WO2016043004A1 - Procédé de formation de motifs, film à motifs, procédé de fabrication de dispositif électronique, dispositif électronique, copolymère séquencé et matériau de formation de motifs - Google Patents

Procédé de formation de motifs, film à motifs, procédé de fabrication de dispositif électronique, dispositif électronique, copolymère séquencé et matériau de formation de motifs Download PDF

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WO2016043004A1
WO2016043004A1 PCT/JP2015/074110 JP2015074110W WO2016043004A1 WO 2016043004 A1 WO2016043004 A1 WO 2016043004A1 JP 2015074110 W JP2015074110 W JP 2015074110W WO 2016043004 A1 WO2016043004 A1 WO 2016043004A1
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group
repeating unit
block copolymer
pattern
acid
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PCT/JP2015/074110
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English (en)
Japanese (ja)
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隼人 吉田
木村　桂三
水谷　一良
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富士フイルム株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • 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
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Definitions

  • the present invention is a pattern forming method, a pattern film, an electronic device manufacturing method, an electronic device, and a block co-use, which are preferably used in an ultramicrolithography process such as manufacturing an ultra LSI or a high-capacity microchip and other photofabrication processes.
  • the present invention relates to a polymer and a patterning material.
  • a microphase separation structure is formed by annealing treatment in a solvent atmosphere or heating.
  • the pattern can be formed by selectively removing specific blocks of the block copolymer by oxygen plasma treatment, ozone treatment, UV irradiation treatment, thermal decomposition treatment, or chemical decomposition treatment.
  • a copolymer having two or more segments capable of causing microphase separation can be used.
  • block copolymer In order to form microphase separation, it is advantageous to use, for the block copolymer, blocks whose values of interaction parameters of Flory-Huggins are separated from each other.
  • a block copolymer a block copolymer of polystyrene or a derivative thereof and polymethacrylic acid acrylate or a derivative thereof has been reported (for example, see Patent Document 1 and Non-Patent Document 1).
  • the present invention has been made in view of the above, and an object of the present invention is to provide a composition containing a block copolymer because the solubility of the block copolymer for forming a self-assembled resist film in a solvent is high. It is excellent in the applicability of physical solutions and can achieve high quality pattern refinement (for example, a line and space pattern with a pitch of 40 nm or less and a hole pattern with a hole diameter of 20 nm or less can be formed with high quality).
  • An object of the present invention is to provide a pattern forming method, a pattern film using the pattern forming method, an electronic device manufacturing method and an electronic device, and a block copolymer and a patterning material used in the pattern forming method.
  • the present invention is as follows.
  • the guide pattern exposes the actinic ray-sensitive or radiation-sensitive film with an ArF excimer laser, extreme ultraviolet light, or an electron beam, and develops the exposed actinic ray-sensitive or radiation-sensitive film using a developer.
  • [11] Forming a topcoat layer on the block copolymer layer between the step (i) and the step (ii) or between the step (ii) and the step (iii); The pattern forming method according to any one of [1] to [10].
  • [12] A pattern film obtained by the pattern forming method according to any one of [1] to [11] above.
  • An electronic device manufacturing method comprising the pattern forming method according to any one of [1] to [11] above.
  • [15] A first repeating unit block and a second repeating unit block different from the first repeating unit used in the pattern forming method according to any one of [1] to [11] above.
  • a block copolymer comprising:
  • the first repeating unit has a functional group whose polarity changes when triggered by at least one external stimulus selected from the group consisting of heating and irradiation with actinic rays or radiation, and the second repeating unit.
  • the unit is a block copolymer having no functional group whose polarity is changed by the external stimulus.
  • the solubility of a block copolymer for forming a self-assembled resist film in a solvent is excellent, so that the coating property of the composition solution containing the block copolymer is excellent and the pattern has a high pattern.
  • Pattern formation method capable of achieving high quality for example, a line and space pattern with a pitch of 40 nm or less or a hole pattern with a hole diameter of 20 nm or less can be formed with high quality
  • a pattern using the pattern formation method A film, a method for manufacturing an electronic device and an electronic device, and a block copolymer and a patterning material used in the pattern forming method can be provided.
  • FIGS. 1A to 1D are schematic cross-sectional views for explaining a form in which a highly refined line and space pattern is formed by a graphoepitaxy method using a line and space pattern as a guide pattern.
  • 1 (e) is a schematic top view of the same.
  • 2 (a) to 2 (d) are schematic cross-sectional views for explaining a form in which a highly refined hole pattern is formed by a graphoepitaxy method using the hole pattern as a guide pattern
  • FIG. FIG. 2 is a schematic top view of the same.
  • the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • active light or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do.
  • light means actinic rays or radiation.
  • exposure in the present specification is not limited to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams, ion beams, and the like, unless otherwise specified. The exposure with the particle beam is also included in the exposure.
  • the pattern forming method of the present invention comprises: (I) The process of forming a block copolymer layer by apply
  • the first repeating unit has a functional group whose polarity changes when triggered by the external stimulus
  • the second repeating unit has a functional group whose polarity changes when triggered by the external stimulus. Absent.
  • the pattern forming method of the present invention is excellent in the applicability of the composition containing a block copolymer for forming a self-assembled resist film, and the reason why the pattern can be miniaturized is not clear, for example, Is estimated as follows.
  • the block copolymer contained in the composition applied to form the block copolymer layer is composed of the first repeating unit block and the second repeating unit. And a block of repeating units.
  • the first repeating unit has a functional group whose polarity changes when triggered by at least one external stimulus selected from the group consisting of heating and irradiation with actinic rays or radiation.
  • the second repeating unit does not have a functional group whose polarity is changed by the external stimulus.
  • both of them have a low polarity repeating unit, but the first repeating unit triggered by an external stimulus
  • the first repeating unit and the second repeating unit both have a highly polar repeating unit, but are triggered by an external stimulus.
  • a block copolymer in which only one repeating unit is converted to a repeating unit having a low polarity can be formed.
  • the block copolymer since the polarity of the first repeating unit is close to the polarity of the second repeating unit before receiving an external stimulus, a solvent having a polarity close to these polarities is contained in the block copolymer.
  • a solvent By adopting it as a solvent in the composition, it is possible to prepare a composition solution having a high solubility of the block copolymer.
  • the coating property of the composition containing the block copolymer is improved. It can be considered excellent.
  • the block copolymer after receiving the external stimulus, the block copolymer can make the polarity of the first repeating unit far from the polarity of the second repeating unit. Therefore, it is considered that the phase separation of the block copolymer layer can be surely carried out by performing the above step (iii) after the above step (ii), so that the pattern can be miniaturized. .
  • FIGS. 1A to 1D are schematic cross-sectional views for explaining a form in which a highly refined line and space pattern is formed by a graphoepitaxy method using a line and space pattern as a guide pattern.
  • 1 (e) is a schematic top view of the same.
  • 2 (a) to 2 (d) are schematic cross-sectional views for explaining a form in which a highly refined hole pattern is formed by a graphoepitaxy method using the hole pattern as a guide pattern
  • FIG. FIG. 2 is a schematic top view of the same.
  • substrate The substrate used in the step (i) is not particularly limited, and silicon, SiN, inorganic substrates such as SiO 2 and SiN, coated inorganic substrates such as SOG, semiconductor manufacturing processes such as IC, liquid crystal, thermal A substrate generally used in a manufacturing process of a circuit board such as a head, and also in other photo-fabrication lithography processes can be used. Further, if necessary, an antireflection film may be formed between the film and the substrate.
  • any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used.
  • organic antireflection film commercially available organic antireflection films such as Brewer Science DUV30 series, DUV-40 series, Shipley AR-2, AR-3 and AR-5 may be used. it can.
  • a base layer containing a base agent may be provided on the substrate.
  • phase separation of the block copolymer layer may be more reliably caused in the step (iii) described in detail later.
  • a base layer containing as a base material a material having affinity for any block constituting the block copolymer, it is possible to prevent only a specific phase from contacting the substrate. May be possible.
  • the underlayer Polymers obtained by copolymerizing monomer components are preferably used as the underlayer.
  • a base agent is not particularly limited as long as the above-described functions are exhibited, and the description of paragraphs [0331] to [0333] of International Publication 2012/169620 can be referred to. The contents are incorporated herein.
  • the base layer containing the base agent is suitably formed by applying a liquid obtained by dissolving the base agent with a solvent using a spinner, a coater or the like and drying.
  • the thickness of the underlayer is preferably 3 to 100 nm, more preferably 5 to 50 nm, and still more preferably 10 to 30 nm.
  • the pattern forming method of the present invention can be applied to the above graphoepitaxy method and the above chemical registration method, but is preferably applied to the graphoepitaxy method. Therefore, the substrate is preferably a substrate on which a guide pattern is formed.
  • the guide pattern provided on the substrate is not particularly limited.
  • the guide pattern 21 that forms a line and space pattern see the schematic sectional view of FIG. 1A
  • the guide pattern 22 that forms a hole pattern FIG. 2
  • the thickness of the guide pattern is preferably 10 to 250 nm, more preferably 20 to 200 nm, and still more preferably 30 to 100 nm.
  • the guide pattern is preferably a guide pattern formed by exposing an actinic ray-sensitive or radiation-sensitive film and developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.
  • the actinic ray-sensitive or radiation-sensitive film is obtained by applying an actinic ray-sensitive or radiation-sensitive resin composition, which will be described in detail later, to a substrate (for example, a substrate used for manufacturing precision integrated circuit elements, imprint molds, etc.) (Example: the above-mentioned substrate, silicon / silicon dioxide coating, silicon nitride and chromium-deposited quartz substrate, etc.) are applied using a spinner, coater, etc., and then dried to obtain It is preferred that Examples of the actinic ray or radiation used for exposure include infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams.
  • actinic rays or radiation for example, those having a wavelength of 250 nm or less, particularly 220 nm or less are more preferable.
  • actinic rays or radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F 2 excimer laser (157 nm), X-rays, and electron beams.
  • Preferable actinic rays or radiation include, for example, KrF excimer laser, ArF excimer laser, electron beam, X-ray and extreme ultraviolet light (EUV light). More preferred are ArF excimer laser, electron beam and extreme ultraviolet light.
  • an immersion exposure method when performing exposure using an ArF excimer laser, an immersion exposure method can be applied.
  • the immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a modified illumination method.
  • a step of washing the surface of the membrane with an aqueous chemical may be performed.
  • JP2013-76991A the descriptions in paragraphs [0059] and [0060] of JP2013-76991A can be referred to, and the contents thereof are incorporated in the present specification.
  • the receding contact angle of the actinic ray-sensitive or radiation-sensitive film is 70 ° or more at a temperature of 23 ⁇ 3 ° C. and a humidity of 45 ⁇ 5%, which is suitable for exposure through an immersion medium, and at 75 ° or more. It is preferable that the angle is 75 to 85 °.
  • the receding contact angle is too small, it cannot be used suitably for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited.
  • a hydrophobic resin (HR) described later is included in the actinic ray-sensitive or radiation-sensitive resin composition described later.
  • the receding contact angle may be improved by forming a coating layer (so-called “topcoat”) of a hydrophobic resin composition on the actinic ray-sensitive or radiation-sensitive film.
  • the immersion head In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern.
  • the contact angle of the immersion liquid with respect to the actinic ray-sensitive or radiation-sensitive film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.
  • the actinic ray sensitivity or sensation of the present invention is used for the purpose of suppressing outgas, the purpose of suppressing blob defects, the deterioration of collapse due to reverse taper shape improvement, and the deterioration of LWR due to surface roughness.
  • a hydrophobic resin (HR) described later may be added. By adding the hydrophobic resin (HR), effects such as outgas suppression can be obtained as in the case where the top coat is formed.
  • the topcoat composition used for forming the topcoat will be described.
  • the solvent is preferably water or an organic solvent. More preferred is water or an alcohol solvent.
  • the solvent is an organic solvent, it is preferably a solvent that does not dissolve the film formed from the actinic ray-sensitive or radiation-sensitive resin composition.
  • an alcohol solvent, a fluorine solvent, or a hydrocarbon solvent is preferably used, and a non-fluorine alcohol solvent is more preferably used.
  • the alcohol solvent a primary alcohol is preferable from the viewpoint of applicability, and a primary alcohol having 4 to 8 carbon atoms is more preferable.
  • a linear, branched or cyclic alcohol can be used, but a linear or branched alcohol is preferred. Specific examples include 1-butanol, 1-hexanol, 1-pentanol, and 3-methyl-1-butanol.
  • the solvent for the topcoat composition may be one type or a combination of two or more types.
  • the solvent of the top coat composition is water, an alcohol solvent or the like
  • a water-soluble resin By containing a water-soluble resin, it is considered that the uniformity of solubility in a developer can be further improved.
  • Preferred water-soluble resins include polyacrylic acid, polymethacrylic acid, polyhydroxystyrene, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl ether, polyvinyl acetal, polyacrylimide, polyethylene glycol, polyethylene oxide, polyethyleneimine, polyester polyol and polyether polyol. , Polysaccharides, and the like.
  • the water-soluble resin is not limited to a homopolymer, and may be a copolymer.
  • it may be a copolymer having monomers corresponding to the repeating units of the homopolymers listed above and other monomer units.
  • acrylic acid-methacrylic acid copolymer, acrylic acid-hydroxystyrene copolymer and the like can also be used in the present invention.
  • resins having an acidic group described in JP-A-2009-134177 and JP-A-2009-91798 can also be preferably used.
  • the weight average molecular weight of the water-soluble resin is not particularly limited, but is preferably from 2,000 to 1,000,000, more preferably from 5,000 to 500,000, particularly preferably from 10,000 to 100,000.
  • the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).
  • GPC carrier: THF or N-methyl-2-pyrrolidone (NMP)
  • One type of resin for the top coat composition may be used, or two or more types may be used in combination.
  • the pH of the top coat composition is not particularly limited, but is preferably 0 to 10, more preferably 0 to 8, and particularly preferably 1 to 7.
  • the topcoat composition contains a hydrophobic resin such as a hydrophobic resin (HR) described later in the section of the actinic ray-sensitive or radiation-sensitive resin composition. You may do it.
  • a hydrophobic resin such as a hydrophobic resin (HR) described later in the section of the actinic ray-sensitive or radiation-sensitive resin composition. You may do it.
  • HR hydrophobic resin
  • the concentration of the resin in the top coat composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.3 to 3% by mass.
  • the topcoat material may contain components other than the resin, but the ratio of the resin to the solid content of the topcoat composition is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and particularly preferably Is from 95 to 100% by weight.
  • the solid content concentration of the top coat composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 6% by mass, and still more preferably 0.3 to 5% by mass. . By setting the solid content concentration within the above range, the topcoat composition can be uniformly applied onto the resist film.
  • Components other than the resin that can be added to the top coat material include surfactants, acid generators, basic compounds, and the like.
  • Specific examples of the acid generator and the basic compound include compounds that generate an acid upon irradiation with actinic rays or radiation described later and compounds similar to the basic compound.
  • the amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the topcoat composition.
  • the surfactant include nonionic, anionic, cationic and amphoteric surfactants.
  • Nonionic surfactants include BALF's Plufrac series, Aoki Yushi Kogyo's ELEBASE series, Fine Surf series, Braunon series, Asahi Denka Kogyo's Adekapluronic P-103, Kao Chemical's Emulgen Series, Amit series, Aminone PK-02S, Emanon CH-25, Rheodor series, Surflon S-141 from AGC Seimi Chemical Co., Neugen series from Daiichi Kogyo Seiyaku, New Calgen series from Takemoto Yushi DYNOL604 manufactured by Nissin Chemical Industry Co., Ltd., Envirogem AD01, Olphine EXP series, Surfynol series, Footage 300 manufactured by Hishie Chemical Co., etc.
  • As the cationic surfactant Acetamine 24, Acetamine 86, etc. manufactured by Kao Chemical Co., Ltd. can be used.
  • Surflon S-131 manufactured by AGC Seimi Chemical Co., Ltd.
  • Enajicol C-40H Lipomin LA (manufactured by Kao Chemical Co., Ltd.) or the like can be used.
  • These surfactants can also be mixed and used.
  • the top coat is formed by applying and drying the top coat composition by the same means as the method for forming the actinic ray sensitive or radiation sensitive film formed from the actinic ray sensitive or radiation sensitive resin composition.
  • the film thickness of the top coat is preferably 10 to 200 nm, more preferably 20 to 100 nm, and particularly preferably 40 to 80 nm.
  • the film having the top coat as an upper layer is usually irradiated with an electron beam (EB), X-rays or EUV light through a mask, preferably baked (heated) and developed. Thereby, a good pattern can be obtained.
  • EB electron beam
  • EUV light X-rays
  • EUV light preferably baked (heated) and developed.
  • a developer When developing the topcoat after exposure, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. From the viewpoint that the peeling step can be performed simultaneously with the development processing step of the film, it is preferable that the peeling step can be performed with a developer.
  • the step of exposing the actinic ray-sensitive or radiation-sensitive film may be performed a plurality of times.
  • a preheating step may be performed before the exposure step.
  • a plurality of preheating steps may be performed.
  • PEB Post Exposure Bake
  • a plurality of post-exposure heating steps may be performed.
  • the heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. for both PB and PEB.
  • the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds. Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like. The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.
  • the developer used for forming the guide pattern may be a developer containing an organic solvent or an alkali developer.
