ethyladamantyl-2-yl ester, and (meth) acrylic acid-2.
  • -Methylbicyclo [2.2.1] hept-2-yl ester (meth) acrylic acid-2-ethylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid 1- (bicyclo [2.2.1] Hept-2-yl) -1-methyl ethyl ester, (meth) acrylic acid 1- (adamantan-1-yl) -1-methyl ethyl ester, (meth) acrylic acid 1-methyl- 1-cyclopentyl ester, 1-ethyl-1-cyclopentyl ester of (meth) acrylic acid, 1-methyl-1-cyclohexyl ester of (meth) acrylic acid, (meth ) Acrylic acid 1-ethyl-1-cyclohexyl
  • structural unit (3) As the compound containing a lactone skeleton, for example, the same unit as the structural unit (II) of the polymer [A] can be used (hereinafter referred to as “structural unit (3)”).
  • R 5 represents a hydrogen atom, a methyl group, or a trifluoromethyl group
  • Y is an alicyclic hydrocarbon group having 4 to 20 carbon atoms.
  • Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by Y in the above formula (22) include cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, and bicyclo [2.2.
  • hydrocarbon groups composed of alicyclic rings derived from cycloalkanes such as These cycloalkane-derived alicyclic rings may have a substituent, and examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, 2-
  • the alkyl group may be substituted with one or more linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms such as a methylpropyl group, 1-methylpropyl group, and t-butyl group. These are not limited to those substituted with these alkyl groups, but may be those substituted with a hydroxyl group, a cyano group, a hydroxyalkyl
  • Preferred monomers giving the structural unit (4) include (meth) acrylic acid-bicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid-bicyclo [2.2.2] octa -2-yl ester, (meth) acrylic acid-tricyclo [5.2.1.02,6] dec-7-yl ester, (meth) acrylic acid-tetracyclo [6.2.1.13, 6.02 , 7] dodeca-9-yl ester, (meth) acrylic acid-tricyclo [3.3.1.13,7] dec-1-yl ester, (meth) acrylic acid-tricyclo [3.3.1.13. , 7] Dec-2-yl ester and the like.
  • examples of a preferable monomer that generates an aromatic compound include, for example, styrene, ⁇ -methylstyrene, 2-methylstyrene, and 3-methylstyrene.
  • the structural unit (2) In the [C] polymer in the present invention, only one type of “other structural units” represented by the structural unit (2), the structural unit (3), the structural unit (4), and the structural unit (5) is contained. Or two or more of them may be contained.
  • the content of these other structural units is usually 80 mol% or less, preferably 75 mol% or less, more preferably 70 mol% or less, assuming that all the structural units in the [C] polymer are 100 mol%. .
  • the polymer may contain structural units other than the structural units (1) to (5) as long as the effects of the present invention are not impaired.
  • the fluorine content (% by mass) of the [A] polymer and [C] polymer can be determined by measuring 13 C-NMR, 1 H-NMR, and IR spectrum.
  • content of [C] polymer contained in solid content (component except a solvent) of the radiation sensitive resin composition used for this invention 1 to 10 mass% is preferable, and 1.5 mass% The content is more preferably 8% by mass or less and further preferably 2% by mass or more and 3% by mass or less.
  • the polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator.
  • radical initiator and solvent used in the polymerization examples include the same radical initiator and solvent as those mentioned in the method for synthesizing [A] polymer.
  • the reaction temperature in the polymerization is usually preferably 40 ° C to 150 ° C, more preferably 50 ° C to 120 ° C.
  • the reaction time is usually preferably 1 hour to 48 hours, more preferably 1 hour to 24 hours.
  • the Mw of the [C] polymer is preferably 1,000 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000.
  • Mw of the polymer is less than 1,000, a sufficient advancing contact angle cannot be obtained.
  • Mw exceeds 50,000 the developability of the resist tends to decrease.
  • the ratio of Mw to Mn (Mw / Mn) of the polymer is usually 1 to 3, and preferably 1 to 2.
  • the composition can contain other optional components as long as the effects of the present invention are not impaired.
  • other optional components include an acid diffusion controller, a solvent, an acid generator other than the [B] acid generator, a surfactant, an alicyclic skeleton-containing compound, and a sensitizer.
  • the acid diffusion controller controls the diffusion phenomenon in the resist film of the acid generated from the [B] acid generator by exposure, has the effect of suppressing undesirable chemical reactions in the non-exposed areas, and the resulting radiation sensitive resin composition
  • the storage stability of the product is further improved, the resolution as a resist is further improved, and the line width of the resist pattern due to fluctuations in the holding time from exposure to development processing can be suppressed, and the process stability is extremely excellent.
