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WO2018180069A1 - Procédé de formation de motif et procédé de production de dispositif électronique - Google Patents

Procédé de formation de motif et procédé de production de dispositif électronique Download PDF

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Publication number
WO2018180069A1
WO2018180069A1 PCT/JP2018/006602 JP2018006602W WO2018180069A1 WO 2018180069 A1 WO2018180069 A1 WO 2018180069A1 JP 2018006602 W JP2018006602 W JP 2018006602W WO 2018180069 A1 WO2018180069 A1 WO 2018180069A1
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Prior art keywords
group
general formula
acid
atom
represented
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PCT/JP2018/006602
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English (en)
Japanese (ja)
Inventor
創 古谷
三千紘 白川
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富士フイルム株式会社
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Publication of WO2018180069A1 publication Critical patent/WO2018180069A1/fr

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    • 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
    • C08F30/00—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F30/08—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—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
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/36—Imagewise removal not covered by groups G03F7/30 - G03F7/34, e.g. using gas streams, using plasma

Definitions

  • the present invention relates to a pattern forming method and an electronic device manufacturing method.
  • Patent Document 1 discloses an actinic ray-sensitive or radiation-sensitive resin composition containing an acid-decomposable resin containing Si atoms.
  • Patent Document 2 discloses an actinic ray-sensitive or radiation-sensitive resin composition containing a maleimide resin.
  • the maleimide-based resin has a structure in which an amino group is protected by a leaving group containing Si atoms, and the leaving group is released by the action of an acid generated from a photoacid generator during exposure.
  • the present inventors use the actinic ray-sensitive or radiation-sensitive resin composition described in Patent Documents 1 and 2 and a pattern formed by the pattern forming method as a mask, and an object to be etched (for example, an SOC film).
  • an object to be etched for example, an SOC film.
  • the pattern uniformity of the object to be etched is not always sufficient, and it is clear that there is room for further improvement.
  • the present inventors made further investigations and found that the inferior pattern uniformity of the object to be etched is due to the pattern used as a mask during etching.
  • this invention makes it a subject to provide the pattern formation method which forms the pattern which can give the to-be-etched object which has the outstanding pattern uniformity. Moreover, this invention makes it a subject to provide the manufacturing method of an electronic device containing the said pattern formation method.
  • the present inventors have found that the above problems can be solved by a pattern forming method using a resin having a specific structure, and have completed the present invention. That is, it has been found that the above object can be achieved by the following configuration.
  • a resist film forming step of forming a resist film using a chemically amplified actinic ray-sensitive or radiation-sensitive resin composition comprising:
  • the chemically amplified actinic ray-sensitive or radiation-sensitive resin composition is A resin having a group that is decomposed by the action of an acid to increase polarity;
  • a photoacid generator The group that is decomposed by the action of an acid and increases in polarity has a structure in which the polar group is protected by a leaving group that is eliminated by the action of an acid.
  • the pattern forming method wherein the leaving group contains Si atoms, and the molecular weight of the leaving group is 500 or less.
  • the group which is decomposed by the action of the acid and increases in polarity has a structure represented by the general formula (a) described later, or a structure represented by the general formula (b) described later.
  • the pattern according to [1] or [2], wherein the resin has a repeating unit represented by the following general formula (1A) or a repeating unit represented by the following general formula (2A). Forming method.
  • X 1 is an organic group represented by general formula (1A-2) described later.
  • the pattern formation method which forms the pattern which can give the to-be-etched object which has the outstanding pattern uniformity can be provided.
  • the manufacturing method of an electronic device containing the said pattern formation method can be provided.
  • active light or “radiation” refers to, for example, an emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light: Extreme Ultraviolet), X-ray, and electron beam (EB). : Electron Beam) or the like.
  • light means actinic rays or radiation.
  • exposure in the present specification includes not only exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, EUV light, etc., but also electron beams, and This includes drawing with particle beams such as ion beams.
  • to is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • (meth) acrylate represents acrylate and methacrylate.
  • the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by Tosoh Corporation) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ L, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: differential refractive index It is defined as a polystyrene-converted value by a detector (Refractive Index Detector).