  • a developer containing an organic solvent When a developer containing an organic solvent is used, a negative guide pattern can be formed.
  • an alkaline developer is used, a positive guide pattern can be formed.
  • a step of developing using an alkali developer may be further carried out, whereas in the case where the developer is an alkali developer, an organic solvent is included.
  • a portion with low exposure intensity is removed by the organic solvent development step, but a portion with high exposure strength is also removed by performing an alkali development step.
  • the order of the alkali development step and the organic solvent development step is not particularly limited, but the alkali development is more preferably performed before the organic solvent development step.
  • examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia.
  • Inorganic alkalis primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine and triethanolamine Alcohol amines such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, etc.
  • the alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
  • the pH of the alkali developer is usually from 10.0 to 15.0. In particular, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.
  • a step of washing with a rinsing solution may be performed, but from the viewpoint of throughput (productivity), the amount of rinsing solution used, etc., washing with a rinsing solution is performed. It is not necessary to carry out the process of.
  • a rinsing solution in the rinsing treatment performed after alkali development pure water can be used, and an appropriate amount of a surfactant can be added.
  • a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.
  • a developer containing an organic solvent in the formation of the guide pattern As the developer in the step (hereinafter also referred to as an organic developer), a ketone solvent, an ester solvent, Polar solvents such as alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.
  • ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
  • ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, Diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, lactic acid Mention may be made of propyl, methyl 2-hydroxyisobutyrate, butyl butanoate and the like.
  • alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, 4-methyl-2-pentanol, tert-butyl alcohol, isobutyl alcohol, n -Alcohols such as hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, may be mentioned glycol monoethyl ether and methoxymethyl butanol.
  • ether solvent examples include anisole, dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
  • amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like.
  • hydrocarbon solvent examples include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
  • the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture. That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.
  • the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .
  • the vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
  • Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, formate , Ester solvents
  • vapor pressure of 2 kPa or less examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropio , Ester solvents such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl
  • Glycol solvents ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol and other glycol ether solvents, N- Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide Amide solvents, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.
  • the organic developer may contain a basic compound as described in JP-A-2013-11833, particularly [0032] to [0063].
  • Specific examples and preferred examples of the basic compound that can be contained in the developer used in the present invention are the same as those in the basic compound that can be contained in the actinic ray-sensitive or radiation-sensitive resin composition described later.
  • the surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.
  • fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in US Pat. Nos.
  • the amount of the surfactant used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and particularly preferably 0.0005 to 1% by mass with respect to the total amount of the developer.
  • One type of surfactant may be used, or two or more types may be used in combination.
  • 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 discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
  • dip method a method in which a substrate is immersed in a tank filled with a developer for a certain period of time
  • paddle 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
  • spray method a method of spraying the developer on the substrate surface
  • the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm 2 or less, More preferably, it is 1.5 mL / sec / mm 2 or less, More preferably, it is 1 mL / sec / mm 2 or less.
  • There is no particular lower limit on the flow rate but 0.2 mL / sec / mm 2 or more is preferable in consideration of throughput.
  • the details of this mechanism are not clear, but perhaps by making the discharge pressure within the above range, the pressure applied to the resist film by the developer is reduced, and the actinic ray-sensitive or radiation-sensitive film / guide pattern is inadvertently used. This is considered to be suppressed from being scraped or broken.
  • the developer discharge pressure (mL / sec / mm 2 ) is a value at the developing nozzle outlet in the developing device.
  • Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.
  • a step of stopping development may be performed while substituting with another solvent.
  • a step of washing with a rinse solution may be included. From the viewpoint of throughput (productivity), the amount of rinse solution used, etc. It is not necessary to carry out the step of using and washing.
  • the rinsing solution used in the rinsing step after the step of developing using a developer containing an organic solvent is not particularly limited as long as the guide pattern is not dissolved, and a solution containing a general organic solvent can be used.
  • the rinsing liquid contains at least one organic solvent selected from the group consisting of hydrocarbon solvents (preferably decane), ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. It is preferable to use a rinse solution.
  • specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.
  • it contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents after the step of developing using a developer containing an organic solvent.
  • a step of washing with a rinsing liquid is performed, more preferably, a step of washing with a rinsing liquid containing an alcohol solvent or an ester solvent is carried out, and particularly preferably, a rinsing liquid containing a monohydric alcohol is used. And, most preferably, the step of cleaning with a rinse solution containing a monohydric alcohol having 5 or more carbon atoms is performed.
  • examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols. Specific examples include 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms are 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It can be.
  • a plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.
  • 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 vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable.
  • An appropriate amount of a surfactant can be added to the rinse solution.
  • the wafer that has been developed using the developer containing the organic solvent is cleaned using the rinse solution containing the organic solvent.
  • the cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied.
  • a cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.
  • a heating step Post Bake
  • the heating step after the rinsing step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
  • the guide pattern is organic as a developer. It is preferably a negative type guide pattern formed using a system developer. This negative type guide pattern has a polar group generated by decomposition of the resin in the pattern due to the action of an acid, so it is difficult to dissolve in an organic solvent in a composition containing a block copolymer to be described in detail later. It is.
  • the guide pattern may be created by nanoimprint.
  • Step (i) for forming the block copolymer layer is performed.
  • a block copolymer is formed on a substrate 10 on which a guide pattern 21 is formed as shown in the schematic cross-sectional view of FIG. Layer 31 is formed.
  • a block copolymer is formed on the substrate 10 on which the guide pattern 22 is formed, as shown in the schematic sectional view of FIG. Layer 35 is formed.
  • a composition containing a block copolymer is applied onto the substrate 10 using a spinner, a coater, or the like. Then, this can be dried and the block copolymer layers 31 and 35 can be formed.
  • the thickness of the block copolymer layers 31 and 35 is not particularly limited as long as phase separation occurs in the step (iii), but is preferably 10 to 250 nm and used at a thickness of 20 to 200 nm. More preferably, the thickness is 30 to 100 nm.
  • Step of applying at least one external stimulus selected from the group consisting of heating and irradiation with actinic rays or radiation to the block copolymer layer the block copolymer layer is subjected to a step (ii) of applying at least one external stimulus selected from the group consisting of heating and irradiation with actinic rays or radiation.
  • the heating temperature is preferably 50 to 300 ° C, more preferably 100 to 270 ° C, and further preferably 150 to 250 ° C.
  • the heating time is preferably 1 second to 10 hours.
  • the specific examples of actinic rays or radiation can be similarly employed as specific examples of actinic rays or radiation in the formation of a guide pattern.
  • the external stimulus may be given one or more times selected from the group consisting of heating and irradiation with actinic rays or radiation, and is selected from the group consisting of heating and irradiation with actinic rays or radiation. Two or more of them may be given simultaneously or sequentially.
  • External stimulation is preferably applied to the entire surface (all regions) of the block copolymer layer.
  • a known method can be used as it is as a method of applying an external stimulus (heating method, exposure method, etc.).
  • Step (iii) of phase-separating block copolymer layer
  • Step (iii) typically develops a phase separation structure in which at least a portion of the substrate is exposed by heating the block copolymer layer and selectively removing the phase in step (iV) described in detail later. It is a process to make.
  • the heating temperature is preferably not less than the glass transition temperature of the block copolymer and not more than the thermal decomposition temperature of the block copolymer.
  • the heating temperature is preferably 50 to 300 ° C, more preferably 100 to 270 ° C, and further preferably 150 to 250 ° C.
  • the heating time is preferably 1 second to 10 hours.
  • phase that is not selectively removed in step (iv) among the plurality of phases constituting the phase-separated block copolymer layer is a non-removed phase
  • the phase that is selectively removed is a removed phase
  • the removed phase 32 and the non-removed phase 33 are arranged along the guide patterns 21 and 21 as shown in the schematic sectional view of FIG.
  • An alternately arranged lamella structure can be formed between the guide patterns 21 and 21.
  • the phase containing one of the first repeating unit block and the second repeating unit block in the block copolymer constitutes the removed phase 32, and the phase containing the other constitutes the non-removed phase 33.
  • the phase containing the other constitutes the non-removed phase 33.
  • the shape and size of the removed phase and the non-removed phase are defined by the component ratio of each block constituting the block copolymer, the molecular weight of the block copolymer, and the like.
  • step (iii) may be combined with step (ii), and typically, heating as step (ii) and heating as step (iii) may be performed simultaneously.
  • the process in the pattern forming method can be simplified.
  • Step (iv) Step of selectively removing at least one of a plurality of phases in the block copolymer layer is performed.
  • Step (iv) is typically a step of exposing at least a portion of the substrate by selective removal of the phase (ie, the removal phase described above).
  • Examples of the method for removing the removal phase include oxygen plasma treatment, ozone treatment, ultraviolet irradiation treatment, thermal decomposition treatment, and chemical decomposition treatment.
  • a fluorine treatment such as dry etching with fluorine can be preferably exemplified.
  • the pattern is selectively removed and the non-removed phase 33 is left, so that the pattern is made finer (for example, a line and space pattern with a pitch of 40 nm or less).
  • the removal phase 37 in the cylinder structure is formed as shown in the schematic cross-sectional view of FIG. 2D and the schematic top view of FIG.
  • pattern refinement for example, a hole pattern with a hole diameter of 20 nm or less
  • corresponds to performing what is called a shrink process with respect to a guide pattern.
  • the pattern forming method of the present invention forms a topcoat layer on the block copolymer layer between step (i) and step (ii) or between step (ii) and step (iii). May be.
  • a topcoat layer By providing such a topcoat layer, there are cases where the phase separation of the block copolymer layer can be caused more reliably in the step (iii) described above.
  • a topcoat layer containing a material having affinity for any block constituting the block copolymer only a specific phase is unevenly distributed in the surface layer of the block copolymer layer. It may be possible to suppress.
  • the material, the forming method, and the preferred thickness of such a top coat layer are the same as those described in the above underlayer.
  • a guide pattern of a 2: 9 line and space pattern having a line width of 20 nm and a space width of 90 nm is formed by the development, and the step (iii) and the step (iv) are performed in the space of the guide pattern.
  • four non-removed phases each having a line width of 10 nm are formed with a pitch of 20 nm.
  • the pattern forming method of the present invention is suitably used for the production of semiconductor microcircuits such as the manufacture of VLSI and high-capacity microchips.
  • the patterned resist film is used for circuit formation and etching, and the remaining resist film portion is finally removed with a solvent or the like.
  • the pattern film obtained by the pattern forming method of the present invention does not remain in the final product such as a microchip.
  • the present invention also relates to a pattern film obtained by the pattern forming method of the present invention described above.
  • the thickness of the pattern film is preferably 10 to 250 nm, more preferably 20 to 200 nm, and even more preferably 30 to 100 nm, like the thickness of the block copolymer layer described above.
  • the present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.
  • the electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).
  • Block copolymer and composition containing the same Block copolymer and composition containing the same
  • block copolymer in the present invention and the composition containing the same will be described in detail.
  • the block copolymer in the present invention has a first repeating unit block and a second repeating unit block.
  • the first repeating unit has a functional group whose polarity changes with at least one external stimulus selected from the group consisting of heating and irradiation with actinic rays or radiation,
  • the repeating unit does not have a functional group whose polarity is changed by the external stimulus.
  • the first repeating unit may have a group that increases in polarity by the external stimulus or a group that decreases in polarity.
  • the second repeating unit does not have a group that increases when triggered by the external stimulus.
  • the first repeating unit has a group that decreases in polarity when triggered by the external stimulus
  • the functional group whose polarity changes with the external stimulus in the first repeating unit is preferably a group whose polarity increases with the external stimulus. That is, the first repeating unit may have a group that increases polarity when triggered by the external stimulus, and the second repeating unit may not have a group that increases polarity when triggered by the external stimulus. preferable.
  • “functional group whose polarity changes with external stimulation” refers to a functional group whose polarity changes with external stimulation itself and other substances (for example, acid And a functional group whose polarity changes depending on an active species (for example, an acid or a base) generated from a generator or a base generator.
  • the absolute value of the difference between the solubility parameter (SP value) of the first repeating unit and the solubility parameter (SP value) of the second repeating unit is increased by the external stimulus. It is preferable to do.
  • examples of the reaction that occurs when the first repeating unit is triggered by the external stimulus include an acetal group deprotection reaction, a tertiary ester group hydrolysis reaction, a carbamate group A hydrolysis reaction etc. can be mentioned.
  • the solubility parameter (SP value) is obtained by the Okitsu method (Toshinao Okitsu, “Journal of the Adhesion Society of Japan” 29 (3) (1993)), which is one of the methods for calculating the SP value known in the industry. be able to.
  • the solubility parameter (SP value) of the repeating unit constituting the specific block of the block copolymer corresponds to the solubility parameter (SP value) of the specific block (in other words, a homopolymer composed only of the repeating unit).
  • the SP value of a styrene unit constituting polystyrene as a homopolymer is 18.7 (MPa 1/2 )
  • the SP value of a t-butyl methacrylate unit constituting poly (t-butyl methacrylate) as a homopolymer Is 18.0 (MPa 1/2 )
  • the SP value difference between the blocks of the block copolymer made of polystyrene and poly (t-butyl methacrylate) is 0.7 (MPa 1/2 ).
  • the block copolymer composed of polystyrene and poly (t-butyl methacrylate) is converted into a block copolymer composed of polystyrene and polymethacrylic acid in response to the external stimulus.
  • the SP value of methacrylic acid constituting the polymethacrylic acid is 24.0 (MPa 1/2 )
  • the SP value of the methacrylic acid unit constituting the polymethacrylic acid as a homopolymer is 24.0 (MPa 1).
  • the SP value difference between the blocks of the block copolymer made of polystyrene and polymethacrylic acid is 5.3 (MPa 1/2 )
  • the block before receiving the external stimulus is between It increases from 0.7 (MPa 1/2 ), which is the difference in SP value. Therefore, a block copolymer comprising polystyrene and poly (t-butyl methacrylate) is preferable as the block copolymer in the present invention.
  • the amount of increase in the absolute value of the difference between the solubility parameter (SP value) of the first repeating unit and the solubility parameter (SP value) of the second repeating unit triggered by the external stimulus is preferably 1.0. (MPa 1/2 ) or more, more preferably 2.0 (MPa 1/2 ) or more, and further preferably 4.0 (MPa 1/2 ) or more.
  • the absolute value of the difference between the solubility parameter (SP value) of the first repeating unit and the solubility parameter (SP value) of the second repeating unit is 4.0 (MPa 1/2 ). Or less, more preferably 3.0 (MPa 1/2 ) or less, and still more preferably 2.0 (MPa 1/2 ) or less.
  • the absolute value is 0 (MPa 1/2 ) or more, and typically 0.1 (MPa 1/2 ) or more.
  • the block copolymer in the present invention has an absolute difference between the solubility parameter (SP value) of the first repeating unit and the solubility parameter (SP value) of the second repeating unit after receiving the external stimulus.
  • the value is preferably 4.1 (MPa 1/2 ) or more, more preferably 5.0 (MPa 1/2 ) or more, and further preferably 6.0 (MPa 1/2 ) or more. preferable.
  • the absolute value is typically 15.0 (MPa 1/2 ) or less.
  • the pattern is particularly fine (for example, formation of a line and space pattern with a pitch of 40 nm or less or a hole pattern with a hole diameter of 20 nm or less).
  • the block polymer layer tends to be difficult to phase-separate.
  • the absolute value exceeds 15.0 (MPa 1/2 )
  • the diffusion rate of the block copolymer becomes too slow, and the phase separation of the block copolymer layer tends not to be performed with high quality.
  • the first repeating unit in the block copolymer preferably has a group whose polarity is increased by the external stimulus.
  • Preferred examples of the group whose polarity increases upon the external stimulus include a group capable of decomposing by the action of an acid to generate a polar group (hereinafter also referred to as “acid-decomposable group”). That is, preferred examples of the first repeating unit include a repeating unit having an acid-decomposable group.
  • polar groups generated by the decomposition of acid-decomposable groups include alcoholic hydroxyl groups, amino groups, thiol groups, ester groups, amide groups, and acidic groups.
  • the amino group means a monovalent functional group obtained by removing hydrogen from ammonia, a primary amine or a secondary amine.
  • the acidic group is preferably a phenolic hydroxyl group, carboxylic acid group, sulfonic acid group, fluorinated alcohol group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) It is a methylene group, More preferably, acidic groups, such as a carboxylic acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a phenolic hydroxyl group, a
  • a preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.
  • Examples of the group leaving with an acid include —C (R 36 ) (R 37 ) (R 38 ), —C (R 36 ) (R 37 ) (OR 39 ), —C (R 01 ) (R 02 ). ) (OR 39 ) and the like.
  • each of R 36 to R 39 independently represents an alkyl group, a cycloalkyl group, an aryl group, a group in which an alkylene group and an aryl group are combined, or an alkenyl group.
  • R 36 and R 37 may be bonded to each other to form a ring.
  • R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a group in which an alkylene group and an aryl group are combined, or an alkenyl group.
  • the acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like.
  • a repeating unit represented by the following general formula (V) can be preferably exemplified.
  • R 51 , R 52 , and R 53 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
  • R 52 may be bonded to L 5 to form a ring, and R 52 in this case represents an alkylene group.
