WO2012046581A1 - Procédé de formation de motif et composition de résine sensible à un rayonnement - Google Patents

Procédé de formation de motif et composition de résine sensible à un rayonnement Download PDF

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WO2012046581A1
WO2012046581A1 PCT/JP2011/071739 JP2011071739W WO2012046581A1 WO 2012046581 A1 WO2012046581 A1 WO 2012046581A1 JP 2011071739 W JP2011071739 W JP 2011071739W WO 2012046581 A1 WO2012046581 A1 WO 2012046581A1
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group
acid
polymer
resist film
resin composition
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PCT/JP2011/071739
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English (en)
Japanese (ja)
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宏和 榊原
雅史 堀
亘史 伊藤
泰一 古川
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Jsr株式会社
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Publication of WO2012046581A1 publication Critical patent/WO2012046581A1/fr

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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
    • G03F7/039—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
    • 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
    • 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

Definitions

  • the present invention relates to a pattern forming method and a radiation sensitive resin composition.
  • a fine resist pattern having a line width of about 90 nm can be formed by using, for example, an ArF excimer laser, but a finer pattern formation is required.
  • an advantage of using an organic solvent as a developer is that the optical contrast can be increased as compared with the case where a trench pattern or a hole pattern is formed using an alkaline aqueous solution.
  • the present invention has been made on the basis of the above circumstances, and its purpose is to satisfy the basic characteristics such as sensitivity in the lithography process, and to suppress the roughness of the upper surface of the pattern of the resist film, thereby improving the resolution.
  • Another object of the present invention is to provide a trench pattern and / or hole pattern forming method and a radiation-sensitive resin composition that are excellent in pattern size uniformity, cross-sectional shape, and the like.
  • 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 of exposing the resist film; and (3) a trench pattern and / or hole pattern forming method including a development step of developing the exposed resist film with a developer,
  • the developer contains 80% by mass or more of an organic solvent
  • the radiation sensitive resin composition is [A] a polymer having a structural unit containing an acid dissociable group and having increased polarity by the action of an acid (hereinafter also referred to as “[A] polymer”), [B] Radiation sensitive acid generator (hereinafter also referred to as “[B] acid generator”), and [C] Acid diffusion controller having a polar group (hereinafter also referred to as “[C] acid diffusion controller”). .) It is a pattern formation method characterized by containing.
  • the occurrence of roughness at the top of the resist pattern is suppressed.
  • the [C] acid diffusion controller contained in the radiation-sensitive resin composition used in the forming method has a polar group, so that the solvent resistance to the organic developer in the resist film exposed portion is increased.
  • the [C] acid diffusion controller is likely to interact with the resin and other components via the polar group, it is difficult to evaporate in a treatment process at a high temperature such as PB. Therefore, according to the pattern formation method, the concentration distribution of the [C] acid diffusion controller in the film thickness direction of the resist film is difficult to be formed, and a pattern having excellent cross-sectional shape and pattern size uniformity can be formed. Conceivable.
  • the acid diffusion controller is preferably a nitrogen-containing compound represented by the following formula (1).
  • R 1 , R 2 and R 3 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or an alkoxycarbonyl group. it. However, although any two of R 1 ⁇ R 3 may be bonded to each other to form a hetero ring together with the nitrogen atom to which they are attached. However, R 1, R 2, R 3 or above At least one of the heterocyclic hydrogen atoms is substituted with a polar group.
  • the acid diffusion controller is a nitrogen-containing compound represented by the above formula (1)
  • the acid diffusion controller has an appropriate basicity and is suitable for the diffusion phenomenon of acid generated from the acid generator upon exposure in the resist film. Can be controlled. Furthermore, since at least one of R 1 , R 2 , R 3 in the formula (1) or the hydrogen atom of the heterocycle is substituted with a polar group, according to the pattern formation method, the resist film at the time of pattern formation The occurrence of surface roughness is suppressed, and the uniformity in resolution, cross-sectional shape, and pattern size is also excellent.
  • the polar group is preferably a hydroxy group or a carboxy group.
  • the polar group is a hydroxy group or a carboxy group, it interacts with a lactone group or a polar group in the polymer via the polar group, so that transpiration in PB can be suppressed.
  • the pattern forming method the roughness of the resist film surface can be suppressed, and the uniformity in resolution, cross-sectional shape, and pattern size is excellent.
  • R 1 , R 2 and R 3 is preferably represented by the following formula (2).