  • a composition is obtained.
  • the inclusion form of the acid diffusion controller in the composition may be in the form of a free compound, incorporated as part of the polymer, or both forms.
  • Examples of the acid diffusion controller include amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.
  • Examples of the amine compound include mono (cyclo) alkylamines; di (cyclo) alkylamines; tri (cyclo) alkylamines; substituted alkylanilines or derivatives thereof; ethylenediamine, N, N, N ′, N′— Tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis ( 4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4- Aminophenyl) -2- (4-hydroxyphenyl) propane, , 4-bis (1- (4-aminophenyl)
  • amide group-containing compound examples include Nt-butoxycarbonyl group-containing amino compounds such as Nt-butoxycarbonyl-4-hydroxypiperidine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N -Methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, N-acetyl-1-adamantylamine, isocyanuric acid tris (2-hydroxyethyl) and the like.
  • Nt-butoxycarbonyl group-containing amino compounds such as Nt-butoxycarbonyl-4-hydroxypiperidine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N -Methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, N-acetyl-1-adamant
  • urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea, etc. Is mentioned.
  • nitrogen-containing heterocyclic compound examples include imidazoles; pyridines; piperazines; pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, Nt-butoxycarbonylpyrrolidine, piperidine, piperidineethanol, 3-piperidino-1, 2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3- (N-morpholino) -1,2-propanediol, N-cyclohexylcarbonyloxyethylmorpholine, 1 , 4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, and the like.
  • a photodegradable base that generates a weak acid by exposure can also be used.
  • the photodegradable base there is an onium salt compound that is decomposed by exposure and loses acid diffusion controllability.
  • the onium salt compound include a sulfonium salt compound represented by the following formula (23) and an iodonium salt compound represented by the following formula (24). Of these, triphenylsulfonium salicylate is preferable.
  • R 6 to R 10 are each independently a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom.
  • Formula (23) and Formula (24 Z ⁇ is OH ⁇ , R 11 —COO ⁇ , R 11 —SO 3 — or an anion represented by the following formula (25), provided that R 11 is an alkyl group, an aryl group, or an alkaryl group. is there.
  • R 12 represents a linear or branched alkyl group having 1 to 12 carbon atoms, in which some or all of hydrogen atoms may be substituted with fluorine atoms, or a group having 1 to 12 carbon atoms.
  • a straight or branched alkoxyl group, u is an integer of 0 to 2)
  • These acid diffusion control agents may be used alone or in combination of two or more.
  • content of an acid diffusion control agent less than 5 mass parts is preferable with respect to 100 mass parts of [A] polymers.
  • the total amount used exceeds 5 parts by mass, the sensitivity as a resist tends to decrease.
  • the composition usually contains a solvent.
  • the solvent is not particularly limited as long as it can dissolve at least the above-mentioned [A] polymer, [B] acid generator, [C] polymer and optional components added as necessary.
  • the solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, and mixed solvents thereof.
  • solvent examples include the same organic solvents listed above. Of these, propylene glycol monomethyl ether acetate and cyclohexanone are preferred. These solvents may be used alone or in combination of two or more.
  • the composition may contain an acid generator other than the [B] acid generator as long as the effects of the present invention are not impaired.
  • an acid generator include onium salt compounds other than [B] acid generators, sulfonimide compounds, halogen-containing compounds, diazoketone compounds, and the like.
  • onium salt compounds examples include sulfonium salts (including tetrahydrothiophenium salts), iodonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.
  • sulfonium salt examples include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium camphorsulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate.
  • tetrahydrothiophenium salt examples include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium.
  • Nonafluoro-n-butanesulfonate 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio Phenium camphorsulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium nonafluoro-n- Butanesulfone 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium camphorsulfonate, -(3,5-
  • iodonium salt examples include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate.
  • sulfonimide compound examples include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N- (2- (3-tetracyclo [4.4.0.1 2,5 .1 7,10 ] dodecanyl) -1,1-difluoroethanesulf
  • Surfactants have the effect of improving coatability, striation, developability, and the like.
  • the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol
  • nonionic surfactants such as distearate, KP341 (Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no.
  • the alicyclic skeleton-containing compound has the effect of improving dry etching resistance, resist pattern shape, adhesion to the substrate, and the like.