  • L 5 represents a single bond or a divalent linking group, and in the case of forming a ring with R 52 , represents a trivalent linking group.
  • R 54 represents an alkyl group, and R 55 and R 56 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
  • R 55 and R 56 may combine with each other to form a ring. However, no and R 55 and R 56 are hydrogen atoms at the same time.
  • the alkyl group of R 51 to R 53 in the general formula (V) is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, which may have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, and particularly preferably alkyl groups having 3 or less carbon atoms.
  • the alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in R 51 to R 53 described above.
  • the cycloalkyl group may be monocyclic or polycyclic. Preferred examples include a monocyclic cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
  • Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls.
  • the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group. Groups. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 to 2 carbon atoms is particularly preferable.
  • the ring formed by combining R 52 and L 5 is particularly preferably a 5- or 6-membered ring.
  • R 51 and R 53 in Formula (V) are more preferably a hydrogen atom, an alkyl group, or a halogen atom, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF 3 ), a hydroxymethyl group (—CH 3 ).
  • 2- OH), a chloromethyl group (—CH 2 —Cl), and a fluorine atom (—F) are particularly preferred.
  • R 52 is more preferably a hydrogen atom, an alkyl group, a halogen atom or an alkylene group (forming a ring with L 5 ), a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF 3 ), a hydroxymethyl group Particularly preferred are (—CH 2 —OH), chloromethyl group (—CH 2 —Cl), fluorine atom (—F), methylene group (forms a ring with L 5 ), and ethylene group (forms a ring with L 5 ). .
  • L 1 represents an alkylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which an alkylene group and a divalent aromatic ring group are combined.
  • L 5 is preferably a single bond, a group represented by —COO—L 1 —, or a divalent aromatic ring group.
  • L 1 is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene or propylene group.
  • examples of the trivalent linking group represented by L 5 examples include groups formed by removing any hydrogen atom.
  • the alkyl group of R 54 to R 56 is preferably one having 1 to 20 carbon atoms, more preferably one having 1 to 10 carbon atoms, and includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Particularly preferred are those having 1 to 4 carbon atoms such as a group, isobutyl group and t-butyl group.
  • the cycloalkyl group represented by R 55 and R 56 is preferably one having 3 to 20 carbon atoms, and may be monocyclic such as cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, Polycyclic ones such as a tetracyclodecanyl group and a tetracyclododecanyl group may be used.
  • the ring formed by combining R 55 and R 56 with each other preferably has 3 to 20 carbon atoms, and may be monocyclic such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group.
  • a polycyclic group such as an adamantyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group.
  • R 54 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.
  • the aryl group represented by R 55 and R 56 preferably has 6 to 20 carbon atoms, and may be monocyclic or polycyclic, and may have a substituent.
  • a phenyl group, 1-naphthyl group, 2-naphthyl group, 4-methylphenyl group, 4-methoxyphenyl group and the like can be mentioned.
  • one of R 55 and R 56 is a hydrogen atom, the other is preferably an aryl group.
  • the aralkyl group represented by R 55 and R 56 may be monocyclic or polycyclic and may have a substituent. Preferably, it has 7 to 21 carbon atoms, and examples thereof include a benzyl group and a 1-naphthylmethyl group.
  • the repeating unit represented by the general formula (V) is also preferably a repeating unit represented by the following general formula (V-1).
  • R 1 and R 2 each independently represent an alkyl group
  • R 11 and R 12 each independently represent an alkyl group
  • R 13 represents a hydrogen atom or an alkyl group.
  • R 11 and R 12 may be linked to form a ring
  • R 11 and R 13 may be linked to form a ring.
  • Ra represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom
  • L 5 represents a single bond or a divalent linking group.
  • the alkyl group as R 1 , R 2 , R 11 to R 13 is preferably an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group Group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, neopentyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group.
  • the alkyl group for R 1 and R 2 is more preferably an alkyl group having 2 to 10 carbon atoms.
  • R 1 and R 2 is an alkyl group having 2 to 10 carbon atoms, more preferably both of R 1 and R 2 is an alkyl group having 2 to 10 carbon atoms, R 1 and More preferably, any of R 2 is an ethyl group.
  • the alkyl group for R 11 and R 12 is more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
  • R 13 is more preferably a hydrogen atom or a methyl group. It is particularly preferable R 11 and R 12 are linked to form a ring, R 11 and R 13 are linked may form a ring.
  • the ring formed by connecting R 11 and R 12 is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring.
  • the ring formed by connecting R 11 and R 13 is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring.
  • R 11 and R 13 are linked to form a ring, it is preferably when R 11 and R 12 are linked to form a ring.
  • the ring formed by connecting R 11 and R 12 (or R 11 and R 13 ) is more preferably an alicyclic group described later as X in the general formula (V-2).
  • the ring formed by linking R 1 , R 2 , an alkyl group as R 11 to R 13 , and R 11 and R 12 (or R 11 and R 13 ) may further have a substituent.
  • substituents that the alkyl group as R 1 , R 2 , R 11 to R 13 and the ring formed by linking R 11 and R 12 (or R 11 and R 13 ) may further include cycloalkyl Group, aryl group, amino group, hydroxy group, carboxy group, halogen atom, alkoxy group, aralkyloxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group and nitro group.
  • the above substituents may be bonded to each other to form a ring, and examples of the ring when the above substituents are bonded to each other to form a ring include a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group. .
  • the alkyl group for Ra may have a substituent, and is preferably an alkyl group having 1 to 4 carbon atoms.
  • substituents that the alkyl group of Ra may have include a hydroxyl group and a halogen atom.
  • the halogen atom for Ra include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms (for example, a trifluoromethyl group), and particularly preferably a methyl group.
  • L 5 is a phenylene group
  • Ra is preferably a hydrogen atom.
  • L 5 represents the same as those described in L 5 of the general formula (V).
  • R 11 and R 12 are preferably linked to form a ring, and the repeating unit represented by the general formula (V-1) is represented by the following general formula (V-2). It is more preferable that it is the repeating unit represented by these.
  • X represents an alicyclic group.
  • R 1, R 2, Ra and L 5, respectively, have the same meaning as R 1, R 2, Ra and L 5 in formula (V-1), specific example, also general formula for preferred embodiments (V-1 The same as R 1 , R 2 , Ra and L 5 in
  • the alicyclic group as X may be monocyclic, polycyclic or bridged, and preferably represents an alicyclic group having 3 to 25 carbon atoms.
  • the alicyclic group may have a substituent.
  • the substituent include an alkyl group as R 1 , R 2 , R 11 to R 13 , R 11 and R 12 (or R 11 and R 11). 13 )
  • the same substituents as those described above as the substituent which the ring formed by linking may have, and alkyl groups (methyl group, ethyl group, propyl group, butyl group, perfluoroalkyl group (for example, trifluoro) Methyl group) and the like.
  • X preferably represents an alicyclic group having 3 to 25 carbon atoms, more preferably an alicyclic group having 5 to 20 carbon atoms, and particularly preferably a cycloalkyl group having 5 to 15 carbon atoms.
  • X is preferably a 3- to 8-membered alicyclic group or a condensed ring group thereof, and more preferably a 5- or 6-membered ring or a condensed ring group thereof. Below, the structural example of the alicyclic group as X is shown.
  • Preferred examples of the alicyclic group include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, A cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group can be exemplified.
  • a cyclohexyl group, a cyclopentyl group, an adamantyl group and a norbornyl group are more preferred, a cyclohexyl group and a cyclopentyl group are more preferred, and a cyclohexyl group is particularly preferred.
  • Rx and Xa 1 represent a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
  • Rxa and Rxb each independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 19 carbon atoms.
  • Z represents a substituent.
  • Z represents 0 or a positive integer, preferably 0 to 2, and more preferably 0 or 1.
  • Z is preferably a group consisting of only a hydrogen atom and a carbon atom from the viewpoint of increasing the dissolution contrast with respect to the developer before and after acid decomposition, for example, a linear or branched alkyl group or a cycloalkyl group. It is preferable.
  • the repeating unit having an acid-decomposable group is also preferably a repeating unit represented by the following general formula (VI).
  • R 61 , R 62 and R 63 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 62 may be bonded to Ar 6 to form a ring, and R 62 in this case represents a single bond or an alkylene group.
  • X 6 represents a single bond, —COO—, or —CONR 64 —.
  • R 64 represents a hydrogen atom or an alkyl group.
  • L 6 represents a single bond or an alkylene group.
  • Ar 6 represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R 62 to form a ring.
  • Y 2 independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ⁇ 2. However, at least one of Y 2 represents a group capable of leaving by the action of an acid.
  • n represents an integer of 1 to 4.
  • the alkyl group of R 61 to R 63 in the general formula (VI) is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, which may have a substituent,
  • An alkyl group having 20 or less carbon atoms such as a hexyl group, 2-ethylhexyl group, octyl group or dodecyl group is exemplified, and an alkyl group having 8 or less carbon atoms is more preferred.
  • the alkyl group contained in the alkoxycarbonyl group the same alkyl groups as those described above for R 61 to R 63 are preferable.
  • the cycloalkyl group may be monocyclic or polycyclic, and is preferably a monocyclic type having 3 to 10 carbon atoms such as a cyclopropyl group, cyclopentyl group or cyclohexyl group which may have a substituent.
  • a cycloalkyl group is mentioned.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferable.
  • R 62 represents an alkylene group
  • the alkylene group preferably has 1 to 8 carbon atoms such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc.
  • -CONR 64 represented by X 6 - R 64 represents a hydrogen atom, an alkyl group
  • X 6 is preferably a single bond, —COO— or —CONH—, and more preferably a single bond or —COO—.
  • the alkylene group for L 6 is preferably an alkylene group having 1 to 8 carbon atoms such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group.
  • the ring formed by combining R 62 and L 6 is particularly preferably a 5- or 6-membered ring.
  • Ar 6 represents an (n + 1) -valent aromatic ring group.
  • the divalent aromatic ring group when n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group or a naphthylene group, or, for example, Preferred examples include divalent aromatic ring groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.
  • a substituent for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group or a naphthylene group, or, for example, Preferred examples include divalent aromatic ring groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine
  • Specific examples of the (n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group.
  • the group formed can be preferably mentioned.
  • the (n + 1) -valent aromatic ring group may further have a substituent.
  • Ar 6 may have a plurality of substituents, and in this case, the plurality of substituents may be bonded to each other to form a ring.
  • n is preferably 1 or 2, and more preferably 1.
  • n Y 2 each independently represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of n represents a group capable of leaving by the action of an acid.
  • Examples of the group Y 2 leaving by the action of an acid include —C (R 36 ) (R 37 ) (R 38 ), —C ( ⁇ O) —O—C (R 36 ) (R 37 ) (R 38 ), —C (R 01 ) (R 02 ) (OR 39 ), —C (R 01 ) (R 02 ) —C ( ⁇ O) —O—C (R 36 ) (R 37 ) (R 38 ) , —CH (R 36 ) (Ar) and the like.
  • each of R 36 to R 39 independently represents an alkyl group, a cycloalkyl group, an aryl group, a group in which an alkylene group and an aryl group are combined, or an alkenyl group.
  • R 36 and R 37 may be bonded to each other to form a ring.
  • R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a group in which an alkylene group and an aryl group are combined, or an alkenyl group.
  • Ar represents an aryl group.
  • the alkyl group of R 36 to R 39 , R 01 and R 02 may be linear or branched and is preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, A propyl group, n-butyl group, sec-butyl group, hexyl group, octyl group and the like can be mentioned.
  • the cycloalkyl group of R 36 to R 39 , R 01 and R 02 may be monocyclic or polycyclic.
  • the monocyclic type is preferably a cycloalkyl group having 3 to 10 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • the polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms.
  • a part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
  • the aryl group of R 36 to R 39 , R 01 , R 02 and Ar is preferably an aryl group having 6 to 10 carbon atoms, such as an aryl group such as a phenyl group, a naphthyl group and an anthryl group, thiophene, furan, pyrrole, Mention may be made of divalent aromatic ring groups containing heterocycles such as benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and the like.
  • the group in which the alkylene group of R 36 to R 39 , R 01 and R 02 and the aryl group are combined is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group. be able to.
  • the alkenyl group of R 36 to R 39 , R 01 and R 02 is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
  • the ring formed by combining R 36 and R 37 with each other may be monocyclic or polycyclic.
  • the monocyclic type is preferably a cycloalkyl structure having 3 to 10 carbon atoms, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure.
  • the polycyclic type is preferably a cycloalkyl structure having 6 to 20 carbon atoms, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure.
  • a part of carbon atoms in the cycloalkyl structure may be substituted with a hetero atom such as an oxygen atom.
  • Each of the groups as R 36 to R 39 , R 01 , R 02 , and Ar may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, and an amino group.
  • the number of carbon atoms is preferably 8 or less.
  • a structure represented by the following general formula (VI-A) is more preferable.
  • L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
  • M represents a single bond or a divalent linking group.
  • Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. At least two of Q, M, and L 1 may combine to form a ring (preferably a 5-membered or 6-membered ring).
  • the alkyl group as L 1 and L 2 is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group. Preferred examples include a group and an octyl group.
  • the cycloalkyl group as L 1 and L 2 is, for example, a cycloalkyl group having 3 to 15 carbon atoms, and specific examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like. Can do.
  • the aryl group as L 1 and L 2 is, for example, an aryl group having 6 to 15 carbon atoms, and specific examples include a phenyl group, a tolyl group, a naphthyl group, an anthryl group, and the like.
  • the group combining the alkylene group and the aryl group as L 1 and L 2 has, for example, 6 to 20 carbon atoms, and examples thereof include aralkyl groups such as benzyl group and phenethyl group.
  • the divalent linking group as M is, for example, an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc.), cycloalkylene group (for example, cyclopentylene group, cyclohexylene group).
  • alkylene group for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc.
  • cycloalkylene group for example, cyclopentylene group, cyclohexylene group.
  • alkenylene group eg, ethylene group, propenylene group, butenylene group, etc.
  • divalent aromatic ring group eg, phenylene group, tolylene group, naphthylene group, etc.
  • S— —O
  • R 0 is a hydrogen atom or an alkyl group (eg, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group). Octyl group, etc.).
  • an alkyl group eg, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group). Octyl group, etc.
  • the alkyl group as Q is the same as each group as L 1 and L 2 described above.
  • an aliphatic hydrocarbon ring group containing no hetero atom and an aryl group containing no hetero atom Includes the cycloalkyl group as L 1 and L 2 described above, an aryl group, and the like, and preferably has 3 to 15 carbon atoms.
  • Examples of the cycloalkyl group containing a hetero atom and the aryl group containing a hetero atom include, for example, thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, Examples thereof include groups having a heterocyclic structure such as pyrrolidone, but are not limited thereto as long as the structure is generally called a heterocyclic ring (a ring formed of carbon and a heteroatom or a ring formed of a heteroatom).
  • Each group represented by L 1 , L 2 , M, Q in the general formula (VI-A) may have a substituent.
  • the group represented by —MQ is preferably a group composed of 1 to 30 carbon atoms, more preferably a group composed of 5 to 20 carbon atoms.
  • the repeating unit represented by the general formula (VI) is preferably a repeating unit represented by the following general formula (3).
  • Ar 3 represents an aromatic ring group.
  • R 3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
  • M 3 represents a single bond or a divalent linking group.
  • Q 3 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. At least two of Q 3 , M 3 and R 3 may be bonded to form a ring.
  • the aromatic ring group represented by Ar 3 is the same as Ar 6 in the general formula (VI) when n in the general formula (VI) is 1, more preferably a phenylene group or a naphthylene group. More preferred is a phenylene group.
  • Ar 3 may have a substituent, and examples of the substituent that Ar 3 may have include the same substituents that Ar 6 in the general formula (VI) may have.
  • the alkyl group or cycloalkyl group represented by R 3 has the same meaning as the alkyl group or cycloalkyl group represented by the aforementioned R 36 to R 39 , R 01 and R 02 .
  • the aryl group represented by R 3 has the same meaning as the aryl group represented by R 36 to R 39 , R 01 and R 02 described above, and the preferred range is also the same.
  • the aralkyl group represented by R 3 is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
  • the alkyl group portion of the alkoxy group represented by R 3 is the same as the alkyl group represented by R 36 to R 39 , R 01 and R 02 described above, and the preferred range is also the same.
  • the acyl group represented by R 3 include an aliphatic acyl group having 1 to 10 carbon atoms such as formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, pivaloyl group, benzoyl group and naphthoyl group. , An acetyl group or a benzoyl group is preferred.
  • Examples of the heterocyclic group represented by R 3 include the aforementioned cycloalkyl groups containing a hetero atom and aryl groups containing a hetero atom, and a pyridine ring group or a pyran ring group is preferable.
  • R 3 is preferably an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group or a heterocyclic group, and a linear or branched alkyl group having 1 to 8 carbon atoms (specifically, Is a methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, neopentyl group, hexyl group, 2-ethylhexyl group, octyl group), 3 to More preferably, it is 15 cycloalkyl groups (specifically, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, etc.).
  • R 3 is more preferably a methyl group, an ethyl group, an i-propyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a cyclohexyl group, an adamantyl group, a cyclohexylmethyl group or an adamantanemethyl group, , Sec-butyl group, neopentyl group, cyclohexylmethyl group or adamantanemethyl group is particularly preferable.
  • alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, acyl group or heterocyclic group described above may further have a substituent, and examples of the substituent which may be included include the aforementioned R 36- R 39, R 01, R 02 , and Ar can be mentioned those described as the substituent which may have.
  • the divalent linking group represented by M 3 has the same meaning as M in the structure represented by the above general formula (VI-A), and the preferred range is also the same.
  • M 3 may have a substituent, and the substituent that M 3 may have is the same group as the substituent that M in the group represented by the general formula (VI-A) may have Is mentioned.
  • the alkyl group, cycloalkyl group and aryl group represented by Q 3 have the same meanings as those in Q in the structure represented by the above general formula (VI-A), and the preferred ranges are also the same.
  • Examples of the heterocyclic group represented by Q 3 include a cycloalkyl group containing a hetero atom as Q and an aryl group containing a hetero atom in the structure represented by the aforementioned general formula (VI-A). It is the same.
  • Q 3 may have a substituent, and the substituent that Q 3 may have is the same group as the substituent that Q in the group represented by the general formula (VI-A) may have Is mentioned.
  • a ring formed by combining at least two of Q 3 , M 3 and R 3 is a ring which may be formed by combining at least two of Q, M and L 1 in the general formula (VI-A). It is synonymous and the preferable range is also the same.
  • repeating unit represented by the general formula (VI) are shown below, but the present invention is not limited thereto.
  • the repeating unit having an acid-decomposable group is also preferably a repeating unit represented by the following general formula (4).
  • R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 42 may be bonded to L 4 to form a ring, and R 42 in this case represents an alkylene group.
  • L 4 represents a single bond or a divalent linking group, and in the case of forming a ring with R 42 , represents a trivalent linking group.
  • R 44 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
  • M 4 represents a single bond or a divalent linking group.
  • Q 4 represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. At least two of Q 4 , M 4 and R 44 may be bonded to form a ring.
  • R 41 , R 42 and R 43 have the same meanings as R 51 , R 52 and R 53 in the general formula (V), and preferred ranges thereof are also the same.
  • L 4 has the same meaning as L 5 in the general formula (V), and the preferred range is also the same.
  • R 44 has the same meaning as R 3 in the general formula (3), and the preferred range is also the same.
  • M 4 has the same meaning as M 3 in the general formula (3), and the preferred range is also the same.
  • Q 4 has the same meaning as Q 3 in the general formula (3), and the preferred range is also the same.
  • Examples of the ring formed by combining at least two of Q 4 , M 4 and R 44 include rings formed by combining at least two of Q 3 , M 3 and R 3 , and the preferred range is the same. It is.
  • the repeating unit having an acid-decomposable group is also preferably a repeating unit represented by the following general formula (BZ).
  • AR represents an aryl group.
  • Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
  • Rn and AR may be bonded to each other to form a non-aromatic ring.
  • R 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.
  • the aryl group for AR is preferably a group having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, an anthryl group, or a fluorene group, and more preferably a group having 6 to 15 carbon atoms.
  • AR is a naphthyl group, anthryl group, or fluorene group
  • the bonding position between the carbon atom to which Rn is bonded and AR is not particularly limited.
  • this carbon atom may be bonded to the ⁇ -position of the naphthyl group or may be bonded to the ⁇ -position.
  • AR when AR is an anthryl group, this carbon atom may be bonded to the 1-position, the 2-position, or the 9-position of the anthryl group.
  • Each of the aryl groups as AR may have one or more substituents. Specific examples of such substituents include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group and dodecyl group.
  • a linear or branched alkyl group having 1 to 5 carbon atoms and an alkoxy group containing the alkyl group moiety are preferable, and a paramethyl group
  • the aryl group as AR has a plurality of substituents
  • at least two of the plurality of substituents may be bonded to each other to form a ring.
  • the ring is preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring.
  • this ring may be a heterocycle containing a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member.
  • this ring may have a substituent.
  • the repeating unit represented by general formula (BZ) contains two or more aromatic rings from a viewpoint of roughness performance.
  • the number of aromatic rings contained in this repeating unit is usually preferably 5 or less, and more preferably 3 or less.
  • AR preferably contains two or more aromatic rings, and AR is more preferably a naphthyl group or a biphenyl group.
  • the number of aromatic rings possessed by AR is usually preferably 5 or less, and more preferably 3 or less.
  • Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
  • the alkyl group of Rn may be a straight chain alkyl group or a branched chain alkyl group.
  • the alkyl group is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc. Examples thereof include those having 1 to 20 carbon atoms.
  • the alkyl group of Rn preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms.
  • Examples of the cycloalkyl group represented by Rn include those having 3 to 15 carbon atoms such as a cyclopentyl group and a cyclohexyl group.
  • As the aryl group of Rn for example, those having 6 to 14 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthryl group are preferable.
  • Each of the alkyl group, cycloalkyl group and aryl group as Rn may further have a substituent.
  • substituents include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, a dialkylamino group, an alkylthio group, an arylthio group, an aralkylthio group, and a thiophenecarbonyloxy group.
  • Thiophenemethylcarbonyloxy group and heterocyclic residues such as pyrrolidone residues.
  • R 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkyloxycarbonyl group as described above.
  • Examples of the alkyl group and cycloalkyl group for R 1 include the same groups as those described above for Rn.
  • Each of these alkyl groups and cycloalkyl groups may have a substituent. Examples of this substituent include the same as those described above for Rn.
  • R 1 is an alkyl group or a cycloalkyl group having a substituent
  • R 1 includes, for example, a trifluoromethyl group, an alkyloxycarbonylmethyl group, an alkylcarbonyloxymethyl group, a hydroxymethyl group, and an alkoxymethyl group.
  • the halogen atom for R 1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is particularly preferable.
  • Rn and AR are preferably bonded to each other to form a non-aromatic ring, and in particular, roughness performance can be further improved.
  • the non-aromatic ring that may be formed by bonding Rn and AR is preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring.
  • the non-aromatic ring may be an aliphatic ring or a heterocycle containing a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member.
  • the non-aromatic ring may have a substituent. As this substituent, the thing similar to having demonstrated previously about the further substituent which Rn may have is mentioned, for example.
  • repeating unit represented by the general formula (BZ) are shown below, but are not limited thereto.
  • the embodiment of the repeating unit having an acid-decomposable group different from the repeating unit exemplified above may be an embodiment of a repeating unit that produces an alcoholic hydroxyl group.
  • it is preferably represented by at least one selected from the group consisting of the following general formulas (I-1) to (I-10).
  • This repeating unit is more preferably represented by at least one selected from the group consisting of the following general formulas (I-1) to (I-3), and is represented by the following general formula (I-1) More preferably.
  • Ra independently represents a hydrogen atom, an alkyl group or a group represented by —CH 2 —O—Ra 2 .
  • Ra 2 represents a hydrogen atom, an alkyl group, or an acyl group.
  • R 1 represents an (n + 1) valent organic group.
  • R 2 independently represents a single bond or an (n + 1) -valent organic group when m ⁇ 2.
  • OP each independently represents the above group which decomposes by the action of an acid to produce an alcoholic hydroxy group. When n ⁇ 2 and / or m ⁇ 2, two or more OPs may be bonded to each other to form a ring.
  • W represents a methylene group, an oxygen atom or a sulfur atom.
  • n and m represent an integer of 1 or more.
  • n is 1 when R 2 represents a single bond.
  • l represents an integer of 0 or more.
  • L 1 represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO 3 — or —SO 2 NH—.
  • Ar represents a divalent aromatic ring group.
  • Each R independently represents a hydrogen atom or an alkyl group.
  • R 0 represents a hydrogen atom or an organic group.
  • L 3 represents a (m + 2) -valent linking group.
  • R L each independently represents an (n + 1) -valent linking group when m ⁇ 2.
  • R S each independently represents a substituent when p ⁇ 2. For p ⁇ 2, plural structured R S may be bonded to each other to form a ring.
  • p represents an integer of 0 to 3.
  • Ra represents a hydrogen atom, an alkyl group, or a group represented by —CH 2 —O—Ra 2 .
  • Ra is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group.
  • W represents a methylene group, an oxygen atom or a sulfur atom. W is preferably a methylene group or an oxygen atom.
  • R 1 represents an (n + 1) valent organic group.
  • R 1 is preferably a non-aromatic hydrocarbon group. In this case, R 1 may be a chain hydrocarbon group or an alicyclic hydrocarbon group.
  • R 1 is more preferably an alicyclic hydrocarbon group.
  • R 2 represents a single bond or an (n + 1) valent organic group.
  • R 2 is preferably a single bond or a non-aromatic hydrocarbon group.
  • R 2 may be a chain hydrocarbon group or an alicyclic hydrocarbon group.
  • the chain hydrocarbon group may be linear or branched.
  • the chain hydrocarbon group preferably has 1 to 8 carbon atoms.
  • R 1 and / or R 2 is an alkylene group
  • R 1 and / or R 2 is a methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group or sec- A butylene group is preferred.
  • R 1 and / or R 2 is an alicyclic hydrocarbon group
  • the alicyclic hydrocarbon group may be monocyclic or polycyclic.
  • This alicyclic hydrocarbon group has, for example, a monocyclo, bicyclo, tricyclo or tetracyclo structure.
  • the carbon number of the alicyclic hydrocarbon group is usually 5 or more, preferably 6 to 30, and more preferably 7 to 25.
  • Examples of the alicyclic hydrocarbon group include those having the partial structures listed below. Each of these partial structures may have a substituent.
  • the methylene group (—CH 2 —) includes an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl group [—C ( ⁇ O) —], a sulfonyl group [— —S ( ⁇ O) 2 —], sulfinyl group [—S ( ⁇ O) —], or imino group [—N (R) —] (where R is a hydrogen atom or an alkyl group) may be substituted.
  • R 1 and / or R 2 when R 1 and / or R 2 is a cycloalkylene group, R 1 and / or R 2 may be an adamantylene group, a noradamantylene group, a decahydronaphthylene group, a tricyclodecanylene group, a tetracyclododeca group.
  • Nylene group, norbornylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclodecanylene group, or cyclododecanylene group are preferable, and adamantylene group, norbornylene group, cyclohexylene group, cyclopentylene It is more preferable that they are a len group, a tetracyclododecanylene group, or a tricyclodecanylene group.
  • the non-aromatic hydrocarbon group of R 1 and / or R 2 may have a substituent.
  • substituents examples include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms.
  • the above alkyl group, alkoxy group and alkoxycarbonyl group may further have a substituent.
  • a hydroxy group, a halogen atom, and an alkoxy group are mentioned, for example.
  • L 1 represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO 3 — or —SO 2 NH—.
  • Ar represents a divalent aromatic ring group.
  • L 1 is preferably a linking group represented by —COO—, —CONH— or —Ar—, and more preferably a linking group represented by —COO— or —CONH—.
  • R represents a hydrogen atom or an alkyl group.
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.
  • R is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • R 0 represents a hydrogen atom or an organic group.
  • the organic group include an alkyl group, a cycloalkyl group, an aryl group, an alkynyl group, and an alkenyl group.
  • R 0 is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group.
  • L 3 represents a (m + 2) -valent linking group. That is, L 3 represents a trivalent or higher linking group. Examples of such a linking group include corresponding groups in specific examples described later.
  • R L represents a (n + 1) -valent linking group. That is, R L represents a divalent or higher linking group.
  • R L may be bonded to each other or bonded to the following R S to form a ring structure.
  • R S represents a substituent.
  • the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, and a halogen atom.
  • n is an integer of 1 or more.
  • n is preferably an integer of 1 to 3, and more preferably 1 or 2. When n is 2 or more, it is possible to further improve the dissolution contrast with respect to a developer containing an organic solvent.
  • m is an integer of 1 or more.
  • m is preferably an integer of 1 to 3, and more preferably 1 or 2.
  • l is an integer of 0 or more.
  • l is preferably 0 or 1.
  • p is an integer of 0 to 3.
  • Ra and OP have the same meanings as in general formulas (I-1) to (I-3).
  • the corresponding ring structure is represented as “OPO” for convenience.
  • the group that decomposes by the action of an acid to produce an alcoholic hydroxy group is preferably represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-4).
  • R 3 each independently represents a hydrogen atom or a monovalent organic group.
  • R 3 may be bonded to each other to form a ring.
  • R 4 each independently represents a monovalent organic group.
  • R 4 may be bonded to each other to form a ring.
  • R 3 and R 4 may be bonded to each other to form a ring.
  • R 5 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. At least two R 5 may be bonded to each other to form a ring.
  • R 5 when one or two of the three R 5 are hydrogen atoms, at least one of the remaining R 5 represents an aryl group, an alkenyl group, or an alkynyl group.
  • the group capable of decomposing by the action of an acid to produce an alcoholic hydroxy group is also preferably represented by at least one selected from the group consisting of the following general formulas (II-5) to (II-9).
  • R 6 each independently represents a hydrogen atom or a monovalent organic group. R 6 may be bonded to each other to form a ring.
  • the group that decomposes by the action of an acid to produce an alcoholic hydroxy group is more preferably represented by at least one selected from the general formulas (II-1) to (II-3). More preferably, it is represented by 1) or (II-3), and particularly preferably represented by formula (II-1).
  • R 3 represents a hydrogen atom or a monovalent organic group as described above.
  • R 3 is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group.
  • the alkyl group for R 3 may be linear or branched.
  • the number of carbon atoms of the alkyl group represented by R 3 is preferably 1 to 10, and more preferably 1 to 3.
  • Examples of the alkyl group for R 3 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • the cycloalkyl group for R 3 may be monocyclic or polycyclic.
  • the number of carbon atoms of the cycloalkyl group represented by R 3 is preferably 3 to 10, and more preferably 4 to 8.
  • Examples of the cycloalkyl group represented by R 3 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.
  • R 3 is preferably a monovalent organic group.
  • R 4 represents a monovalent organic group.
  • R 4 is preferably an alkyl group or a cycloalkyl group, and more preferably an alkyl group. These alkyl groups and cycloalkyl groups may have a substituent.
  • the alkyl group represented by R 4 preferably has no substituent, or preferably has one or more aryl groups and / or one or more silyl groups as substituents.
  • the carbon number of the unsubstituted alkyl group is preferably 1-20.
  • the alkyl group moiety in the alkyl group substituted with one or more aryl groups preferably has 1 to 25 carbon atoms.
  • the number of carbon atoms of the alkyl group moiety in the alkyl group substituted with one or more silyl groups is preferably 1-30.
  • the carbon number thereof is preferably 3-20.
  • R 5 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group.
  • R 5 when one or two of the three R 5 are hydrogen atoms, at least one of the remaining R 5 represents an aryl group, an alkenyl group, or an alkynyl group.
  • R 5 is preferably a hydrogen atom or an alkyl group.
  • the alkyl group may have a substituent or may not have a substituent.
  • the carbon number thereof is preferably 1 to 6, and preferably 1 to 3.
  • R 6 represents a hydrogen atom or a monovalent organic group as described above.
  • R 6 is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or an alkyl group having no substituent.
  • R 6 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and having no substituent.
  • Examples of the alkyl group and cycloalkyl group of R 4 , R 5, and R 6 include the same as those described above for R 3 . Below, the specific example of the group which decomposes
  • Xa 1 represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
  • the first repeating unit is represented by the repeating unit represented by the general formula (V) or at least one selected from the group consisting of the general formulas (I-1) to (I-10).
  • a repeating unit is preferable, and a repeating unit represented by the above general formula (I-1) is more preferable.
  • Preferred examples of the group whose polarity is increased by the external stimulus include a group capable of decomposing by the action of a base to generate a polar group (hereinafter also referred to as “base-decomposable group”). That is, preferred examples of the first repeating unit include a repeating unit having a base decomposable group. Examples of the polar group generated by the decomposition of the base-decomposable group are the same as those described above as examples of the polar group generated by the decomposition of the acid-decomposable group, but an amino group is preferable.
  • a preferable group as a base decomposable group is a group in which a hydrogen atom of a polar group is substituted with a group capable of leaving with a base.
  • Examples of the group capable of leaving with a base include 9-fluorenylmethyloxycarbonyl (Fmoc) group.
  • repeating unit having a base decomposable group a repeating unit represented by the following general formula (II) can be preferably exemplified.
  • Rb each independently represents a hydrogen atom, an alkyl group or a group represented by —CH 2 —O—Ra 3 .
  • Ra 3 represents a hydrogen atom, an alkyl group, or an acyl group.
  • L 11 represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar 11 —, —SO 3 — or —SO 2 NH—.
  • Ar 11 represents a divalent aromatic ring group.
  • R 11 represents a divalent organic group.
  • R 12 represents a hydrogen atom or an alkyl group.
  • Rb and Ra 3 are the same as those described for Ra and Ra 2 in formulas (I-1) to (I-10), respectively.
  • L 11 is preferably a linking group represented by —COO—, —CONH— or —Ar 11 —, more preferably a linking group represented by —COO— or —CONH—.
  • R 11 are the same as those described for the divalent organic group as R 1 in formulas (I-1) to (I-10).
  • R 12 represents a hydrogen atom or an alkyl group.
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.
  • R is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • repeating unit having a base decomposable group Specific examples of the repeating unit having a base decomposable group are shown below, but the present invention is not limited thereto.
  • the second repeating unit increases in polarity when triggered by the external stimulus. It preferably has no group.