  • R 4 , R 5 and R 6 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 4 to 12 carbon atoms. However, R 4 and R 5 may be bonded to each other to form a cycloalkanediyl group having 4 to 12 carbon atoms together with the carbon atom to which they are bonded, * indicates a site bonded to a nitrogen atom.
  • R 1, R 2 or R 3 is, to have a structure represented by the above formula (2), in order to improve the affinity of [C] the acid diffusion controller and the acid, [B] a radiation-sensitive acid generator It is thought that the acid generated from the body can be quickly captured. Moreover, since molecular weight becomes large, it becomes difficult to evaporate also in the case of PB.
  • the acid dissociable group of the polymer preferably has an alicyclic group.
  • the resist film can be made highly transparent with respect to an ArF excimer laser or the like. Therefore, according to the pattern forming method, a pattern with higher resolution can be formed.
  • a resist film forming step of applying a radiation sensitive resin composition on a substrate (2) An exposure step of exposing the resist film, and (3) A radiation-sensitive resin composition used in a trench pattern and / or hole pattern forming method including a development step of developing the exposed resist film with a developer.
  • the developer contains 80% by mass or more of an organic solvent
  • the radiation sensitive resin composition is [A] a polymer having a structural unit containing an acid-dissociable group and having increased polarity by the action of an acid;
  • the radiation sensitive resin composition characterized by containing [B] a radiation sensitive acid generator, and [C] the acid diffusion control body which has a polar group is also contained.
  • the pattern formation method of the present invention the formation of a pattern that satisfies basic characteristics such as sensitivity and the occurrence of roughness on the upper surface of the resist film pattern and is excellent in resolution, pattern size uniformity, cross-sectional shape, etc. Is possible. Thereby, it is possible to sufficiently cope with various electronic device structures such as semiconductor devices and liquid crystal devices that require further miniaturization.
  • the present invention includes (1) a resist film forming step of applying a radiation sensitive resin composition on a substrate, (2) an exposure step of exposing the resist film, and (3) developing the exposed resist film with a developer.
  • 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 PB if necessary.
  • 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.
  • an isotrench pattern can be formed by performing reduced projection exposure through a mask having an isoline pattern in a desired region.
  • 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. Reduced projection exposure is performed.
  • the first exposure part and the second exposure part are preferably orthogonal. By being orthogonal, it becomes easy to form a circular contact hole pattern in the unexposed portion surrounded by the exposed portion.
  • 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
  • an additive that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens.
  • 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. In the pattern forming method of the present invention, the exposure process may be performed a plurality of times, and the plurality of exposures may be performed using the same light source or different light sources, but ArF excimer laser light is used for the first exposure. Is preferably used.
  • PEB post-exposure baking
  • Step (3) In this step, after the exposure in step (2), development is performed using a negative developer containing 80% by mass or more of an organic solvent to form a trench pattern and / or a hole 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 solvents include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-pentanol, i-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-hept
  • ether solvent examples include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether and the like.
  • ketone solvent examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n- And ketone solvents such as hexyl ketone, di-i-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, n-butyl acetate, i-butyl acetate, sec-butyl acetate, isoamyl acetate.
  • hydrocarbon solvent examples include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane and cyclohexane.
  • Aliphatic hydrocarbon solvents such as methylcyclohexane; Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene Group hydrocarbon solvents and the like.
  • Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propyl
  • n-butyl acetate isoamyl acetate
  • n-pentyl acetate methyl ethyl ketone
  • methyl n-butyl ketone methyl n-pentyl ketone
  • organic solvents may be used alone or in combination of two or more.
  • the content of the organic solvent in the developer is 80% by mass or more, preferably 90% by mass or more. Most preferably, it is 99 mass% or more.
  • the developer contains 80% by mass or more of the organic solvent, good development characteristics can be obtained, and a pattern with more excellent lithography characteristics can be formed.
  • components other than the organic solvent include water, silicone oil, and surfactant.
  • 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.
  • a rinsing liquid it is preferable to wash the resist film with a rinsing liquid 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 monohydric alcohols 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-pentanol.
  • 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] acid diffusion controller.
  • [A] The polymer contains an acid dissociable group, and this acid dissociable group is dissociated by the action of the acid generated from the [B] acid generator.
  • the polarity of the [A] polymer increases and the poor solubility in the exposed area increases.
  • the radiation-sensitive resin composition used in the present invention further contains a [C] acid diffusion controller, the diffusion phenomenon of the acid generated from the [B] acid generator upon exposure in the resist film is controlled, and the unexposed region Undesirable chemical reactions in are suppressed.