  • Examples of the alicyclic skeleton-containing compound include adamantane derivatives such as 1-adamantanecarboxylic acid, 2-adamantanone, and 1-adamantanecarboxylic acid t-butyl; Deoxycholic acid esters such as t-butyl deoxycholic acid, t-butoxycarbonylmethyl deoxycholic acid, 2-ethoxyethyl deoxycholic acid; Lithocholic acid esters such as tert-butyl lithocholic acid, tert-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid; 3- [2-hydroxy-2,2-bis (trifluoromethyl) ethyl] tetracyclo [4.4.0.1 2,5 .
  • adamantane derivatives such as 1-adamantanecarboxylic acid, 2-adamantanone, and 1-adamantanecarboxylic acid t-butyl
  • Deoxycholic acid esters such
  • dodecane 2-hydroxy-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 3,7 ] nonane, and the like.
  • These alicyclic skeleton containing compounds may be used independently and may use 2 or more types together.
  • the sensitizer exhibits the effect of increasing the amount of [B] acid generators produced, and has the effect of improving the “apparent sensitivity” of the composition.
  • sensitizer examples include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines, and the like. These sensitizers may be used alone or in combination of two or more.
  • the composition can be prepared, for example, by mixing [A] polymer, [B] acid generator, [C] polymer and other optional components in a predetermined ratio in an organic solvent.
  • the composition can be prepared and used in a state dissolved or dispersed in a suitable organic solvent.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by gel permeation chromatography (GPC) under the following conditions using GPC columns (Tosoh Corporation, 2 G2000HXL, 1 G3000HXL, 1 G4000HXL). Monodispersed polystyrene was measured as a standard substance.
  • the [A] polymer, [B] acid generator, [C] polymer, acid diffusion controller and solvent used in the preparation of the composition are as follows.
  • Examples of the acid diffusion controller include (D-1) Nt-butoxycarbonyl-4-hydroxypiperidine, (D-2) triphenylsulfonium salicylate, and (D-3) N-cyclohexylcarbonyloxyethylmorpholine. Was used.
  • Example 1 ⁇ Preparation of radiation-sensitive resin composition> Polymer (A-1) 100 parts by mass, (B-1) 9.5 parts by mass, Polymer (C-1) 3 parts by mass, (D-1) 0.94 parts by mass, (E-1) 2 010 parts by mass and (E-2) 860 parts by mass were mixed to obtain a uniform solution. Then, the radiation sensitive resin composition (henceforth, composition 1) was prepared by filtering using a membrane filter with a hole diameter of 200 nm. The total solid content was 5% by mass.
  • Example 1 A radiation-sensitive resin composition (hereinafter, referred to as “Example 1”) except that the types and blending amounts of the polymer, [B] acid generator, and acid diffusion controller were changed to Table 3 below. Compositions 2 to 19) were prepared.
  • Example 1 A radiation-sensitive resin composition (hereinafter, referred to as “Example 1”) except that the types and blending amounts of the polymer, [B] acid generator, and acid diffusion controller were changed to Table 3 below. Compositions 20-25) were prepared.
  • Example 20 ⁇ Resist pattern formation> An antireflection film forming agent (Burewer Science, trade name “ARC66”) was spin-coated on a 12-inch silicon wafer using “CLEAN TRACK Lithius Pro i” (Tokyo Electron), and then at 205 ° C. Pre-baking (PB) was performed for 60 seconds to form a lower antireflection film having a thickness of 105 nm. The composition 1 obtained above was spin-coated on this substrate using “CLEAN TRACK Lithius Pro i” (manufactured by Tokyo Electron Ltd.), pre-baked (PB) at 90 ° C. for 60 seconds, and then at 30 ° C. for 30 seconds.
  • CLEAN TRACK Lithius Pro i manufactured by Tokyo Electron Ltd.
  • a resist layer having a thickness of 100 nm was formed by cooling for 2 seconds.
  • a resist pattern having a 48 nm hole / 96 nm pitch was formed by spin-drying at 2000 rpm for 15 seconds.
  • Example 21 to 38, Comparative Examples 7 to 12 A resist pattern was formed in the same manner as in Example 20 except that the type of coating liquid, PB temperature, and PEB temperature were changed to the following Table 4. The evaluation results of the obtained resist pattern are also shown in Table 4.
  • the composition used in the resist pattern formation method of the present invention is excellent in sensitivity, and according to the resist pattern formation method using the composition of the present invention, the occurrence of missing contact holes It was found that a hole pattern with a good shape can be formed.