  • the second repeating unit is preferably a repeating unit (H) having neither the acid-decomposable group nor the base-decomposable group.
  • repeating unit (H) include repeating units represented by the following general formula (I).
  • R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group or an aralkyl group, and is bonded to a carbon atom adjacent to the carbon atom to which R 1 is bonded. And may be condensed with a benzene ring.
  • the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group or aralkyl group in R 1 may further have a substituent.
  • the further substituent include an alkoxy group, a hydroxyl group, a halogen atom (fluorine atom, chlorine atom, etc.), a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, a dialkylamino group, an alkylthio group, and an arylthio group.
  • heterocyclic residues such as a group, an aralkylthio group, a thiophenecarbonyloxy group, a thiophenemethylcarbonyloxy group, and a pyrrolidone residue.
  • the carbon number of the alkyl group which may have a substituent is preferably 1 to 12, more preferably 2 to 9, and still more preferably 4 to 6.
  • the carbon number of the alkenyl group and alkynyl group which may have a substituent is preferably 2 to 12, more preferably 2 to 9, and still more preferably 4 to 6.
  • the carbon number of the cycloalkyl group which may have a substituent is preferably 3 to 12, more preferably 3 to 9, and further preferably 3 to 6.
  • the number of carbon atoms of the aryl group which may have a substituent is preferably 6 to 12, and more preferably 6 to 9.
  • the carbon number of the aralkyl group which may have a substituent is preferably 7 to 12, and more preferably 7 to 9.
  • the carbon number in R 1 being within the above-mentioned preferable range is that the non-removability (typically etching resistance) in step (iv) is further improved and the repeating unit represented by the general formula (I) It is preferable from the viewpoint of further improving the phase separation property between the block of the repeating unit represented by the general formula (I) and the block of the first repeating unit accompanying the further improvement of the hydrophobicity of.
  • R 1 is bonded to the carbon atom adjacent to the carbon atom to which R 1 is bonded (that is, the ortho-position carbon atom constituting the benzene ring when R 1 is used as a reference), and is condensed with the benzene ring.
  • the ring formed additionally is preferably a benzene ring (that is, a naphthalene ring is preferably formed as the whole condensed ring structure).
  • the repeating unit (H) preferably has no polar group.
  • the polar group is the same as that described for the acid-decomposable group in the first repeating unit. Therefore, in the general formula (I), when the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group or aralkyl group in R 1 further has a substituent, the substituent may not contain a polar group. preferable.
  • repeating unit (H) the repeating unit which has a linear or cyclic hydrocarbon structure which does not have a polar group can also be mentioned suitably.
  • the repeating unit having a chain or cyclic hydrocarbon structure having no polar group include a repeating unit represented by the following general formula (IV).
  • R 5 represents a linear or cyclic hydrocarbon group having no polar group.
  • Ra represents a hydrogen atom, an alkyl group, or a —CH 2 —O—Ra 2 group.
  • Ra 2 represents a hydrogen atom, an alkyl group, or an acyl group.
  • Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
  • JP2013-76991A For the description of each group in the general formula (IV), the description in paragraphs [0212] to [0216] of JP2013-76991A can be referred to, and the contents thereof are incorporated in the present specification.
  • Ra represents H, CH 3 , CH 2 OH, or CF 3 .
  • a block copolymer in which any one of the first repeating unit and the second repeating unit is a styrene repeating unit or a (meth) acrylate repeating unit can be preferably exemplified.
  • one of the first repeating unit and the second repeating unit is a styrenic repeating unit.
  • Preferred examples include a polymer; and a block copolymer in which one of the first repeating unit and the second repeating unit is a (meth) acrylate-based repeating unit and the other is a siloxane-based repeating unit.
  • a siloxane-based resin is used for the purpose of more surely expressing the removal resistance of the block of the siloxane-based repeating unit.
  • the repeating unit block is typically vitrified by oxygen plasma treatment.
  • the block copolymer is a block copolymer in which one of the first repeating unit and the second repeating unit is a styrenic repeating unit and the other is a (meth) acrylate repeating unit. It is preferable.
  • the block copolymer further has a repeating unit different from the first repeating unit and the second repeating unit within a range where phase separation of the block of the first repeating unit and the block of the second repeating unit occurs. May be.
  • the mass ratio of each block constituting the block copolymer is appropriately determined according to the type of the phase separation structure to be developed in the step (iii), but the second repeating unit block in the block copolymer
  • the mass ratio of the first repeating unit block is preferably 40:60 to 90:10, and more preferably 45:55 to 80:20.
  • the number average molecular weight (Mn) of the block copolymer is preferably 100000 or less, more preferably 50000 or less, further preferably less than 25000, and more preferably less than 20000 as a polystyrene-converted value by the GPC method. More preferably it is.
  • the number average molecular weight (Mn) of the block copolymer is preferably 3000 or more, more preferably 5000 or more, and still more preferably 6000 or more as a polystyrene conversion value by the GPC method.
  • the degree of dispersion (Mw / Mn) of the block copolymer is preferably 1.0 to 1.5, more preferably 1.0 to 1.2, and 1.0 to 1.1. More preferably.
  • the number average molecular weight (Mn), the weight average molecular weight (Mw) and the dispersity of the resin including the block copolymer are, for example, HLC-8120 (manufactured by Tosoh Corporation), As TSK gel Multipore HXL-M (Tosoh Co., Ltd., 7.8 mm HD ⁇ 30.0 cm) and THF (tetrahydrofuran) or NMP (N-methyl-2-pyrrolidone) as the eluent. .
  • the block copolymer can be synthesized by a known method by radical polymerization or anionic polymerization.
  • living polymerization such as known living anion polymerization and living radical polymerization.
  • living anionic polymerization is particularly advantageous and more preferable for monodispersion. It is also preferable to perform living anionic polymerization using a microreactor apparatus (flow reaction system) as described in JP-A-2009-67999.
  • ⁇ SP represents the absolute value (MPa 1/2 ) of the difference between the SP values described above, and ⁇ SP before conversion is ⁇ SP before the polarity of the functional group in the first repeating unit is changed due to external stimulation.
  • ⁇ SP after conversion indicates ⁇ SP after the polarity of the functional group in the first repeating unit is changed by external stimulation.
  • the content of the block copolymer with respect to the total solid content of the composition containing the block copolymer is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 99% by mass, More preferably, it is 70 mass% to 98 mass%.
  • the composition containing the block copolymer is a compound that generates an acid by the above external stimulus (hereinafter, It is preferable to contain an “acid generator”.
  • the acid generator is not particularly limited as long as it is a publicly known acid generator, but upon irradiation with actinic rays or radiation, at least any of organic acids such as sulfonic acid, bis (alkylsulfonyl) imide, and tris (alkylsulfonyl) methide. Compounds that generate such are preferred.
  • the acid generator is preferably a low molecular compound, in which case the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. Examples of the acid generator include compounds represented by the following general formula (ZI), (ZII), or (ZIII).
  • R 201 , R 202 and R 203 each independently represents an organic group.
  • the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
  • Examples of the group formed by combining two members out of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group).
  • Z ⁇ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).
  • Non-nucleophilic anions include, for example, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyls). Carboxylate anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.
  • alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent.
  • description in paragraph [0236] of JP2013-76991A can be referred to, and the contents thereof are incorporated in the present specification.
  • JP2013-76991A As other non-nucleophilic anions, the description in paragraph [0240] of JP2013-76991A can be referred to, and the contents thereof are incorporated in the present specification.
  • non-nucleophilic anion examples include an aliphatic sulfonate anion in which at least ⁇ -position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom.
  • the non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane.
  • the pKa of the generated acid is preferably ⁇ 1 or less in order to improve sensitivity.
  • an anion represented by the following general formula (AN1) can be mentioned as a preferred embodiment.
  • Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R 1 and R 2 , they may be the same or different.
  • L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
  • A represents a cyclic organic group.
  • x represents an integer of 1 to 20
  • y represents an integer of 0 to 10
  • z represents an integer of 0 to 10.
  • the alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
  • Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
  • Xf include fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 , CH 2 CH 2 C 4 F 9 may be mentioned, among which a fluorine atom and CF 3 are preferable. In particular, it is preferable that both Xf are fluorine atoms.
  • the alkyl group of R 1 and R 2 may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferred is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent for R 1 and R 2 include CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 , and C 7 F 15.
  • R 1 and R 2 are preferably a fluorine atom or CF 3 .
  • x is preferably from 1 to 10, and more preferably from 1 to 5.
  • y is preferably 0 to 4, more preferably 0.
  • z is preferably 0 to 5, and more preferably 0 to 3.
  • the divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO 2 —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these groups are linked can be exemplified, and a linking group having a total carbon number of 12 or less is preferred.
  • —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.
  • the cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having aromaticity but also aromaticity). And the like).
  • the alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group.
  • a polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred.
  • an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like is present in the film in the post-exposure heating step. Diffusivity can be suppressed, which is preferable from the viewpoint of improving MEEF.
  • Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
  • Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring and a pyridine ring are preferred.
  • examples of the cyclic organic group may include a lactone structure, and specific examples thereof may be represented by general formulas (LC1-1) to (LC1-17) that may be included in the resin (A) described later. Can be mentioned.
  • the cyclic organic group may have a substituent, and the description of paragraph [0251] of JP2013-76991A can be referred to as the substituent, and the contents thereof are incorporated in the present specification. It is.
  • Examples of the organic group for R 201 , R 202, and R 203 include an aryl group, an alkyl group, and a cycloalkyl group.
  • R 201 , R 202 and R 203 at least one is preferably an aryl group, more preferably all three are aryl groups.
  • the aryl group, the alkyl group, and the cycloalkyl group the description in paragraph [0252] of JP2013-76991A can be referred to, and the contents thereof are incorporated in the present specification.
  • preferable structures in the case where at least one of R 201 , R 202 and R 203 is not an aryl group include paragraphs 0046 to 0048 of JP-A-2004-233661 and paragraphs 0040 to 0040 of JP-A-2003-35948.
  • R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 are the same as the aryl group described as the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI).
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent. Examples of this substituent include those that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI) may have.
  • Z ⁇ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ⁇ in formula (ZI).
  • Examples of the acid generator further include compounds represented by general formulas (ZIV), (ZV), and (ZVI) described in paragraphs [0262] to [0264] of JP2013-76991A.
  • An acid generator can be used individually by 1 type or in combination of 2 or more types.
  • the content of the acid generator in the composition containing the block copolymer is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, based on the total solid content of the composition. More preferably, it is 1 to 30% by mass.
  • the composition containing the block copolymer is a compound that generates a base by the above external stimulus (hereinafter, It is also preferable to contain a “base generator”.
  • Known base generators can be used.
  • M.M. Shirai, and M Tsunooka Prog. Polym. Sci. , 21, 1 (1996); Masahiro Tsunooka, Sakai Polymer Processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A. Sarker, and D. Neckers, Chem. Mater. , 11, 170 (1999); Tachi, M. Shirai, and M.M. Tsunooka, J.A. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.K. Graziano, J.M. Photopolym. Sci. Technol.
  • the base generator one kind can be used alone, or two or more kinds can be used in combination.
  • Specific examples of the ionic compound used as the base generator include those represented by the following structural formula. Needless to say, the present invention is not limited to these examples.
  • examples of the oxime ester derivative as a base generator include those represented by the following structural formula.
  • acyl compound examples include those represented by the following structural formula.
  • examples of the carbamate compound as the base generator include the following compounds.
  • examples of the base generator suitably used in the present invention include compounds represented by the following formula (5).
  • R C each independently represents a hydrogen atom or a monovalent organic group, and may be the same or different.
  • R C is bonded to form a cyclic structure. And may contain a heteroatom bond, provided that at least one of R C is a monovalent organic group, and R 5 , R 6 , R 7 and R 8 are each Independently, hydrogen, halogen, hydroxyl group, nitro group, nitroso group, mercapto group, silyl group, silanol group or monovalent organic group, which may be the same or different, R 5 , R 6 , R 7 and R 8 may combine two or more of them to form a cyclic structure, and may include a bond of a hetero atom.
  • Examples of the basic substance generated in the base generator in the present invention include an amine represented by the following formula (A) and an amidine represented by the following formula (B).
  • R C each independently represents a hydrogen atom or a monovalent organic group, and may be the same or different.
  • R C may combine to form a cyclic structure, It may contain a heteroatom bond, provided that at least one of R C is a monovalent organic group, and each R d is independently a hydrogen atom or a monovalent organic group, and the same R d may be bonded to each other to form a cyclic structure or may contain a hetero atom bond.
  • R C of the formula (A) has an amidine structure as contained in the formula (B)
  • the generated base is not the amine of the formula (A) but the formula (B ) Belonging to amidine.
  • the generated basic substance is preferably an aliphatic amine or amidine because it is a highly basic amine.
  • the generated basic substance is preferably an aliphatic amine or amidine because it is a highly basic amine.
  • secondary or tertiary aliphatic amines or amidines are preferable.
  • the aliphatic amine is generated to achieve high sensitivity, and further, from the viewpoint of increasing the solubility contrast of the unexposed area of the exposed area, the nitrogen atom of R c in formula (A), etc. , All the atoms directly bonded to the nitrogen atom constituting the amino group of the generated amine are hydrogen atoms or carbon atoms having SP3 orbitals (except when all of R c are hydrogen atoms). Is preferred.
  • the substituent in which the atom directly bonded to the nitrogen atom is a carbon atom having an SP3 orbital include a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon.
  • An aliphatic hydrocarbon group composed of a group or a combination thereof.
  • the said aliphatic hydrocarbon group may have substituents, such as an aromatic group, or may contain bonds other than hydrocarbons, such as a hetero atom, in a hydrocarbon chain.
  • substituents such as an aromatic group
  • bonds other than hydrocarbons such as a hetero atom, in a hydrocarbon chain.
  • Preferred are straight-chain or branched saturated or unsaturated alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 4 to 13 carbon atoms, phenoxyalkyl groups having 7 to 26 carbon atoms, and aryls having 7 to 26 carbon atoms. Examples thereof include an alkyl group and a hydroxyalkyl group having 1 to 20 carbon atoms.
  • R c has the above cyclic aliphatic hydrocarbon group or the above cycloalkyl group, a heterocyclic structure containing a nitrogen atom to which two of R c are linked to form a ring and R c is bonded Including the case of forming.
  • aliphatic hydrocarbon group examples include a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a cyclohexyl group, an isobornyl group, a norbornyl group, and an adamantyl group.
  • a benzyl group and the like but are not limited thereto.
  • the heterocyclic structure when forming a heterocyclic structure containing a nitrogen atom to which R c is attached, for example, aziridine (three-membered ring) Azetidine (4-membered ring), pyrrolidine (5-membered ring), piperidine (6-membered ring), azepane (7-membered ring), azocane (8-membered ring) and the like.
  • These heterocyclic structures may have a substituent such as a linear or branched alkyl group.
  • a monoalkylaziridine such as methylaziridine, a dialkylaziridine such as dimethylaziridine, and methylazetidine
  • Monoalkyl azetidine such as dialkyl azetidine such as dimethyl azetidine, trialkyl azetidine such as trimethyl azetidine
  • monoalkyl pyrrolidine such as methyl pyrrolidine
  • dialkyl pyrrolidine such as dimethyl pyrrolidine
  • trialkyl pyrrolidine such as trimethyl pyrrolidine
  • tetra Tetraalkylpyrrolidines such as methylpyrrolidine
  • monoalkylpiperidines such as methylpiperidine
  • dialkylpiperidines such as dimethylpiperidine
  • trialkylpiperidines such as trimethylpiperidine Lysine
  • a tetraalkyl piperidine such as tetramethylpiperidine
  • penta-alkyl piperidines such as such as such
  • Examples of the compound represented by the formula (A) include the following compounds.
  • a base generator described in JP-A-2008-247747 is also preferably used, the contents of which are incorporated herein.
  • amines generated when the base generator is decomposed in the present invention include primary amines such as n-butylamine, amylamine, hexylamine, cyclohexylamine, octylamine, and benzylamine, diethylamine, and dipropylamine.
  • Secondary amines such as linear secondary amines such as diisopropylamine and dibutylamine, cyclic secondary amines such as aziridine, azetidine, pyrrolidine, piperidine, azepane, and azocan, and alkyl substituents thereof, trimethylamine
  • Aliphatic tertiary amines such as triethylamine, tripropylamine, tributylamine, triethylenediamine, 1,4-diazabicyclo [2.2.2] octane, quinuclidine and 3-quinuclidinol, and aromatic tertiary amines such as dimethylaniline.
  • Grade amines, and isoquinoline, pyridine, collidine, and heterocyclic tertiary amines such as beta-picoline and the like.
  • amidine generated when the base generator is decomposed in the present invention include secondary amidines such as imidazole, purine, triazole, and guanidine and derivatives thereof, pyrimidine, triazine, 1,8-diazabicyclo [5.4. 0.0] undec-7-ene (DBU) and tertiary amidines such as 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) and their derivatives.
  • secondary amidines such as imidazole, purine, triazole, and guanidine and derivatives thereof
  • pyrimidine triazine
  • tertiary amidines such as 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) and their derivatives.
  • R c will be omitted here because may be the same as R c in the formula (A).
  • the generated base include primary and secondary amines containing NH groups and amidines containing NH groups among the above-mentioned bases.