  • the [C] acid diffusion controller has a polar group, the poor solubility of the exposed area in the negative developer increases, and the dissolution contrast between the exposed / unexposed areas increases. As a result, the solvent resistance to the organic developer above the pattern is increased, so that the roughness of the resist film surface is suppressed.
  • the said composition may contain another arbitrary component, unless the effect of this invention is impaired. Hereinafter, each component will be described in detail.
  • the polymer [A] is a polymer that contains a structural unit containing an acid dissociable group and whose polarity increases by the action of an acid.
  • the polymer preferably has a structural unit (I) represented by the following formula (3).
  • R 7 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R p is an acid-dissociable group.
  • R p1 is an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms.
  • R p2 and R p3 are each independently a carbon number.
  • a divalent alicyclic hydrocarbon group may be formed.
  • 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 a 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 a polycyclic alicyclic group having a bridged skeleton such as an adamantane skeleton and a norbornane skeleton. Group; a monocyclic alicyclic group having a cycloalkane skeleton such as cyclopentane or 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.
  • R p1 is an alkyl group having 1 to 4 carbon atoms
  • R p2 and R p3 are bonded to each other, and each is a divalent group having an adamantane skeleton or a cycloalkane skeleton together with the bonded carbon atoms. Is preferably formed.
  • Examples of the structural unit (I) include structural units represented by the following formulas (1-1) to (1-4).
  • R 7 is .R p1, R p2 and R p3 as defined in the above formula (3) is as defined in the above formula (4) .
  • n p is (It is an integer from 1 to 3.)
  • Examples of the structural unit represented by the above formula (3) 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 is 20 mol% to 80 mol%. More preferably, it is 25 mol% to 70 mol%.
  • the [A] polymer may have 1 type, or 2 or more types of structural units (I).
  • Monomers that give the structural unit (I) include monomers containing an acid-dissociable group having a monocyclic alicyclic group such as 1-alkyl-cycloalkyl ester, 2-alkyl-2-dicycloalkyl, etc. And monomers containing an acid-dissociable group having a polycyclic alicyclic group such as esters and 2-alkyl-2-tricycloalkyl esters.
  • the polymer preferably has a structural unit (II) containing a lactone structure.
  • the lactone structure represents a 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.
  • Examples of the structural unit (II) include structural units represented by the following formulas. (In the formula, R L1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.)
  • the monomer that generates the structural unit (II) is 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 site that binds to R L2 in the above formula (L-1), provided that it is represented by formulas (L3-1) to (L3-6). Group may have a substituent.
  • Examples of preferable monomers that give the structural unit (II) include monomers described in paragraph [0043] of International Publication No. 2007/116664.
  • the content of the structural unit (II) in the polymer is preferably 20 mol% to 80 mol%, and more preferably 30 mol% to 70 mol%.
  • the polymer may contain other structural units in addition to the structural unit (I) and the structural unit (II) as long as the effects of the present invention are not impaired.
  • other structural units include structural units having a polar group.
  • the polymer can be synthesized according to a conventional method such as radical polymerization.
  • a method in which a solution containing a monomer and a radical initiator is dropped into a reaction solvent or a solution containing a monomer to cause a polymerization reaction; a solution containing a monomer and a solution containing a radical initiator A method in which a polymerization reaction is carried out by dropping a reaction solvent or a monomer-containing solution separately; a plurality of types of solutions containing each monomer and a solution containing a radical initiator are separately added to the reaction solvent.
  • the monomer amount in the dropped monomer solution is 30 mol with respect to the total amount of monomers used for polymerization. % Or more is preferable, 50 mol% or more is more preferable, and 70 mol% or more is particularly preferable.
  • the reaction temperature in these methods may be appropriately determined depending on the initiator type. Usually, it is 30 ° C to 180 ° C, preferably 40 ° C to 160 ° C, and more preferably 50 ° C to 140 ° C.
  • the dropping time varies depending on the reaction temperature, the type of initiator, the monomer to be reacted, etc., but is usually 30 minutes to 8 hours, preferably 45 minutes to 6 hours, more preferably 1 hour to 5 hours. .
  • the total reaction time including the dropping time varies depending on the conditions as in the dropping time, but is usually from 30 minutes to 8 hours, preferably from 45 minutes to 7 hours, and more preferably from 1 hour to 6 hours.
  • 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 can be used alone or in admixture of two or more.
  • the polymerization solvent is not limited as long as it is a solvent other than a solvent that inhibits polymerization (nitrobenzene having a polymerization inhibiting effect, mercapto compound having a chain transfer effect, etc.) and can dissolve the monomer.