  • the notation that does not indicate substitution or unsubstituted includes a group having a substituent together with a group not having 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).
  • the “organic group” refers to a group containing at least one carbon atom.
  • the type of substituent, the position of the substituent, and the number of substituents when “may have a substituent” are not particularly limited.
  • the number of substituents may be, for example, 1, 2, 3, or more.
  • the substituent include a monovalent nonmetallic atomic group excluding a hydrogen atom.
  • the substituent can be selected from the following substituent group T.
  • substituent T examples include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group An alkyl sulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; an arylsulfanyl group such as a phenylsulf
  • the pattern forming method of the present invention includes a resist film forming step of forming a resist film using a chemically amplified actinic ray-sensitive or radiation-sensitive resin composition, an exposure step of exposing the resist film, and an exposure step.
  • the chemically amplified actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method is a resin having a group that is decomposed by the action of an acid to increase polarity (hereinafter referred to as “acid-decomposable resin”). Or a “resin (A)”) and a photoacid generator, and a group that is decomposed by the action of the acid to increase its polarity (hereinafter also referred to as “acid-decomposable group”).
  • the polar group is protected by a leaving group that decomposes and leaves by the action of an acid.
  • the leaving group contains Si atoms and has a molecular weight of 500 or less.
  • the “chemically amplified actinic ray-sensitive or radiation-sensitive resin composition” means a resin composition in which a chemical reaction in a system initiated by exposure is chained catalytically.
  • the acid generated from the photoacid generator upon exposure causes a deprotection reaction of the acid-decomposable group (that is, a reaction in which the leaving group is eliminated by the action of the acid), and the polar group of the resin and the acid In which this chemical reaction proceeds in a chained manner.
  • the actinic ray-sensitive or radiation-sensitive resin composition described in Patent Document 2 is a so-called chemically amplified actinic ray-sensitive resin composition because the amino group of the maleimide resin formed after exposure deactivates the acid. It does not correspond to a radiation sensitive resin composition.
  • the development step is carried out by dry development instead of conventional liquid development.
  • the pattern uniformity of the object to be etched is excellent.
  • the leaving group for protecting the polar group contains Si atoms, the molecular weight is 500 or less, and the post-exposure heating. The point which implements a process is mentioned.
  • an acid-decomposable group in the acid-decomposable resin is deprotected by an acid generated from the photoacid generator upon irradiation with actinic rays or radiation. That is, a reaction occurs in which the leaving group in the acid-decomposable group is eliminated by the action of an acid in the exposed portion of the resist film.
  • image development is implemented by dry image development (for example, oxygen plasma etching). This dry development may also serve to etch the object to be etched as shown in the example column.
  • the dry development process after exposure of the resist film formed on the object to be etched and the etching of the object to be etched may be performed as the same process.
  • the etching when the leaving group containing Si atoms remains in the resist film after the exposure, the difference in the content of Si atoms between the exposed portion and the unexposed portion is reduced. It has been found that the pattern uniformity of the object to be etched is inferior.
  • the polar group in the acid-decomposable resin, the polar group is protected with a leaving group containing a Si atom and having a molecular weight of 500 or less, and a post-exposure heating step is performed. It is solved by.
  • the leaving group is easily volatilized in the post-exposure heating step, and this configuration can increase the difference in Si atom content between the exposed and unexposed areas during dry development. That is, the unexposed portion has high etching resistance, and the exposed portion has low etching resistance. As a result, the pattern uniformity of the object to be etched is excellent.
  • the acid-decomposable resin has a repeating unit represented by the general formula (1A) (preferably, X 1 in the general formula (1A) is represented by the general formula (1A-2).
  • a group having a repeating unit represented by the general formula (2A) preferably, X 2 in the general formula (2A) is a group represented by the general formula (2A-2)
  • the leaving group is more likely to volatilize in the post-exposure heating process, resulting in a greater difference in Si atom content between the exposed and unexposed areas, and the pattern uniformity of the etched object. Better.