  • produce is a secondary amine and / or amidine, it is preferable from the point that the sensitivity as a base generator becomes high. It is presumed that this is because the use of secondary amine or amidine eliminates active hydrogen at the amide bond site, thereby changing the electron density and improving the sensitivity of isomerization.
  • R 5 , R 6 , R 7 and R 8 are each independently hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group Group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group or monovalent organic group, which may be the same or different.
  • Two or more of R 5 , R 6 , R 7 and R 8 may be bonded to form a cyclic structure, and may include a hetero atom bond.
  • halogen atom examples include a fluorine atom, a chlorine atom, and a bromine atom.
  • the monovalent organic group is not particularly limited, and may be a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group, a cyano group, an isocyano group, Examples include cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, carboxyl group, carboxylate group, acyl group, acyloxy group, and hydroxyimino group. These organic groups may contain bonds and substituents other than hydrocarbon groups such as heteroatoms in the organic group, and these may be linear or branched.
  • the bond other than the hydrocarbon group in the organic group of R 5 to R 8 is not particularly limited as long as the effect of the present invention is not impaired, and is an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond.
  • the substituent other than the hydrocarbon group in the organic group of R 5 to R 8 is not particularly limited as long as the effect of the present invention is not impaired, and includes a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, Isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group Acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, saturated or unsaturated alkyl ether group
  • the hydrogen contained in the substituent may be substituted with a hydrocarbon group.
  • the hydrocarbon group contained in the substituent may be any of linear, branched, and cyclic.
  • examples of the substituent other than the hydrocarbon group in the organic group represented by R 5 to R 8 include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, and an isothiocyanato group.
  • Examples of monovalent organic groups include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, and a propyl group; cycloalkyl groups having 4 to 23 carbon atoms such as a cyclopentyl group and a cyclohexyl group; a cyclopentenyl group and a cyclohexenyl group.
  • a cycloalkenyl group having 4 to 23 carbon atoms such as a group; an aryloxyalkyl group having 7 to 26 carbon atoms such as phenoxymethyl group, 2-phenoxyethyl group and 4-phenoxybutyl group (—ROAr group); benzyl group, 3
  • An aralkyl group having 7 to 20 carbon atoms such as a phenylpropyl group; an alkyl group having 2 to 21 carbon atoms having a cyano group such as a cyanomethyl group or ⁇ -cyanoethyl group; 1 to 20 carbon atoms having a hydroxyl group such as a hydroxymethyl group Alkyl groups, methoxy groups, ethoxy groups and the like, alkoxy groups having 1 to 20 carbon atoms, acetamide groups, benzenesulfonamide groups C 6 H 5 SO 2 NH 2 -) amide group having 2 to 21 carbon atoms such as a methylthio group, an al
  • An aryl group of ⁇ 20 an aryl group having 6 to 20 carbon atoms substituted with an electron donating group and / or an electron withdrawing group, a benzyl group substituted with an electron donating group and / or an electron withdrawing group, a cyano group, and It is preferably a methylthio group (—SCH 3 ).
  • the alkyl moiety may be linear, branched or cyclic.
  • R 5 to R 8 may be bonded to each other to form a cyclic structure.
  • the cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, heterocycles, and condensed rings, and the alicyclic hydrocarbons, heterocycles, and condensed rings.
  • the structure which becomes may be sufficient.
  • R 5 ⁇ R 8 is formed by two or more of them are combined, naphthalene share atoms of the benzene ring of R 5 ⁇ R 8 are attached, anthracene, phenanthrene, and fused ring indene
  • the absorption wavelength is preferable from the viewpoint of increasing the wavelength.
  • At least one of R 5 , R 6 , R 7 and R 8 is a hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, A phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, or an ammonio group is desirable.
  • R 5 when at least one of R 6, R 7 and R 8 is a hydroxyl group, and R 5, R 6, does not contain a hydroxyl group at R 7 and R 8 compound, This is preferable from the viewpoint of improving the solubility in a basic aqueous solution or the like and increasing the absorption wavelength.
  • R 8 when R 8 is a phenolic hydroxyl group, a reaction site for cyclization of a compound isomerized to a cis isomer increases, which is preferable from the viewpoint of easy cyclization.
  • the structure represented by the chemical formula (5) has a geometric isomer at the (—CH ⁇ CH—C ( ⁇ O) —) moiety, but it is preferable to use only the trans isomer.
  • cis isomers that are geometric isomers may be mixed during synthesis and purification steps and storage, and in this case, a mixture of trans isomers and cis isomers may be used. It is preferable that the ratio of cis-isomer is less than 10%.
  • a base generator can be used individually by 1 type or in combination of 2 or more types.
  • the content of the base generator in the composition containing the block copolymer is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, based on the total solid content of the composition. More preferably, it is 1 to 30% by mass.
  • the composition containing a block copolymer contains a solvent.
  • the solvent is not particularly limited as long as it can dissolve the block copolymer.
  • the solvent that dissolves the block copolymer well can be determined using the solubility parameter (SP value).
  • SP value solubility parameter
  • a solvent having an SP value close to the median SP value of the repeating units constituting each block of the block copolymer is a solvent that dissolves the block copolymer well.
  • the composition containing the block copolymer may contain one type of solvent or two or more types of solvents.
  • the solvent is preferably an organic solvent.
  • organic solvent examples include lactones such as ⁇ -butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol, di- Polyhydric alcohols such as propylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, the polyhydric alcohols or compounds having the ester bond Monoalkyl ether such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether Derivatives of polyhydric alcohols such as compounds having an ether bond [in these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PG
  • Esters Halogen-based organic solvents such as chloroform; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethyl benzene, di Aromatic organic solvents such as ethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene and mesitylene can be exemplified.
  • the solvent is preferably a highly hydrophobic solvent such as toluene, xylene, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate and chloroform.
  • the solid content concentration of the composition containing the block copolymer is usually 1.0 to 10% by mass, preferably 1.5 to 6.0% by mass, more preferably 1.5 to 5.5% by mass. It is.
  • the present invention provides a block copolymer having a first repeating unit block and a second repeating unit block different from the first repeating unit, which is provided for the pattern forming method of the present invention described above.
  • the first repeating unit has a functional group whose polarity changes when triggered by at least one external stimulus selected from the group consisting of heating and irradiation with actinic rays or radiation
  • the second repeating unit also relates to a block copolymer that does not have a functional group whose polarity changes with the external stimulus.
  • resin is a block copolymer
  • each glass transition temperature (Tg) corresponding to each block constituting the block copolymer can be confirmed by measuring.
  • the resin is a diblock block copolymer having a first repeating unit block and a second repeating unit block
  • the glass transition temperature corresponding to the first repeating unit block. (Tg 1 ) and the glass transition temperature (Tg 2 ) corresponding to the second repeating unit block are confirmed.
  • a Tg of 105 ° C.
  • the glass transition temperature (Tg 1 ) and the glass transition temperature (Tg 2 ) are the glass transition temperatures. Only the glass transition temperature (Tm) during is confirmed. In this case, in a random copolymer having a styrene repeating unit and a methyl methacrylate repeating unit, only Tg at 112 ° C. is observed.
  • a glass transition temperature is temperature measured on temperature increase rate conditions of 10 degree-C / min in model number Q1000 which is a scanning scanning calorimeter (DSC) made from TA instruments.
  • the present invention also relates to a patterning material comprising the block copolymer of the present invention described above, a compound that generates an acid by the external stimulus or a compound that generates a base by the external stimulus, and a solvent. Related.
  • the actinic ray-sensitive or radiation-sensitive resin composition that is preferably used in the formation of the guide pattern will be described.
  • the actinic ray-sensitive or radiation-sensitive resin composition is positively developed (when exposed, the solubility in the developer increases, and the unexposed area is patterned. And development for removing the exposed portion).
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is an actinic ray-sensitive or radiation-sensitive resin composition for alkali development used for development using an alkali developer. Can do.
  • the term “for alkali development” means at least an application provided for a development process using an alkali developer.
  • an actinic ray-sensitive or radiation-sensitive resin composition uses an organic developer as a developer
  • negative-type development when exposed, the solubility in the developer decreases and the exposed portion is exposed. Remains as a pattern and is used for development in which unexposed portions are removed.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is an actinic ray-sensitive or radiation-sensitive resin composition for developing an organic solvent used in development using a developer containing an organic solvent. It can be a thing.
  • the term “for organic solvent development” means an application that is used in a step of developing using a developer containing at least an organic solvent.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is typically a resist composition, and even a negative resist composition (that is, a resist composition for developing an organic solvent) is positive. It may be a mold resist composition (that is, a resist composition for alkali development).
  • the composition according to the present invention is typically a chemically amplified resist composition.
  • (A) Resin having a group that decomposes by the action of an acid to generate a polar group
  • the actinic ray-sensitive or radiation-sensitive resin composition is a group that decomposes by the action of an acid to generate a polar group (hereinafter “ It is preferable to contain a resin (A) (hereinafter also referred to as “resin (A)”) having an “acid-decomposable group”.
  • the resin (A) is, for example, a resin having an acid-decomposable group in the main chain or side chain of the resin or in both the main chain and the side chain.
  • Examples of polar groups generated by the decomposition of acid-decomposable groups include alcoholic hydroxyl groups, amino groups, and acidic groups.
  • the polar group generated by the decomposition of the acid-decomposable group is preferably an acidic group.
  • an acidic group the acidic group similar to what was demonstrated in the acid-decomposable group of the 1st repeating unit of the said block copolymer is mentioned.
  • the resin (A) preferably has a repeating unit (a) having an acid-decomposable group.
  • the repeating unit (a) include the same repeating units as those described for the repeating unit having an acid-decomposable group that can be suitably contained in the first repeating unit of the block copolymer.
  • the resin (A) is a resin having a repeating unit represented by the general formula (V), the general formula (VI) or the general formula (4) as the repeating unit (a) having an acid-decomposable group. It is preferable.
  • the resin (A) is a resin having the repeating unit represented by the general formula (VI) as the repeating unit (a), and an alkaline developer is used as a developer.
  • a form in which a positive guide pattern is formed may be mentioned.
  • the resin (A) is a resin having a repeating unit represented by the general formula (V) or the general formula (4) as the repeating unit (a), and The negative guide pattern is formed using a developer containing an organic solvent as the developer.
  • repeating unit (a) having an acid-decomposable group may be used, or two or more types may be used in combination.
  • the content of the repeating unit having an acid-decomposable group in the resin (A) (when there are a plurality of types) is 15 mol% to 95 mol% with respect to all the repeating units in the resin (A). However, it is more preferably 20 mol% to 95 mol%. In particular, when organic solvent development is performed, the content of repeating units having an acid-decomposable group in the resin (A) (the total when there are plural types) is 20 with respect to all the repeating units in the resin (A). It is preferably at least mol%, more preferably at least 45 mol%.
  • the content of the repeating unit having an acid-decomposable group is preferably 80 mol% or less, more preferably 75 mol% or less, based on all repeating units in the resin (A).
  • the resin (A) It is preferable to have a repeating unit represented by Formula (1).
  • R 11 , R 12 and R 13 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 13 may be bonded to Ar 1 to form a ring, in which case R 13 represents an alkylene group.
  • X 1 represents a single bond or a divalent linking group.
  • Ar 1 represents an (n + 1) -valent aromatic ring group, and when bonded to R 13 to form a ring, represents an (n + 2) -valent aromatic ring group.
  • n represents an integer of 1 to 4.
  • alkyl group, cycloalkyl group, halogen atom, alkoxycarbonyl group of R 11 , R 12 , and R 13 in formula (1), and the substituents that these groups may have include those represented by the general formula (V).
  • V The general formula (V).
  • Ar 1 represents an (n + 1) -valent aromatic ring group.
  • the divalent aromatic ring group in the case where n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, an anthracenylene group, or the like.
  • Examples of preferred aromatic ring groups include heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole.
  • n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group.
  • the group formed can be preferably mentioned.
  • the (n + 1) -valent aromatic ring group may further have a substituent.
  • Examples of the substituent that the above-described alkylene group and (n + 1) -valent aromatic ring group may have include an alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, and a propoxy group, which are exemplified as R 51 to R 53 in the general formula (V).
  • X 1 As the divalent linking group for X 1 , —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO 2 —, —CONR— (wherein R is A hydrogen atom or an alkyl group), an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), or a plurality thereof. Examples thereof include a combined divalent linking group.
  • X 1 is preferably a single bond, —COO— or —CONH—, and more preferably a single bond or —COO—.
  • an optionally substituted aromatic ring group having 6 to 18 carbon atoms is more preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are particularly preferable.
  • the repeating unit (b) preferably has a hydroxystyrene structure. That is, Ar 1 is preferably a benzene ring group.
  • N represents an integer of 1 to 4, preferably 1 or 2, and more preferably 1.
  • a 1 or 2.
  • Resin (A) may contain two or more types of repeating units represented by general formula (1).
  • the content of the repeating unit represented by the general formula (1) (the total when containing plural types) is within the range of 3 to 98 mol% with respect to all the repeating units in the resin (A). Is more preferably in the range of 10 to 80 mol%, and still more preferably in the range of 25 to 70 mol%.
  • the resin (A) preferably contains a repeating unit (c) having a polar group.
  • the repeating unit (c) is preferably a non-acid-decomposable repeating unit (that is, having no acid-decomposable group).
  • the “polar group” that can be contained in the repeating unit (c) and the repeating unit having a polar group the description in paragraphs [0149] to [0157] of JP2013-76991A can be referred to. It is incorporated herein.
  • the repeating unit (c) When the repeating unit (c) has an alcoholic hydroxy group or a cyano group as a polar group, it is a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group as one preferred repeating unit. Can be mentioned. At this time, it is preferable not to have an acid-decomposable group.
  • the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group.
  • the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group partial structures represented by the following general formulas (VIIa) to (VIIc) are preferred. This improves the substrate adhesion and developer compatibility.
  • R 2 c to R 4 c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R 2 c to R 4 c represents a hydroxyl group. Preferably, one or two of R 2 c to R 4 c are a hydroxyl group and the remaining is a hydrogen atom. In the general formula (VIIa), more preferably, two of R 2 c to R 4 c are a hydroxyl group and the rest are hydrogen atoms.
  • Examples of the repeating unit having a partial structure represented by the general formulas (VIIa) to (VIIc) include the repeating units represented by the following general formulas (AIIa) to (AIIc).
  • R 1 c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
  • R 2 c ⁇ R 4 c is in the general formula (VIIa) ⁇ (VIIc), the same meanings as R 2 c ⁇ R 4 c.
  • the resin (A) may or may not contain a repeating unit having a hydroxyl group or a cyano group. However, when it is contained, the content of the repeating unit having a hydroxyl group or a cyano group is in the resin (A).
  • the amount is preferably 1 to 60 mol%, more preferably 3 to 50 mol%, still more preferably 5 to 40 mol%, based on all repeating units.
  • repeating unit having a hydroxyl group or a cyano group are listed below, but the present invention is not limited thereto.
  • the repeating unit (c) may be a repeating unit having a lactone structure as a polar group.
  • the repeating unit having a lactone structure is more preferably a repeating unit represented by the following general formula (AII).
  • Rb 0 represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group (preferably having 1 to 4 carbon atoms).
  • substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom.
  • the halogen atom for Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Rb 0 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.
  • Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group obtained by combining these.
  • Ab is preferably a single bond or a divalent linking group represented by —Ab 1 —CO 2 —.
  • Ab 1 is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, and preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.
  • V represents a group having a lactone structure.
  • any group having a lactone structure can be used, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is added to the 5- to 7-membered ring lactone structure.
  • Those in which other ring structures are condensed in the form to be formed are preferred.
  • the lactone structure may be directly bonded to the main chain.
  • Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-8), (LC1-13), (LC1-14).
  • the lactone structure portion may or may not have a substituent (Rb 2 ).
  • Preferred examples of the substituent (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a monovalent cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkoxycarbonyl group having 2 to 8 carbon atoms. , Carboxyl group, halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group.
  • n 2 represents an integer of 0 to 4. When n 2 is 2 or more, a plurality of substituents (Rb 2 ) may be the same or different, and a plurality of substituents (Rb 2 ) may be bonded to form a ring. .
  • the repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used.
  • One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
  • the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.
  • the resin (A) may or may not contain a repeating unit having a lactone structure, but when it contains a repeating unit having a lactone structure, the content of the repeating unit in the resin (A) is The range is preferably 1 to 70 mol%, more preferably 3 to 65 mol%, and still more preferably 5 to 60 mol% with respect to the repeating unit. Specific examples of the repeating unit having a lactone structure in the resin (A) are shown below, but the present invention is not limited thereto. In the formula, Rx represents H, CH 3 , CH 2 OH, or CF 3 .
  • the repeating unit (c) may be a repeating unit having a sultone structure as a polar group.
  • the sultone structure is preferably a structure represented by the following general formula (SL1-1) or (SL1-2).
  • Rb 2 and n 2 have the same meanings as in the general formulas (LC1-1) to (LC1-17) described above.
  • repeating unit containing a sultone group contained in the resin (A) those obtained by substituting the lactone group in the repeating unit having a lactone group with a sultone group are preferable.
  • the repeating unit (c) may be a repeating unit having a cyclic carbonate structure as a polar group.
  • the repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).
  • R A 1 represents a hydrogen atom or an alkyl group.
  • R A 2 each independently represents a substituent when n is 2 or more.