  • the polymerization solvent include alcohol solvents, ketone solvents, amide solvents, ester / lactone solvents, nitrile solvents, and mixed solvents thereof. These solvents can be used alone or in combination of two or more.
  • the resin obtained by the polymerization reaction is preferably recovered by a reprecipitation method. That is, after completion of the polymerization reaction, the target resin is recovered as a powder by introducing the polymerization solution into a reprecipitation solvent.
  • a reprecipitation solvent alcohols or alkanes can be used alone or in admixture of two or more.
  • the resin can be recovered by removing low-molecular components such as monomers and oligomers by a liquid separation operation, a column operation, an ultrafiltration operation, or the like.
  • the Mw of the [A] polymer by GPC method is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 30,000. [A] By making Mw of a polymer into the said range, the cross-sectional shape of a resist pattern becomes favorable.
  • the ratio of Mw to Mn (Mw / Mn) of the polymer is usually 1 to 3, and preferably 1 to 2.
  • [B] Acid generator generates an acid by exposure, and the acid dissociable group present in the [A] polymer is dissociated by the acid to generate a polar group such as a carboxy group. As a result, the [A] polymer becomes hardly soluble in the developer.
  • the composition of the [B] acid generator in the composition is incorporated as part of the polymer even in the form of a compound as will be described later (hereinafter sometimes referred to as “[B] acid generator” as appropriate). Or both of these forms.
  • Examples of the acid generator include onium salt compounds, sulfonimide compounds, halogen-containing compounds, diazoketone compounds, and the like. Of these [B] acid generators, onium salt compounds are preferred.
  • 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 2-bicyclo [2.2.1] hept- 2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium camphorsulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexyl Phenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphen
  • triphenylsulfonium trifluoromethanesulfonate triphenylsulfonium nonafluoro-n-butanesulfonate, 2-adamantyl-1,1-difluoroethane-1-sulfonate and triphenylphosphonium 1,1,2,2-tetrafluoro- 6- (1-adamantanecarbonyloxy) -hexane-1-sulfonate is preferred.
  • tetrahydrothiophenium salt examples include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nona.
  • iodonium salt examples include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl- 1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium camphorsulfonate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium nonafluoro-n-butanesulfonate, Bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bic
  • hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate bis (4-t- butylphenyl) iodonium camphorsulfonate, and the like.
  • bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate is preferred.
  • 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
  • [B] acid generators may be used alone or in combination of two or more.
  • the amount used when the acid generator is an acid generator is usually 0.1 mass with respect to 100 parts by mass of the polymer [A] from the viewpoint of ensuring sensitivity and developability as a resist. Part to 20 parts by mass, preferably 0.5 part to 15 parts by mass. [B] By making the usage-amount of an acid generator into the said specific range, sensitivity can fully be satisfied.
  • the acid diffusion controller controls the diffusion phenomenon in the resist film of the acid generated from the [B] acid generator by exposure, and has the effect of suppressing an undesirable chemical reaction in the non-exposed region, And if it has a polar group in the structure, it will not specifically limit.
  • the radiation-sensitive resin composition used in the pattern forming method contains the [C] acid diffusion controller having a polar group, thereby adding an effect of adding a normal acid diffusion controller.
  • the roughness of the upper surface of the pattern of the resist film obtained is suppressed.
  • the reverse taper shape is suppressed in the trench pattern, and the missing contact hole is suppressed in the hole pattern.
  • 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 nitrogen compounds such as amine compounds, amide group-containing compounds, and urea compounds. Of these, nitrogen-containing compounds are preferred.
  • the acid diffusion controller is preferably a nitrogen-containing compound represented by the above formula (1).
  • R 1 , R 2 and R 3 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or an alkoxycarbonyl group. It is. However, any two of R 1 to R 3 may be bonded to each other and form a heterocycle together with the nitrogen atom to which they are bonded. In addition, at least one of R 1 , R 2 , R 3 or the hydrogen atom of the heterocycle is substituted with a polar group.
  • the linear or branched alkyl group having 1 to 10 carbon atoms represented by R 1 , R 2 and R 3 includes a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, A decyl group etc. are mentioned. Of these, a methyl group, an ethyl group, and a propyl group are preferable.
  • the cycloalkyl group having 3 to 20 carbon atoms represented by R 1 , R 2 and R 3 includes a cyclopropyl group, a cyclobutyl group, a cyclopentylpropyl group, a cyclohexylmethyl group, a cyclooctyl group, and a cyclooctyl group.
  • a methyl group etc. are mentioned.
  • R 1 , R 2 or R 3 is preferably a group represented by the above formula (2).
  • the group represented by the above formula (2) is a group having an acid dissociable group.