  • the pattern forming method of the present invention comprises: (I) a step of forming a resist film (actinic ray sensitive or radiation sensitive film) using a chemically amplified actinic ray sensitive or radiation sensitive resin composition described later (resist film forming step); (Ii) a step of exposing the resist film (irradiating actinic rays or radiation) (exposure step); (Iii) A step of heating the exposed resist film (post-exposure heating (PEB: Post (Exposure Bake) step), and (Iv) Development process for dry development of the heated resist film (dry development process)
  • PEB Post (Exposure Bake
  • the pattern forming method of the present invention is not particularly limited as long as it includes the above steps (i) to (iv), and may further include the following steps.
  • the exposure method in the exposure step may be immersion exposure.
  • the pattern forming method of the present invention preferably includes (ii) a preheating (PB) step before the exposure step.
  • the pattern forming method of the present invention may include (ii) an exposure step a plurality of times.
  • the pattern forming method of the present invention may include (v) a preheating step a plurality of times.
  • the pattern forming method of the present invention may include (iii) a post-exposure heating step a plurality of times.
  • the above-mentioned (i) resist film forming step, (ii) exposure step, (iii) post-exposure heating step, and (iv) dry development step are performed by generally known methods. It can be carried out.
  • a protective film (top coat) may be formed on the upper layer of the resist film.
  • the protective film a known material can be appropriately used. For example, U.S. Patent Application Publication No. 2007/0178407, U.S. Patent Application Publication No. 2008/0085466, U.S. Patent Application Publication No. 2007/0275326, U.S. Patent Application Publication No. 2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No.
  • composition for forming a protective film a composition containing an acid diffusion controller described later is preferable. Moreover, you may form a protective film in the upper layer of the resist film containing the hydrophobic resin mentioned later.
  • the resist film is preferably formed on a support.
  • the support is not particularly limited, and for example, an inorganic substrate such as silicon, SiN, SiO 2 , or SiN, or a coating inorganic substrate such as SOG (Spin on Glass) can be used.
  • the support may be a substrate having an inorganic substrate (for example, a SiO 2 substrate) and a lower layer film such as SOC (Spin on Carbon) formed on the inorganic substrate.
  • a substrate generally used in other photofabrication lithography processes can also be used as the support.
  • the heating temperature is preferably 70 to 130 ° C., more preferably 80 to 130 ° C. in both (v) the preheating step and (iii) the post-exposure heating step.
  • the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds in both (v) the preheating step and (iii) the post-exposure heating step.
  • the heating can be performed by means provided in the exposure apparatus and the developing apparatus, and may be performed using a hot plate or the like.
  • the light source wavelength used for an exposure process For example, infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-ray
  • far ultraviolet light is preferable, and the wavelength is preferably 250 nm or less, more preferably 220 nm or less, and further preferably 1 to 200 nm.
  • a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F 2 excimer laser (157 nm), an X-ray, an EUV (13 nm), an electron beam, etc.
  • a KrF excimer laser, an ArF excimer laser, EUV or electron beam is preferred.
  • the method of the dry developing device is not particularly limited, but ICP (Inductive Coupled Plasma) type, dual frequency CCP (Conductive Coupled Plasma capacitive coupling) type, and ECR (Electron cyclotron resonance) type; A method in which the plasma density and the bias voltage can be independently controlled is preferable. Any known method can be used for dry development, and various conditions are appropriately determined according to the type and use of the substrate. For example, Bulletin of International Society of Optical Engineering (Proc. Of SPIE) Vol. Etching can be performed in accordance with 6924, 692420 (2008) and Japanese Patent Application Laid-Open No. 2009-267112. Further, the method described in “Chapter 4 Etching” of “Semiconductor Process Textbook 4th Edition, 2007, Publisher: SEMI Japan” can be used.
  • dry development is preferably oxygen plasma etching.
  • the oxygen plasma etching here means plasma etching using a gas containing oxygen atoms (hereinafter also referred to as “oxygen-containing gas”).
  • oxygen-containing gas include O 2 , O 3 , CO, CO 2 , NO, NO 2 , N 2 O, SO, SO 2 , and COS.
  • the oxygen-containing gas may contain a gas such as Ar, He, Xe, Kr, and N 2 as a dilution gas.