  • A represents a single bond or a divalent linking group.
  • Z represents an atomic group that forms a monocyclic or polycyclic structure together with a group represented by —O—C ( ⁇ O) —O— in the formula.
  • n represents an integer of 0 or more.
  • the alkyl group represented by R A 1 may have a substituent such as a fluorine atom.
  • R A 1 preferably represents a hydrogen atom, a methyl group or a trifluoromethyl group, and more preferably represents a methyl group.
  • the substituent represented by R A 2 is, for example, an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, an amino group, or an alkoxycarbonylamino group.
  • the alkyl group may have a substituent such as a hydroxyl group.
  • n is an integer of 0 or more representing the number of substituents. n is, for example, preferably 0 to 4, more preferably 0.
  • Examples of the divalent linking group represented by A include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, or a combination thereof.
  • an alkylene group an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 5 carbon atoms is more preferable.
  • A is preferably a single bond or an alkylene group.
  • Examples of the polycycle including —O—C ( ⁇ O) —O— represented by Z include, for example, a cyclic carbonate represented by the following general formula (a) together with one or more other ring structures: Examples include a structure forming a condensed ring and a structure forming a spiro ring.
  • the “other ring structure” that can form a condensed ring or a spiro ring may be an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring. .
  • one type of repeating units having a cyclic carbonate structure may be contained alone, or two or more types may be contained.
  • the content of the repeating unit having a cyclic carbonate structure (preferably, the repeating unit represented by the general formula (A-1)) is based on the total repeating units constituting the resin (A). It is preferably 3 to 80 mol%, more preferably 3 to 60 mol%, particularly preferably 3 to 30 mol%, and most preferably 10 to 15 mol%. By setting it as such content rate, developability, low defect property, low LWR, low PEB temperature dependency, profile, etc. can be improved in the formation of the guide pattern.
  • R A 1 in the following specific examples are the same meaning as R A 1 in the general formula (A-1).
  • the polar group that the repeating unit (c) may have is an acidic group.
  • Preferred acidic groups include phenolic hydroxyl groups, carboxylic acid groups, sulfonic acid groups, fluorinated alcohol groups (eg hexafluoroisopropanol group), sulfonamide groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, Alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, A tris (alkylsulfonyl) methylene group is mentioned.
  • the repeating unit (c) is more preferably a repeating unit having a carboxyl group.
  • the repeating unit having an acidic group includes a repeating unit in which an acidic group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an acidic group in the main chain of the resin through a linking group. It is preferable to use a polymerization initiator or a chain transfer agent having a repeating unit bonded to each other, or an acidic group, at the time of polymerization and introduce it at the end of the polymer chain. Particularly preferred are repeating units of acrylic acid or methacrylic acid.
  • the acidic group that the repeating unit (c) may have may or may not contain an aromatic ring, but when it has an aromatic ring, it is preferably selected from acidic groups other than phenolic hydroxyl groups.
  • the content of the repeating unit having an acidic group is preferably 30 mol% or less, and 20 mol% or less with respect to all the repeating units in the resin (A). More preferably.
  • content of the repeating unit which has an acidic group in resin (A) is 1 mol% or more normally.
  • Rx represents H, CH 3 , CH 2 OH, or CF 3 .
  • the resin (A) may have a repeating unit (d) having a plurality of aromatic rings represented by the following general formula (c1).
  • the repeating unit (d) having a plurality of aromatic rings represented by the following general formula (c1).
  • the description in paragraphs [0194] to [0207] of JP2013-76991A can be referred to, and the contents thereof are incorporated in the present specification.
  • the resin (A) may or may not contain the repeating unit (d), but when it is contained, the content of the repeating unit (d) is 1 to 30 with respect to the entire repeating unit of the resin (A). It is preferably in the range of mol%, more preferably in the range of 1 to 20 mol%, still more preferably in the range of 1 to 15 mol%.
  • the repeating unit (d) contained in the resin (A) may contain a combination of two or more types.
  • the resin (A) in the present invention may have a repeating unit other than the repeating units (a) to (d) as appropriate.
  • a repeating unit that has an alicyclic hydrocarbon structure that does not have a polar group (for example, the acid group, hydroxyl group, or cyano group) and does not exhibit acid decomposability can be included.
  • the solubility of the resin can be appropriately adjusted during development using a developer containing an organic solvent.
  • the repeating unit represented by the general formula (IV) described in the second repeating unit of the block copolymer is similarly exemplified.
  • the resin (A) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability.
  • the content is preferably 1 to 20 mol%, more preferably 5 to 15 mol%, based on all repeating units in the resin (A).
  • the resin (A) may further contain a repeating unit represented by the following general formula (5).
  • R 41 represents a hydrogen atom or a methyl group.
  • L 41 represents a single bond or a divalent linking group.
  • L 42 represents a divalent linking group.
  • S represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.
  • repeating unit represented by the general formula (5) Specific examples of the repeating unit represented by the general formula (5) are shown below, but the present invention is not limited thereto. Specific examples of the repeating unit represented by the general formula (P) include paragraphs [0168] to [0210] of JP2013-80002A and paragraphs [0191] to [0191] of JP2013-137537A. [0203] can also be considered, and the contents thereof are incorporated in the present specification.
  • the content of the repeating unit represented by the general formula (5) in the resin (A) is preferably in the range of 1 to 40 mol% with respect to all the repeating units of the resin (A), and in the range of 2 to 30 mol%. Is more preferable, and the range of 5 to 25 mol% is particularly preferable.
  • the resin (A) may contain the following monomer components in view of effects such as improvement of Tg, improvement of dry etching resistance, and the above-described internal filter of out-of-band light.
  • the content molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and further the general required performance of the resist, resolving power, heat resistance, It is set as appropriate to adjust the sensitivity and the like.
  • resin (A) Specific examples of the resin (A) are shown below, but the present invention is not limited thereto.
  • the form of the resin (A) may be any of random type, block type, comb type, and star type.
  • Resin (A) is compoundable by the radical, cation, or anion polymerization of the unsaturated monomer corresponding to each structure, for example. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure. For example, as a general synthesis method, an unsaturated monomer and a polymerization initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the unsaturated monomer and the polymerization initiator is added to the heating solvent for 1 to 10 hours. The dropping polymerization method etc. which are dropped and added over are mentioned, and the dropping polymerization method is preferable.
  • the solvent used for the polymerization examples include a solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition described below, and more preferably the composition of the present invention.
  • Polymerization is preferably carried out using the same solvent as used in the above. Thereby, generation
  • the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
  • a polymerization initiator a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization.
  • an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable.
  • Preferable initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If necessary, the polymerization may be performed in the presence of a chain transfer agent (for example, alkyl mercaptan).
  • the concentration of the reaction is 5 to 70% by mass, preferably 10 to 50% by mass.
  • the reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 40 ° C to 100 ° C.
  • the reaction time is usually 1 to 48 hours, preferably 1 to 24 hours, and more preferably 1 to 12 hours.
  • Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less.
  • Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent
  • a normal method such as a method can be applied.
  • the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.
  • the solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer.
  • a compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use.
  • a precipitation or reprecipitation solvent a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.
  • the amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally, 100 to 10,000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300 to 1000 parts by mass.
  • the temperature at the time of precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.).
  • the precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.
  • the precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).
  • the resin may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).
  • the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
  • a polymerization initiator a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization.
  • azo initiator an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable.
  • Preferable initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like.
  • an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery.
  • the concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass.
  • the reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.
  • the composition of the present invention is used from the viewpoint of transparency to ArF light.
  • the resin (A) used has substantially no aromatic ring (specifically, the content of the repeating unit having an aromatic group is preferably 5 mol% or less, based on the total repeating units of the resin, More preferably, it is preferably 3 mol% or less, ideally 0 mol%, that is, having no aromatic group), and the resin (A) has a monocyclic or polycyclic alicyclic hydrocarbon structure. preferable.
  • the resin (A) does not contain a fluorine atom and a silicon atom from the viewpoint of compatibility with the hydrophobic resin (HR).
  • the resin (A) is preferably one in which all of the repeating units are composed of (meth) acrylate repeating units.
  • all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units.
  • the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.
  • an actinic ray-sensitive or radiation-sensitive film obtained from an actinic ray-sensitive or radiation-sensitive resin composition is applied to a KrF excimer laser, an electron beam, an X-ray, a high-energy ray having a wavelength of 50 nm or less (such as EUV light).
  • the resin (A) may have a repeating unit having an aromatic ring, and preferably has a repeating unit represented by the general formula (1) as described above.
  • the repeating unit having an aromatic ring is not particularly limited, and is also exemplified in the above description of each repeating unit, but a styrene unit, a hydroxystyrene unit, a phenyl (meth) acrylate unit, a hydroxyphenyl (meth) acrylate.
  • examples include units.
  • the resin (A) in this case more specifically, a resin having a hydroxystyrene repeating unit and a hydroxystyrene repeating unit protected by an acid-decomposable group, a repeating unit having the aromatic ring, Examples thereof include a resin having a repeating unit in which the carboxylic acid moiety of (meth) acrylic acid is protected by an acid-decomposable group.
  • the molecular weight of the resin (A) is not particularly limited, but the weight average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 1500 to 60000, and particularly preferably in the range of 2000 to 30000. preferable.
  • the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).
  • the dispersity (Mw / Mn) is preferably 1.00 to 5.00, more preferably 1.00 to 3.50, and still more preferably 1.00 to 2.50.
  • the resin (A) of the present invention can be used alone or in combination of two or more.
  • the content of the resin (A) is preferably 20 to 99% by mass, more preferably 30 to 99% by mass, based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. More preferably, it is 40 to 99% by mass.
  • Actinic ray-sensitive or radiation-sensitive resin composition is usually a compound that generates acid upon irradiation with actinic ray or radiation (hereinafter referred to as “acid generation”). It is preferable to contain "agent” or "compound (B)".
  • the acid generator is not particularly limited as long as it is a publicly known acid generator, but upon irradiation with actinic rays or radiation, at least any of organic acids such as sulfonic acid, bis (alkylsulfonyl) imide, and tris (alkylsulfonyl) methide. Compounds that generate such are preferred.
  • the compound (B) that generates an acid upon irradiation with actinic rays or radiation may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Further, the form of the low molecular compound and the form incorporated in a part of the polymer may be used in combination.
  • the molecular weight is preferably 3000 or less, more preferably 2000 or less, and 1000 or less. Is more preferable.
  • the resin (A) is incorporated into a part of the resin (A) described above.
  • Specific examples and preferred examples of the acid generator include those described for the acid generator that may be contained in the composition containing the block copolymer.
  • the compound (B) has a volume of 240 to 3 or more by irradiation with actinic rays or radiation from the viewpoint of improving the resolution by suppressing the diffusion of the acid generated by exposure to the non-exposed portion. It is preferably a compound that generates an acid having a size, more preferably a compound that generates an acid having a volume of 300 to 3 or more, and a compound that generates an acid having a volume of 350 to 3 or more. Is more preferable, and a compound that generates an acid having a volume of 400 3 or more is particularly preferable. However, from the viewpoint of sensitivity and coating solvent solubility, the volume is preferably 2000 3 or less, and more preferably 1500 3 or less.
  • the volume value was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure. By performing molecular orbital calculation using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated.
  • An acid generator can be used individually by 1 type or in combination of 2 or more types.
  • the content of the acid generator in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, based on the total solid content of the composition. %, More preferably 1 to 30% by mass.
  • the solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition is not particularly limited as long as it can dissolve each component.
  • alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred.
  • solvents may be used alone or in combination of two or more.
  • the mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40.
  • the solvent having a hydroxyl group is preferably an alkylene glycol monoalkyl ether, and the solvent having no hydroxyl group is preferably an alkylene glycol monoalkyl ether carboxylate.
  • the actinic ray-sensitive or radiation-sensitive resin composition preferably further contains a basic compound (D).
  • the basic compound (D) is preferably a compound having a stronger basicity than phenol.
  • this basic compound is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound.
  • nitrogen-containing basic compound that can be used is not particularly limited, for example, compounds classified into the following (1) to (7) can be used.
  • Each R independently represents a hydrogen atom or an organic group. However, at least one of the three Rs is an organic group. This organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group.
  • the number of carbon atoms of the alkyl group as R is not particularly limited, but is usually 1 to 20, and preferably 1 to 12.
  • the number of carbon atoms of the cycloalkyl group as R is not particularly limited, but is usually 3 to 20, and preferably 5 to 15.
  • the number of carbon atoms of the aryl group as R is not particularly limited, but is usually 6 to 20, and preferably 6 to 10. Specific examples include a phenyl group and a naphthyl group.
  • the number of carbon atoms of the aralkyl group as R is not particularly limited, but is usually 7 to 20, preferably 7 to 11. Specific examples include a benzyl group.
  • a hydrogen atom may be substituted with a substituent.
  • substituents include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.
  • Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexyl.
  • preferred basic compounds represented by the general formula (BS-1) include those in which at least one R is an alkyl group substituted with a hydroxy group. Specific examples include triethanolamine and N, N-dihydroxyethylaniline.
  • the alkyl group as R may have an oxygen atom in the alkyl chain. That is, an oxyalkylene chain may be formed.
  • an oxyalkylene chain As the oxyalkylene chain, —CH 2 CH 2 O— is preferable.
  • tris (methoxyethoxyethyl) amine and compounds exemplified in the 60th and subsequent lines of column 3 of US6040112 can be mentioned.
  • Examples of the basic compound represented by the general formula (BS-1) having such a hydroxyl group or an oxygen atom include the following.
  • This nitrogen-containing heterocyclic ring may have aromaticity or may not have aromaticity. Moreover, you may have two or more nitrogen atoms. Furthermore, you may contain hetero atoms other than nitrogen. Specifically, for example, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure [N-hydroxyethylpiperidine and bis (1,2,2) , 6,6-pentamethyl-4-piperidyl) sebacate], compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).
  • Examples of compounds having a preferred nitrogen-containing heterocyclic structure include, for example, guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine and Aminoalkylmorpholine is mentioned. These may further have a substituent.
  • Preferred substituents include, for example, amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group And a cyano group.
  • Particularly preferable basic compounds include, for example, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2 -Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2- Amino-4-methylpyridine, 2-amino5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl ) Piperazine, N- (2-aminoe) L) Piperidine, 4-amino-2,2,6,6 tetra
  • a compound having two or more ring structures is also preferably used.
  • Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.
  • An amine compound having a phenoxy group is a compound having a phenoxy group at the terminal opposite to the N atom of the alkyl group contained in the amine compound.
  • the phenoxy group is, for example, a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxy group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. You may have.
  • This compound more preferably has at least one oxyalkylene chain between the phenoxy group and the nitrogen atom.
  • the number of oxyalkylene chains in one molecule is preferably 3 to 9, and more preferably 4 to 6.
  • —CH 2 CH 2 O— is particularly preferable.
  • the amine compound having a phenoxy group is prepared by reacting, for example, a primary or secondary amine having a phenoxy group with a haloalkyl ether, and adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. And then extracted with an organic solvent such as ethyl acetate and chloroform.
  • the amine compound having a phenoxy group reacts by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the terminal, and a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can also be obtained by adding an aqueous solution and then extracting with an organic solvent such as ethyl acetate and chloroform.
  • ammonium salt As the basic compound, an ammonium salt can also be used as appropriate.
  • the cation of the ammonium salt is preferably a tetraalkylammonium cation substituted with an alkyl group having 1 to 18 carbon atoms, such as tetramethylammonium cation, tetraethylammonium cation, tetra (n-butyl) ammonium cation, tetra (n-heptyl) ammonium.
  • a cation, a tetra (n-octyl) ammonium cation, a dimethylhexadecylammonium cation, a benzyltrimethyl cation, and the like are more preferable, and a tetra (n-butyl) ammonium cation is most preferable.
  • the anion of the ammonium salt include hydroxide, carboxylate, halide, sulfonate, borate, and phosphate. Of these, hydroxide or carboxylate is particularly preferred.
  • halide chloride, bromide and iodide are particularly preferable.
  • sulfonate an organic sulfonate having 1 to 20 carbon atoms is particularly preferable.
  • examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.
  • the alkyl group contained in the alkyl sulfonate may have a substituent.
  • substituents include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group.
  • alkyl sulfonate examples include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.
  • aryl group contained in the aryl sulfonate examples include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have a substituent.
  • this substituent for example, a linear or branched alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms are preferable. Specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl groups are preferred.
  • the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.
  • the carboxylate may be an aliphatic carboxylate or an aromatic carboxylate, and examples thereof include acetate, lactate, birubate, trifluoroacetate, adamantane carboxylate, hydroxyadamantane carboxylate, benzoate, naphthoate, salicylate, phthalate, phenolate and the like.
  • benzoate, naphthoate, phenolate and the like are preferable, and benzoate is most preferable.
  • tetra (n-butyl) ammonium benzoate, tetra (n-butyl) ammonium phenolate and the like are preferable as the ammonium salt.
  • this ammonium salt is a tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide, etc.). It is particularly preferred that
  • a compound having a proton acceptor functional group and generating a compound which is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor property or change from proton acceptor property to acidity PA
  • the actinic ray-sensitive or radiation-sensitive resin composition has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation to decrease, disappear, or It may further contain a compound that generates a compound that has been changed from proton acceptor property to acidity (hereinafter also referred to as compound (PA)).