  • the acid dissociable group is dissociated by the action of an acid, and the basic amino Be the basis. Thereby, it has the effect of improving the lithography performance of the resist film obtained from the radiation sensitive resin composition of the present invention.
  • examples of the polar group possessed by the groups represented by R 1 to R 3 include a hydroxy group, a carboxy group, a cyano group, an amino group, and an amide group. Of these, a hydroxy group or a carboxy group is preferable.
  • the acid diffusion controller has one or more polar groups, and more preferably 1 to 3 polar groups.
  • R 4 , R 5 and R 6 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 4 to 12 carbon atoms. However, R 4 and R 5 may be bonded to each other to form a cycloalkanediyl group having 4 to 12 carbon atoms together with the carbon atom to which they are bonded. * Indicates a site bonded to a nitrogen atom.
  • examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by R 4 , R 5 and R 6 include a methyl group, an ethyl group, a propyl group and a butyl group. Of these, a methyl group and an ethyl group are preferred.
  • a monovalent alicyclic hydrocarbon group R 4, R 5 and 4 to 12 carbon atoms R 6 represents, and R 4 and R 5 are bonded to each other, and they are attached
  • the alicyclic hydrocarbon group having 4 to 12 carbon atoms formed together with the carbon atom include cycloalkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, norbornyl group, tricyclodecyl group, tetra
  • examples thereof include a group derived from a bridged alicyclic group such as a cyclododecyl group and an adamantyl group.
  • Examples of the group represented by the above formula (2) include a group represented by the following formula.
  • (2-16) and (2-17) are preferred.
  • the [C] acid diffusion controller comprising a group having an acid dissociable group represented by the above formula (2) is a compound that is dissociated by the action of an acid to form a basic amino group, It has the effect of improving the lithography performance of a resist obtained from the radiation-sensitive resin composition in the pattern forming method.
  • the number of carbon atoms of the dissociating group is preferably 4-20, and more preferably 4-13. When it is a hydrocarbon group having 4 or more carbon atoms, dissociation by an acid is likely to occur.
  • the acid diffusion controller is preferably represented by the following formula.
  • the content of the acid diffusion controller is preferably 15 parts by mass or less, more preferably 0.001 to 10 parts by mass, and particularly preferably 0.005 to 100 parts by mass with respect to 100 parts by mass of the [A] polymer. 5 parts by mass.
  • the content of the acid diffusion control agent is less than 0.001 part by mass, the pattern shape tends to deteriorate, and when it exceeds 15 parts by mass, the sensitivity as a resist tends to decrease.
  • the radiation-sensitive resin composition is [D] a polymer having a fluorine atom (hereinafter also referred to as “[D] polymer”) and an [E] solvent, as long as the effects of the present invention are not impaired.
  • [D] polymer a polymer having a fluorine atom
  • [E] solvent an [E] solvent
  • a surfactant, an alicyclic skeleton-containing compound, and a sensitizer can be contained.
  • each component will be described in detail.
  • the polymer is a polymer having a fluorine atom.
  • the radiation-sensitive resin composition in the pattern formation contains the [D] polymer, thereby improving the hydrophobicity of the resist film and being excellent in suppressing substance elution during immersion exposure.
  • the receding contact angle between the resist film and the immersion liquid can be sufficiently increased, and there are effects such as no water droplets remaining when scanning exposure is performed at high speed, it is highly useful for immersion exposure.
  • [D] polymer in this invention is formed by superposing
  • Examples of 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 hydrogen at one or more types of vinyl sites is 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 hydrogen at one or more vinyl sites 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.
  • an alicyclic olefin compound here shows the compound
  • the structural unit for imparting fluorine to the [D] polymer is not particularly limited, but the structural unit (III) represented by the following formula (5) is used as the fluorine-providing structural unit. Is preferred.
  • R 8 is hydrogen, a fluorine atom, a methyl group or a trifluoromethyl group.
  • A is a linking group.
  • R 9 has 1 to 6 carbon atoms containing at least one fluorine atom.
  • examples of the linking group represented by A 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.
  • Monomers that give structural unit (III) include trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, Fluoro n-propyl (meth) acrylic acid ester, perfluoro i-propyl (meth) acrylic acid ester, perfluoro n-butyl (meth) acrylic acid ester, perfluoro i-butyl (meth) acrylic acid ester, perfluoro t -Butyl (meth) acrylic acid ester, 2- (1,1,1,3,3,3-hexafluoropropyl) (meth) acrylic acid ester, 1- (2,2,3,3,4,4,4) 5,5-octafluoropentyl) (meth) acrylic acid ester, perfluorocyclohexylmethyl (meth) acrylic Acid ester, 1- (2,2,3,3,3-pentafluoropropyl) (meth
  • the polymer may have only one type of structural unit (III), or may have two or more types.