  • the present invention can provide a resist pattern forming method and a radiation-sensitive resin composition that have excellent sensitivity and are less likely to cause missing contact holes when a developer containing an organic solvent is used, that is, have excellent lithography properties. .

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Abstract

La présente invention concerne un procédé de formation d'un motif de réserve comprenant : (1) une étape de formation d'un film de réserve consistant à appliquer sur un substrat une composition de résine sensible aux rayonnements ; (2) une étape d'exposition ; et (3) une étape de développement à l'aide d'une solution de développement contenant au moins 80 % en masse d'un solvant organique. La composition de résine sensible aux rayonnements contient : [A] un polymère de base contenant un groupe dissociable par un acide ; [B] un générateur d'acide sensible aux rayonnements contenant un cation et un anion, l'anion contenant un groupe alicyclique et le rapport (F/C) des atomes de fluor aux atomes de carbone de l'anion se situant entre 0,1 et 0,5 ; et [C] un polymère contenant du fluor, dans lequel le rapport de teneur des atomes de fluor est supérieur à celui du polymère [A].
PCT/JP2011/070770 2010-10-04 2011-09-12 Procédé de formation d'un motif de réserve et composition de résine sensible aux rayonnements Ceased WO2012046543A1 (fr)

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JP2012189884A (ja) * 2011-03-11 2012-10-04 Tokyo Ohka Kogyo Co Ltd レジストパターン形成方法、及びネガ型現像用レジスト組成物
CN112925167A (zh) * 2021-01-26 2021-06-08 宁波南大光电材料有限公司 具有光酸活性的光刻胶树脂及光刻胶

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JP2009025723A (ja) * 2007-07-23 2009-02-05 Fujifilm Corp ネガ型現像用レジスト組成物及びこれを用いたパターン形成方法
JP2010139996A (ja) * 2008-12-15 2010-06-24 Fujifilm Corp ネガ型現像用レジスト組成物及びこれを用いたパターン形成方法
JP2010152353A (ja) * 2008-11-27 2010-07-08 Fujifilm Corp 有機溶剤を含有する現像液を用いたパターン形成方法及びこれに用いるリンス液
JP2010164958A (ja) * 2008-12-15 2010-07-29 Fujifilm Corp ネガ型現像用レジスト組成物、これを用いたパターン形成方法、レジスト膜、及び、パターン
JP2010197619A (ja) * 2009-02-24 2010-09-09 Fujifilm Corp ネガ型現像用レジスト組成物及びこれを用いたパターン形成方法
JP2010217884A (ja) * 2009-02-20 2010-09-30 Fujifilm Corp 電子線又はｅｕｖ光を用いた有機溶剤系現像又は多重現像パターン形成方法
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WO2008153110A1 (fr) * 2007-06-12 2008-12-18 Fujifilm Corporation Composition de réserve pour un développement de type à travail négatif et procédé pour la création de motif utilisant la composition de réserve
JP2009025723A (ja) * 2007-07-23 2009-02-05 Fujifilm Corp ネガ型現像用レジスト組成物及びこれを用いたパターン形成方法
JP2010152353A (ja) * 2008-11-27 2010-07-08 Fujifilm Corp 有機溶剤を含有する現像液を用いたパターン形成方法及びこれに用いるリンス液
JP2010139996A (ja) * 2008-12-15 2010-06-24 Fujifilm Corp ネガ型現像用レジスト組成物及びこれを用いたパターン形成方法
JP2010164958A (ja) * 2008-12-15 2010-07-29 Fujifilm Corp ネガ型現像用レジスト組成物、これを用いたパターン形成方法、レジスト膜、及び、パターン
JP2010217884A (ja) * 2009-02-20 2010-09-30 Fujifilm Corp 電子線又はｅｕｖ光を用いた有機溶剤系現像又は多重現像パターン形成方法
JP2010197619A (ja) * 2009-02-24 2010-09-09 Fujifilm Corp ネガ型現像用レジスト組成物及びこれを用いたパターン形成方法
JP2011145424A (ja) * 2010-01-13 2011-07-28 Fujifilm Corp パターン形成方法、パターン、化学増幅型レジスト組成物及びレジスト膜

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012189884A (ja) * 2011-03-11 2012-10-04 Tokyo Ohka Kogyo Co Ltd レジストパターン形成方法、及びネガ型現像用レジスト組成物
CN112925167A (zh) * 2021-01-26 2021-06-08 宁波南大光电材料有限公司 具有光酸活性的光刻胶树脂及光刻胶

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