  • PA proton acceptor functional group having a proton acceptor functional group and decomposing upon irradiation with actinic rays or radiation to generate a compound whose proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity
  • a compound (PA) having a proton acceptor functional group and decomposing upon irradiation with actinic rays or radiation to generate a compound whose proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity can be referred to the descriptions in paragraphs [0379] to [0425] of JP 2012-32762 A (corresponding to [0386] to [0435] of the corresponding US Patent Application Publication No. 2012/0003590). Is incorporated herein.
  • composition of the present invention may further contain a guanidine compound having a structure represented by the following formula.
  • the guanidine compound exhibits strong basicity because the positive charge of the conjugate acid is dispersed and stabilized by three nitrogens.
  • the basicity of the guanidine compound (A) of the present invention is preferably such that the pKa of the conjugate acid is 6.0 or more, and 7.0 to 20.0 is high in neutralization reactivity with the acid, It is preferable because of excellent roughness characteristics, and more preferably 8.0 to 16.0.
  • pKa means pKa in an aqueous solution, and is described in, for example, Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value, the higher the acid strength. Specifically, pKa in an aqueous solution can be actually measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the software package 1 below, A value based on a database of constants and known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.
  • log P is a logarithmic value of n-octanol / water partition coefficient (P), and is an effective parameter that can characterize the hydrophilicity / hydrophobicity of a wide range of compounds.
  • P n-octanol / water partition coefficient
  • the distribution coefficient is obtained by calculation without experimentation.
  • CSChemDrawUltraVer The value calculated by 8.0 software package (Crippen's fragmentation method) is shown.
  • logP of the guanidine compound (A) is 10 or less. By being below the above value, it can be contained uniformly in the resist film.
  • the log P of the guanidine compound (A) is preferably in the range of 2 to 10, more preferably in the range of 3 to 8, and still more preferably in the range of 4 to 8.
  • the guanidine compound (A) in the present invention preferably has no nitrogen atom other than the guanidine structure.
  • a low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid The actinic ray-sensitive or radiation-sensitive resin composition has a group having a nitrogen atom and leaving by the action of an acid.
  • a low molecular compound hereinafter, also referred to as “low molecular compound (D)” or “compound (D)”.
  • the low molecular compound (D) preferably has basicity after the group capable of leaving by the action of an acid is eliminated.
  • the description in paragraphs [0324] to [0337] of JP2012-133331A can be referred to, and the contents thereof are incorporated in the present specification.
  • the low molecular compound (D) can be used singly or in combination of two or more.
  • examples of compounds that can be used in the composition according to the present invention include compounds synthesized in Examples of JP-A No. 2002-363146, compounds described in Paragraph 0108 of JP-A No. 2007-298569, and the like. It is done.
  • a photosensitive basic compound may be used as the basic compound.
  • the photosensitive basic compound include JP-T-2003-524799 and J. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995) and the like can be used.
  • the molecular weight of the basic compound is usually 100 to 1500, preferably 150 to 1300, and more preferably 200 to 1000.
  • These basic compounds (D) may be used alone or in combination of two or more.
  • the content of the basic compound (D) contained in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.01 to 8.0% by mass based on the total solid content of the composition.
  • the content is more preferably 0.1 to 5.0% by mass, and particularly preferably 0.2 to 4.0% by mass.
  • the molar ratio of the basic compound (D) to the acid generator is preferably 0.01 to 10, more preferably 0.05 to 5, and still more preferably 0.1 to 3. If this molar ratio is excessively increased, sensitivity and / or resolution may be reduced. If this molar ratio is excessively small, there is a possibility that pattern thinning occurs between exposure and heating (post-bake). More preferably, it is 0.05-5, and still more preferably 0.1-3.
  • the acid generator in the molar ratio is the total of the repeating unit represented by the general formula (5) of the resin (A) and the acid generator that the resin (A) may further contain. It is based on quantity.
  • the actinic ray-sensitive or radiation-sensitive resin composition further contains one or more compounds that decompose by the action of an acid to generate an acid. You may go out.
  • the acid generated from the compound that decomposes by the action of the acid to generate an acid is preferably a sulfonic acid, a methide acid, or an imido acid.
  • Examples of compounds that can be decomposed by the action of an acid that can be used in the present invention to generate an acid are shown below, but are not limited thereto.
  • produces an acid can be used individually by 1 type or in combination of 2 or more types.
  • the content of the compound that generates an acid by being decomposed by the action of an acid is 0.1 to 40% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition.
  • the content is 0.5 to 30% by mass, and more preferably 1.0 to 20% by mass.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may have a hydrophobic resin (HR) separately from the resin (A). Since the hydrophobic resin (HR) is unevenly distributed on the film surface, the hydrophobic resin (HR) preferably contains a group having a fluorine atom, a group having a silicon atom, or a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain. Specific examples of the hydrophobic resin (HR) are shown below.
  • hydrophobic resin those described in JP 2011-248019 A, JP 2010-175859 A, and JP 2012-032544 A can also be preferably used.
  • the actinic ray-sensitive or radiation-sensitive resin composition may further contain a surfactant.
  • a surfactant when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, it is possible to form a pattern with less adhesion and development defects with good sensitivity and resolution. Become.
  • As the surfactant it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.
  • fluorine-based and / or silicon-based surfactant examples include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425.
  • F top EF301 or EF303 manufactured by Shin-Akita Kasei Co., Ltd.
  • Florard FC430, 431 or 4430 manufactured by Sumitomo 3M Co., Ltd.
  • Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.
  • the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). You may synthesize. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.
  • the polymer having a fluoroaliphatic group is preferably a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate or methacrylate and / or (poly (oxyalkylene)) methacrylate. Even if it distributes, block copolymerization may be sufficient.
  • the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, and a poly (oxybutylene) group.
  • units having different chain length alkylene in the same chain such as poly (block connection body of oxyethylene, oxypropylene, and oxyethylene) and poly (block connection body of oxyethylene and oxypropylene) Also good.
  • a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate or methacrylate is composed of a monomer having two or more different fluoroaliphatic groups and two or more different (poly (oxyalkylene). )) It may be a ternary or higher copolymer obtained by copolymerizing acrylate or methacrylate simultaneously.
  • Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by DIC Corporation).
  • surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 may be used.
  • One of these surfactants may be used alone, or two or more thereof may be used in combination.
  • the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, the content thereof is preferably 0 to 2% by mass, more preferably 0.0001, based on the total solid content of the composition. It is ⁇ 2 mass%, more preferably 0.0005 to 1 mass%.
  • the actinic ray-sensitive or radiation-sensitive resin composition is described in carboxylic acid, carboxylic acid onium salt, Proceeding of SPIE, 2724, 355 (1996) and the like. These may contain a dissolution inhibiting compound having a molecular weight of 3000 or less, a dye, a plasticizer, a photosensitizer, a light absorber, an antioxidant, and the like.
  • carboxylic acid is preferably used for improving the performance.
  • aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferable.
  • the content of the carboxylic acid is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, still more preferably 0, based on the total solid concentration of the actinic ray-sensitive or radiation-sensitive resin composition. 0.01 to 3% by mass.
  • the actinic ray-sensitive or radiation-sensitive resin composition is preferably used in a film thickness of 10 to 250 nm, more preferably in a film thickness of 20 to 200 nm, from the viewpoint of improving resolution. It is preferable to use at 30 to 100 nm.
  • a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
  • the solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, more preferably 2.0. Is 5.3 mass%.
  • the resist solution can be uniformly applied on the substrate, and further, a guide pattern having excellent line width roughness can be formed.
  • the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, so that the material in the actinic ray-sensitive or radiation-sensitive resin composition solution, in particular, It is considered that agglomeration of the photoacid generator was suppressed, and as a result, a uniform actinic ray-sensitive or radiation-sensitive film could be formed.
  • the solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the actinic ray-sensitive or radiation-sensitive resin composition.
  • the actinic ray-sensitive or radiation-sensitive resin composition is used by dissolving the above-described components in a predetermined organic solvent, preferably the mixed solvent, filtering the solution, and applying the solution on a predetermined support (substrate).
  • the pore size of the filter used for filter filtration is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and still more preferably 0.03 ⁇ m or less made of polytetrafluoroethylene, polyethylene, or nylon.
  • filter filtration for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel.
  • the composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.
  • Resins (BP-5) and (BP-6) as well as resins (CBP-1) and (CBP-2) were synthesized in the same manner as in Synthesis Example 1.
  • the synthesis examples described above are all synthesis examples in which the block of the first repeating unit and the block of the second repeating unit are formed by living polymerization.
  • These block copolymers contained 1 to 1000 ppm of metal ions, but the amount of metal ions was reduced to 1 to 50 ppb or less by using a known filtration method.
  • the metal was quantified by diluting the sample 10 times with MEK and using an ICP-OES apparatus (Perkin Elmer Optima 7300 DV, organic solvent mode) by the absolute calibration method.
  • Resins (P-2) to (P-10) and Resins (P-12) to (P-42) were synthesized.
  • the polymer structures, weight average molecular weights (Mw), and dispersities (Mw / Mn) of resins (P-1) to (P-42) are shown below.
  • the composition ratio of each repeating unit of the following polymer structure was shown by molar ratio.
  • the acid generator was appropriately selected from the acid generators z1 to z141 listed above.
  • W-1 Megafuck R08 (manufactured by DIC Corporation; fluorine and silicon-based)
  • W-2 Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
  • W-3 Troisol S-366 (manufactured by Troy Chemical Co., Ltd .; fluorine-based)
  • W-4 PF6320 (manufactured by OMNOVA; fluorine-based)
  • Coating solvent As the coating solvent, the following were used. S1: Propylene glycol monomethyl ether acetate (PGMEA) S2: Propylene glycol monomethyl ether (PGME) S3: Ethyl lactate S4: Cyclohexanone
  • SR-1 2-pentanol
  • SR-2 1-hexanol
  • SR-3 methyl isobutyl carbinol
  • Example 2-1 to 2-6 the entire substrate on which the block copolymer layer was formed was subjected to the polarity change of the functional group of the first repeating unit and the phase separation in the block copolymer layer.
  • heating was performed at 200 ° C. for 5 minutes as an external stimulus in order to perform phase separation in the block copolymer layer.
  • Example 2-7 in order to change the polarity of the functional group of the first repeating unit, the entire surface as an external stimulus was applied to the surface of the block copolymer layer using the EUV exposure apparatus. Exposure (light irradiation) was performed, and heating at 200 ° C.
  • the substrate was subjected to oxygen plasma treatment (200 sccm, 40 Pa, 200 W, 30 seconds), and (meth) acrylic acid repeating units or (meta ) A phase consisting of a block of repeating units corresponding to an acrylate repeating unit was selectively removed.
  • ⁇ SP value represents the absolute value of the difference between the solubility parameter (SP value) of the first repeating unit and the solubility parameter (SP value) of the second repeating unit.
  • the “St ratio” represents the content (% by mass) of the block of the styrenic repeating unit with respect to the total amount of the block of the styrenic repeating unit and the block of the (meth) acrylate repeating unit.
  • A A 5% by weight toluene solution of a block copolymer can be prepared without any undissolved residue of the block copolymer.
  • B A 3% by weight toluene solution of a block copolymer that does not satisfy the criterion of determination A but has no undissolved residue of the block copolymer can be prepared.
  • C A 1% by weight toluene solution of a block copolymer that does not satisfy the criterion of the judgment B but has no undissolved block copolymer can be prepared.
  • D The criterion of determination C is not satisfied.
  • the coating liquid compositions (solid content concentration: 1.5% by mass) having the composition of Example 1-3 used for forming the guide patterns in Examples 2-1 to 2-7 are shown in Table 2 above.
  • the same operations as in Examples 2-1 to 2-7 were performed except that the coating liquid compositions having the compositions of 1-1, 1-2, and 1-4 to 1-20 were used. Evaluation results similar to those of 2-1 to 2-7 were obtained.
  • the coating liquid compositions having the composition of Example 1-3 used for the formation of the guide patterns in Examples 2-1 to 2-7 are the coating compositions having the compositions of Examples 3-1 to 3-36 shown in Table 4.
  • Liquid composition solid content concentration: 1.5% by mass
  • TMAH alkaline aqueous solution
  • development was performed with the developer (organic developer) described in Table 4, and instead of water, the developer was listed in Table 4.
  • a toluene solution (solid content concentration of 1.9% by mass) of the components described in Table 3 was changed to a 1.9% by mass propylene glycol monomethyl ether acetate (PGMEA) solution of the components described in Table 3. (Solid content 1.9 quality %) Except that the preparation of the actinic ray-sensitive or radiation-sensitive resin composition, the formation of the guide pattern, the formation of the block copolymer layer, and the like. Phase separation was performed. In Table 4, in the examples not described in the column of the rinsing liquid, rinsing is not performed. As a result, the same evaluation results as in Examples 2-1 to 2-7 were obtained.
  • the solubility of a block copolymer for forming a self-assembled resist film in a solvent is excellent, so that the coating property of the composition solution containing the block copolymer is excellent and the pattern has a high pattern.
  • Pattern formation method capable of achieving high quality for example, a line and space pattern with a pitch of 40 nm or less or a hole pattern with a hole diameter of 20 nm or less can be formed with high quality
  • a pattern using the pattern formation method A film, a method for manufacturing an electronic device and an electronic device, and a block copolymer and a patterning material used in the pattern forming method can be provided.

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Abstract

La présente invention concerne un procédé de formation de motifs qui comprend, dans l'ordre suivant, (i) une étape consistant à former une couche (31) d'un copolymère séquencé sur un substrat (10) par application d'une composition qui contient un copolymère séquencé comprenant une séquence d'un premier motif répété et une séquence d'un second motif répété, (ii) une étape consistant à appliquer sur la couche (31) de copolymère séquencé au moins un stimulus externe qui est choisi dans le groupe constitué par un chauffage et une exposition à de la lumière active ou à un rayonnement, (iii) une étape consistant à soumettre la couche (31) de copolymère séquencé à une séparation de phases, et (iv) une étape consistant à retirer sélectivement au moins une phase (32) parmi la pluralité de phases de la couche (31) de copolymère séquencé. Le premier motif répété comprend un groupe fonctionnel dont la polarité change lors de l'application du stimulus externe, tandis que le second motif répété ne comprend pas de groupe fonctionnel dont la polarité change lors de l'application du stimulus externe.
PCT/JP2015/074110 2014-09-17 2015-08-26 Procédé de formation de motifs, film à motifs, procédé de fabrication de dispositif électronique, dispositif électronique, copolymère séquencé et matériau de formation de motifs WO2016043004A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108231984A (zh) * 2018-01-31 2018-06-29 华南理工大学 一种相分离手段实现的钙钛矿图案化膜片及其制作方法
WO2020022089A1 (fr) * 2018-07-25 2020-01-30 富士フイルム株式会社 Composition de résine sensible à la lumière active ou au rayonnement, film sensible à la lumière active ou au rayonnement, procédé de formation de motif, et procédé de production de dispositif électronique

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
WO2019172156A1 (fr) * 2018-03-07 2019-09-12 富士フイルム株式会社 Composition de formation de film de sous-couche pour impression, composition durcissable pour impression, et kit

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002287377A (ja) * 2001-03-23 2002-10-03 Toshiba Corp ナノパターン形成方法、ナノパターン形成材料および電子部品の製造方法
JP2010125782A (ja) * 2008-11-28 2010-06-10 Fujifilm Corp インプリント材料及びインプリント方法
JP2014160204A (ja) * 2013-02-20 2014-09-04 Tokyo Ohka Kogyo Co Ltd 下地剤、パターン形成方法
JP2014162054A (ja) * 2013-02-22 2014-09-08 Tokyo Ohka Kogyo Co Ltd 相分離構造を含む構造体の製造方法、及びパターン形成方法、並びにトップコート材料
JP2015180931A (ja) * 2014-03-05 2015-10-15 Jsr株式会社 パターン形成用組成物及びパターン形成方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002287377A (ja) * 2001-03-23 2002-10-03 Toshiba Corp ナノパターン形成方法、ナノパターン形成材料および電子部品の製造方法
JP2010125782A (ja) * 2008-11-28 2010-06-10 Fujifilm Corp インプリント材料及びインプリント方法
JP2014160204A (ja) * 2013-02-20 2014-09-04 Tokyo Ohka Kogyo Co Ltd 下地剤、パターン形成方法
JP2014162054A (ja) * 2013-02-22 2014-09-08 Tokyo Ohka Kogyo Co Ltd 相分離構造を含む構造体の製造方法、及びパターン形成方法、並びにトップコート材料
JP2015180931A (ja) * 2014-03-05 2015-10-15 Jsr株式会社 パターン形成用組成物及びパターン形成方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108231984A (zh) * 2018-01-31 2018-06-29 华南理工大学 一种相分离手段实现的钙钛矿图案化膜片及其制作方法
WO2020022089A1 (fr) * 2018-07-25 2020-01-30 富士フイルム株式会社 Composition de résine sensible à la lumière active ou au rayonnement, film sensible à la lumière active ou au rayonnement, procédé de formation de motif, et procédé de production de dispositif électronique
JPWO2020022089A1 (ja) * 2018-07-25 2021-08-02 富士フイルム株式会社 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、電子デバイスの製造方法

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