  • the oxygen-containing gas may contain a gas such as Cl 2 , HBr, BCl 3 , CH 4 , and NH 4 as an additive gas.
  • Various materials used in the pattern forming method of the present invention have impurities such as metal components, isomers, and residual monomers. It is preferably not included.
  • the content of these impurities contained in the above various materials is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and substantially not (less than the detection limit of the measuring device). Is particularly preferred.
  • Examples of a method for removing impurities such as metals from the various materials include filtration using a filter.
  • the pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
  • a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.
  • a filter that has been washed in advance with an organic solvent may be used.
  • a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination.
  • various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
  • a filter with reduced effluent as disclosed in JP-A-2016-201426 is preferable.
  • impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used.
  • adsorbent a known adsorbent can be used.
  • an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.
  • the metal adsorbent include those disclosed in JP-A-2016-206500.
  • a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials.
  • a method of performing distillation under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark) or the like can be mentioned.
  • Teflon registered trademark
  • the preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
  • a method for improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention.
  • a method for improving the surface roughness of the pattern for example, a method of processing a pattern by a plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/0104957 is cited.
  • JP 2004-235468 A, US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” may be applied.
  • the pattern formed by the above method can be used as a core material (Core) of a spacer process disclosed in, for example, JP-A-3-270227 and US Patent Application Publication No. 2013/0209941.
  • the chemical amplification type actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also simply referred to as “the composition of the present invention”) that can be used in the pattern forming method of the present invention will be described below.
  • the composition of the present invention has a resin (hereinafter referred to as “acid-decomposable resin” or “resin (A)”) having a group (hereinafter referred to as “acid-decomposable group”) that is decomposed by the action of an acid to increase polarity. Containing).
  • Resin (A) is a resin having a structure in which a polar group contains a Si atom and has a molecular weight of 500 or less and is protected by a group (leaving group) that is decomposed and eliminated by the action of an acid.
  • the molecular weight of the leaving group is preferably 400 or less, more preferably 300 or less, and even more preferably 110 or less, from the viewpoint of superior volatility in the post-exposure heating step. Since the leaving group is excellent in volatility in the post-exposure heating step, the difference in Si atom content between the exposed portion and the unexposed portion can be increased during the dry development step.
  • the lower limit of the molecular weight of the leaving group is often 60 or more, for example.
  • Examples of polar groups include carboxy group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and alcoholic hydroxyl group.
  • the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group). Excludes aliphatic alcohols substituted with a functional group (for example, a hexafluoroisopropanol group).
  • the alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.
  • Preferred polar groups include carboxy group, phenolic hydroxyl group, fluorinated alcohol group (preferably hexafluoroisopropanol group), and sulfonic acid group.
  • the structure in which the polar group is protected by a leaving group that is eliminated by the action of an acid is intended to be a structure in which the hydrogen atom of these groups is substituted with the above-described leaving group.
  • P s1 and P s2 each independently represent a leaving group having a molecular weight of 500 or less, containing an Si atom that is eliminated by the action of an acid. . * Represents a bonding position linked to the main chain or side chain of the resin.
  • the resin (A) has a repeating unit (hereinafter also referred to as “repeating unit (P)”) having a structure containing a Si atom and having a polar group protected by a leaving group having a molecular weight of 500 or less.
  • it preferably has a repeating unit having the structure represented by the general formula (a) or a repeating unit having the structure represented by the general formula (b), and is represented by the following general formula (1A).
  • a repeating unit represented by the following general formula (2A) is represented by the following general formula
  • R 1 represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 10 carbon atoms.
  • P s1 is a leaving group containing Si atoms and having a molecular weight of 500 or less, which is eliminated by the action of an acid, and is a group represented by the following general formula (1A-1).
  • * -L 1 -X 1 (1A-1) In general formula (1A-1), L 1 represents a divalent linking group.
  • X 1 represents an organic group containing a Si atom. * Represents a binding position.
  • R 2 represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 10 carbon atoms.
  • P s2 is a leaving group containing Si atoms and having a molecular weight of 500 or less, which is eliminated by the action of an acid, and is represented by the following general formula (2A-1).