  • the content of the structural unit (III) in the polymer is preferably 10 mol% or more and 80 mol% or less when the total structural unit in the [D] polymer is 100 mol%, preferably 20 mol%. % To 50% is more preferable. If the content of the structural unit (III) is less than 10 mol%, a receding contact angle of 70 degrees or more cannot be achieved, and elution of the acid generator and the like from the resist film may not be suppressed.
  • the polymer includes, for example, a structural unit having an acid-dissociable group, a lactone skeleton, a hydroxyl group, a carboxyl group, etc. in order to control the dissolution rate in the developer.
  • a structural unit having an acid-dissociable group such as a lactone skeleton, a hydroxyl group, a carboxyl group, etc.
  • One or more “other structural units” such as a structural unit derived from an aromatic compound can be contained in order to suppress scattering of light due to reflection from the unit, a structural unit having an alicyclic compound, and the like.
  • the description of the structural unit (I) of the polymer [A] can be applied to the structural unit having the acid dissociable group.
  • the description of the structural unit (II) of the polymer [A] can be applied.
  • Examples of the structural unit having the alicyclic compound include a structural unit (IV) represented by the following formula (6).
  • R 10 is a hydrogen atom, a methyl group, or a trifluoromethyl group.
  • B 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 B in the above formula (6) include cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, and bicyclo [2.2. 2] Octane, tricyclo [5.2.1.0 2,6 ] decane, tetracyclo [6.2.1.1 3,6 .
  • hydrocarbon groups composed of alicyclic rings derived from cycloalkanes such as 0 2,7 ] dodecane and tricyclo [3.3.1.1 3,7 ] decane.
  • One or all of the hydrogen atoms contained in these cycloalkane-derived alicyclic rings may be substituted with a substituent.
  • substituents examples include a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group, and oxygen.
  • Monomers that give the structural unit (IV) 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 [5.2.1.0 2,6 ] dec-7-yl ester, (meth) acrylic acid-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-9-yl ester, (meth) acrylic acid-tricyclo [3.3.1.1 3,7 ] dec-1-yl ester, (meth) acrylic acid-tricyclo [3.3. 1.1,7 ] dec-2-yl ester and the like are preferable.
  • Examples of the monomer that gives the structural unit (V) derived from the aromatic compound include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4- (2-t-butoxycarbonylethyloxy) styrene 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxy- ⁇ -methylstyrene, 3-hydroxy - ⁇ -methylstyrene, 4-hydroxy- ⁇ -methylstyrene, 2-methyl-3-hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 2-methyl-4-hydroxystyrene , 3-methyl-4-hydroxystyrene, 3,4-dihydroxy Tylene, 2,4,6-trihydroxystyrene, 4-t-but
  • the [D] polymer in the present invention may have only one type of the other structural units (I), (II), (IV) or (V), or two or more types. May be.
  • the content of these structural units is usually 0 mol% or more and 80 mol% or less, preferably 0 mol% or more and 75 mol% or less when the total structural unit in the [D] polymer is 100 mol%, 0 mol% or more and 70 mol% or less are more preferable.
  • the amount of the polymer used is preferably 1 part by mass or more and 15 parts by mass or less, and more preferably 2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the [A] polymer.
  • the fluorine atom content in the polymer is preferably larger than that of the polymer [A].
  • the fluorine atom content in the polymer is usually 5% by mass or more, preferably 5% by mass to 50% by mass, more preferably 5% by mass, with the total amount of the [D] polymer being 100% by mass. % By mass to 45% by mass.
  • the fluorine atom content can be measured by 13 C-NMR.
  • the water repellency of the film surface can be increased, and there is no need to separately form an upper layer film during immersion exposure.
  • the difference between the fluorine atom content in the [A] polymer and the fluorine atom content in the [D] polymer is 1% by mass or more. Preferably, it is 5 mass% or more.
  • the [D] polymer is the same as the above-described method for synthesizing the [A] polymer by polymerizing, for example, a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator. It can manufacture by the method of.
  • the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is preferably 1,000 to 50,000, more preferably 1,000 to 30,000, and 1,000. ⁇ 10,000 is particularly preferred.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • the ratio (Mw / Mn) between the Mw of the polymer and the polystyrene-equivalent number average molecular weight (Mn) by the GPC method is usually 1 to 3, preferably 1 to 2.
  • the composition usually contains a solvent.
  • the solvent is particularly limited as long as it can dissolve at least the above-mentioned [A] polymer, [B] acid generator, [C] acid diffusion controller, and [D] polymer added as necessary, and other optional components.
  • the solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, and mixed solvents thereof.
  • the solvent include the same organic solvents listed in the pattern formation step (3) above. Of these, propylene glycol monomethyl ether acetate, cyclohexanone and ⁇ -butyrolactone are preferred. These solvents may be used alone or in combination of two or more.
  • composition may contain various additives for the purpose of adjusting or improving patterning characteristics and substrate processing characteristics.
  • Surfactant Surfactant have the effect of improving coatability, striation, developability, and the like.
  • the alicyclic skeleton-containing compound has an effect of improving dry etching resistance, pattern shape, adhesion to the substrate, and the like.
  • sensitizer represents the effect
  • the composition contains, for example, [A] polymer, [B] acid generator, [C] acid diffusion controller, [D] polymer added as necessary, and other components in an organic solvent. It can be prepared by mixing in proportions. In addition, the composition can be prepared and used in a state dissolved or dispersed in a suitable organic solvent.
  • Mw and Mn of the polymer were measured under the following conditions using GPC columns (Tosoh Corporation, 2 G2000HXL, 1 G3000HXL, 1 G4000HXL). Column temperature: 40 ° C Elution solvent: Tetrahydrofuran (Wako Pure Chemical Industries) Flow rate: 1.0 mL / min Sample concentration: 1.0 mass% Sample injection volume: 100 ⁇ L Detector: Differential refractometer Standard material: Monodisperse polystyrene
  • the polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the solution is cooled with water and cooled to 30 ° C. or lower. The reaction solution is transferred to a 2 L separatory funnel, and then the polymerization solution is uniformly diluted with 150 g of n-hexane, and 600 g of methanol is added. And mixed. Next, 30 g of distilled water was added, and the mixture was further stirred and allowed to stand for 30 minutes. Thereafter, the lower layer was collected to obtain a propylene glycol monomethyl ether acetate solution.
  • the [B] acid generator, [C] acid diffusion inhibitor and [E] solvent used in the preparation of the radiation sensitive resin composition are as follows.
  • B-1 triphenylsulfonium 1,1,2,2-tetrafluoro-6- (1-adamantanecarbonyloxy) -hexane-1-sulfonate represented by the following formula B-2: represented by the following formula Triphenylsulfonium 2-adamantyl-1,1-difluoroethane-1-sulfonate
  • Example 10 An organic antireflective film forming agent (Nissan Chemical Co., ARC66) was applied to the wafer surface to form an organic antireflective film having a film thickness of 105 nm.
  • the radiation sensitive resin composition (R-1) was applied by spin coating using a clean track (Tokyo Electron, ACT12), and soft baking was performed on a hot plate at 90 ° C. for 60 seconds. Then, a resist film having a thickness of 0.10 ⁇ m was formed.
  • the resist film is immersed between the dot pattern mask and the resist film using a full-field reduction projection exposure apparatus (Nikon Corporation, S610C, numerical aperture 1.30, illumination quadrupole). Through a reduced projection exposure. Thereafter, post exposure baking at 105 ° C. for 60 seconds, development with butyl acetate at 23 ° C. for 30 seconds, rinsing with 4-methyl-2-pentanol solvent for 10 seconds, rotation speed of 2, The wafer was dried by rotating it at 000 rpm for 10 seconds to form a negative resist pattern.
  • a full-field reduction projection exposure apparatus Nakon Corporation, S610C, numerical aperture 1.30, illumination quadrupole
  • Example 11 to 28 and Comparative Examples 3 to 6 A resist pattern was formed in the same manner as in Example 10 except that the radiation-sensitive resin composition of the type described in Table 4 and the developer were used.
  • CDU Current size uniformity
  • a 0.055 ⁇ m hole pattern formed in the resist film on the substrate was observed from the upper part of the pattern using a length measurement SEM (Hitachi High-Technologies Corporation, CG4000).
  • the diameter was measured at an arbitrary point, and the measurement variation was evaluated by 3 ⁇ . When the diameter was 0.004 ⁇ m or less, it was judged as “good”, and when it exceeded 0.004 ⁇ m, it was judged as “bad”.
  • the resist pattern formed by the pattern forming method of the present invention was excellent in cross-sectional shape, pattern size uniformity and resolution. Moreover, the roughness of the pattern upper surface was also suppressed compared with the comparative example.