  • * -L 2 -X 2 (2A-1) In general formula (2A-1), L 2 represents a single bond or a divalent linking group.
  • X 2 represents an organic group containing a Si atom. * Represents a binding position.
  • examples of the halogen atom represented by R 1 and R 2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group having 1 to 10 carbon atoms represented by R 1 and R 2 may be an alkyl group having 1 to 5 carbon atoms. And an alkyl group having 1 to 3 carbon atoms is more preferable.
  • R 1 and R 2 may have a substituent (for example, substituent group T).
  • the divalent linking group represented by L 1 and L 2 is not particularly limited, but for example, an alkylene group having 1 to 5 carbon atoms ( It may be any of linear, branched and cyclic.), More preferably an alkylene group having 1 to 3 carbon atoms, and still more preferably a methylene group.
  • L 1 and L 2 may have a substituent (for example, substituent group T).
  • X 1 and X 2 represent an organic group containing a Si atom.
  • the organic group containing a Si atom is not particularly limited as long as it contains a Si atom, and examples thereof include a group containing a group represented by the following general formula (S).
  • R S1 independently represents a monovalent organic group. * Represents a binding position.
  • R S1 each independently represents a monovalent organic group, and may be an alkyl group (which may be linear, branched or cyclic), an aryl group, An alkenyl group, an alkynyl group, or a silyl ether group is preferred.
  • the alkyl group represented by R S1 is preferably an alkyl group having 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a cyclopropyl group, Examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.
  • Examples of the aryl group represented by R S1 include a phenyl group.
  • the alkenyl group represented by R S1 is preferably an alkenyl group having 2 to 5 carbon atoms, and specific examples include a vinyl group, a propenyl group, and an allyl group.
  • the alkynyl group represented by R S1 is preferably an alkynyl group having 2 to 5 carbon atoms, and specific examples thereof include an ethynyl group, a propynyl group, and a butynyl group.
  • Examples of the silyl ether group represented by R S1 include a group represented by —O—Si (R S2 ) 3 (R S2 : a monovalent organic group).
  • R S2 is an alkyl group having 1 to 10 carbon atoms (which may be linear, branched or cyclic), an aryl group, an alkenyl group having 2 to 5 carbon atoms, or 2 to 2 carbon atoms. An alkynyl group of 5 is preferred.
  • R S1 and R S2 may have a substituent (for example, substituent group T).
  • X 1 is preferably an organic group represented by the following general formula (1A-2) from the viewpoint of excellent volatility in the post-exposure heating step. .
  • L 3 represents a single bond or a divalent linking group.
  • R 3 each independently represents a monovalent organic group. * Represents a binding position.
  • the divalent linking group represented by L 3 is not particularly limited, but may be any alkylene group having 1 to 10 carbon atoms (straight, branched, and cyclic). The alkylene group having 1 to 5 carbon atoms is more preferable, and the alkylene group having 1 to 3 carbon atoms is still more preferable. L 3 may have a substituent (for example, substituent group T).
  • R 3 has the same meaning as R S1 in the above general formula (S), and the preferred embodiment is also the same.
  • X 2 represents an organic group containing a Si atom, and in particular, it is represented by the following general formula (2A-2) in that it is more excellent in volatility in the post-exposure heating step. It is preferable that it is an organic group.
  • L 4 represents a single bond or an oxygen atom.
  • L 5 represents a single bond or a divalent linking group.
  • R 4 each independently represents a monovalent organic group. * Represents a binding position.
  • L 5 and R 4 have the same meanings as L 3 and R 3 in the general formula (1A-2), respectively, and preferred embodiments thereof are also the same.
  • Ra represents a hydrogen atom or an alkyl group.
  • the content of Si atoms is preferably 5.0% by mass or more with respect to the total mass of the repeating unit in that it is more excellent in etching resistance in the unexposed area during the dry development step. 0 mass% or more is more preferable, and 20.0 mass% or more is still more preferable.
  • the upper limit is not particularly limited, but is often 40.0% by mass or less.