  • the roughness of the upper surface of the pattern of the resist film can be suppressed, and a pattern having excellent resolution, pattern size uniformity, cross-sectional shape, and the like can be formed.
  • various electronic device structures such as semiconductor devices and liquid crystal devices that require further miniaturization.

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  • Spectroscopy & Molecular Physics (AREA)
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Abstract

L'invention concerne un procédé pour former des motifs de tranchée et/ou des motifs de trou, qui permet de former des motifs réduisant au minimum la présence de rugosités sur la surface supérieure d'un film de résine photosensible présentant un motif, lesdits motifs présentant d'excellentes caractéristiques de résolution, d'uniformité de taille de motif, de forme en section transversale, etc.; et une composition de résine sensible à un rayonnement. L'invention concerne un procédé pour former des motifs de tranchée et/ou des motifs de trou, qui comprend les étapes suivantes : (1) une étape de formation de film de résine photosensible, dans laquelle une composition de résine sensible à un rayonnement est appliquée sur un substrat ; (2) une étape d'exposition, dans laquelle le film de résine photosensible est exposé ; et (3) une étape de développement, dans laquelle le film de résine photosensible exposé est développé à l'aide d'une solution de développement. Ce procédé est caractérisé en ce que la solution de développement contient au moins 80% en poids d'un solvant organique, et la composition de résine sensible à un rayonnement contient : [A] un polymère qui comprend un motif structural contenant un groupe pouvant être dissocié par un acide, et dont la polarité augmente sous l'effet de l'acide, [B] un corps générateur d'acide sensible à un rayonnement et [C] un corps de régulation de diffusion d'acide comportant un groupe polaire.
PCT/JP2011/071739 2010-10-06 2011-09-22 Procédé de formation de motif et composition de résine sensible à un rayonnement WO2012046581A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016208312A1 (fr) * 2015-06-23 2016-12-29 富士フイルム株式会社 Liquide de rinçage, procédé de formation de motif, et procédé de fabrication de dispositif électronique

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001166476A (ja) * 1999-12-10 2001-06-22 Shin Etsu Chem Co Ltd レジスト材料
JP2005043852A (ja) * 2002-10-29 2005-02-17 Jsr Corp 感放射線性樹脂組成物
JP2006113104A (ja) * 2004-10-12 2006-04-27 Fuji Photo Film Co Ltd ポジ型レジスト組成物及びそれを用いたパターン形成方法
WO2008153109A1 (fr) * 2007-06-12 2008-12-18 Fujifilm Corporation Composition de réserve pour un développement négatif et procédé de création de motif avec celle-ci
JP2008310314A (ja) * 2007-05-15 2008-12-25 Fujifilm Corp パターン形成方法
JP2009258585A (ja) * 2008-03-25 2009-11-05 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
JP2009258586A (ja) * 2008-03-28 2009-11-05 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

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001166476A (ja) * 1999-12-10 2001-06-22 Shin Etsu Chem Co Ltd レジスト材料
JP2005043852A (ja) * 2002-10-29 2005-02-17 Jsr Corp 感放射線性樹脂組成物
JP2006113104A (ja) * 2004-10-12 2006-04-27 Fuji Photo Film Co Ltd ポジ型レジスト組成物及びそれを用いたパターン形成方法
JP2008310314A (ja) * 2007-05-15 2008-12-25 Fujifilm Corp パターン形成方法
WO2008153109A1 (fr) * 2007-06-12 2008-12-18 Fujifilm Corporation Composition de réserve pour un développement négatif et procédé de création de motif avec celle-ci
JP2009258585A (ja) * 2008-03-25 2009-11-05 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
JP2009258586A (ja) * 2008-03-28 2009-11-05 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
V. TRUFFERT ET AL.: "Ultimate contact hole resolution using immersion lithography with line/space imaging", PROCEEDINGS OF SPIE, vol. 7274, 24 February 2009 (2009-02-24), pages 72740N *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016208312A1 (fr) * 2015-06-23 2016-12-29 富士フイルム株式会社 Liquide de rinçage, procédé de formation de motif, et procédé de fabrication de dispositif électronique
JPWO2016208312A1 (ja) * 2015-06-23 2018-02-22 富士フイルム株式会社 リンス液、パターン形成方法、及び電子デバイスの製造方法
US10599038B2 (en) 2015-06-23 2020-03-24 Fujifilm Corporation Rinsing liquid, pattern forming method, and electronic device manufacturing method
TWI694317B (zh) * 2015-06-23 2020-05-21 日商富士軟片股份有限公司 清洗液、圖案形成方法及電子元件的製造方法

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