  • the content of the repeating unit (P) contained in the resin (A) (the total when there are a plurality of repeating units (P)) is excellent in the etching resistance in the unexposed area during the dry development process. 50 mol% or more is preferable with respect to all repeating units of (A), 70 mol% or more is more preferable, and 90 mol% or more is still more preferable.
  • Resin (A) may further have a repeating unit having an acid-decomposable group other than the repeating unit (P) (hereinafter also referred to as “repeating unit (Q)”).
  • the repeating unit (Q) is, for example, a group obtained by substituting a hydrogen atom of the above-described polar group (carboxy group or the like) with a group (leaving group) that is eliminated by the action of an acid.
  • groups of the group (leaving group) leaving by the action of an acid include —C (R 36 ) (R 37 ) (R 38 ), —C (R 36 ) (R 37 ) (OR 39 ), and — C (R 01 ) (R 02 ) (OR 39 ) and the like can be mentioned.
  • R 36 to R 39 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group 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 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • the alkyl group of R 36 to R 39 , R 01 and R 02 is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl Group, and octyl group.
  • the cycloalkyl group of R 36 to R 39 , R 01 and R 02 may be monocyclic or polycyclic.
  • the monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • a cycloalkyl group having 6 to 20 carbon atoms is preferable.
  • an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an ⁇ -pinel group, a tricyclodecanyl group, A tetracyclododecyl group, an androstanyl group, etc. are mentioned.
  • at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
  • the aryl group of R 36 to R 39 , R 01 and R 02 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
  • the aralkyl group of R 36 to R 39 , R 01 and R 02 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 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 is preferably a cycloalkyl group (monocyclic or polycyclic).
  • cycloalkyl group a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferable. .
  • a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group is preferable, and an acetal group or a tertiary alkyl ester group is more preferable.
  • the resin (A) preferably has a repeating unit represented by the following general formula (AI) as the repeating unit (Q).
  • Xa 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • T represents a single bond or a divalent linking group.
  • Rx 1 to Rx 3 each independently represents an alkyl group or a cycloalkyl group. Any two of Rx 1 to Rx 3 may be bonded to form a ring structure, or may not be formed.
  • Examples of the divalent linking group for T include an alkylene group, an arylene group, —COO—Rt—, —O—Rt—, and the like.
  • Rt represents an alkylene group, a cycloalkylene group, or an arylene group.
  • T is preferably a single bond or —COO—Rt—.
  • Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, more preferably —CH 2 —, — (CH 2 ) 2 —, or — (CH 2 ) 3 —. More preferably, T is a single bond.
  • Xa 1 is preferably a hydrogen atom or an alkyl group.
  • the alkyl group of Xa 1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
  • the alkyl group of Xa 1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group.
  • the alkyl group of Xa 1 is preferably a methyl group.
  • the alkyl group of Rx 1 , Rx 2 and Rx 3 may be linear or branched, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, An isobutyl group or a t-butyl group is preferred.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
  • a part of the carbon-carbon bond may be a double bond.
  • cycloalkyl group of Rx 1 , Rx 2 and Rx 3 a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, and the like
  • the polycyclic cycloalkyl group is preferable.
  • the ring structure formed by combining two of Rx 1 , Rx 2 and Rx 3 includes a monocyclic cycloalkane ring such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, and cyclooctane ring, or norbornane ring, tetracyclo ring
  • a polycyclic cycloalkyl ring such as a decane ring, a tetracyclododecane ring and an adamantane ring is preferred.
  • a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferable.
  • the ring structure formed by combining two of Rx 1 , Rx 2 and Rx 3 the structures shown below are also preferable.
  • the resin (A) preferably has a repeating unit described in paragraphs ⁇ 0336> to ⁇ 0369> of US Patent Application Publication No. 2016 / 0070167A1 as the repeating unit (Q).
  • the resin (A) is decomposed by the action of an acid described in paragraphs ⁇ 0363> to ⁇ 0364> of US Patent Application Publication No. 2016 / 0070167A1 as a repeating unit (Q) to produce an alcoholic hydroxyl group. You may have a repeating unit containing group.
  • Resin (A) may contain the repeating unit (Q) alone or in combination of two or more.
  • the repeating unit (Q) has a low Onishi parameter in that the contrast between the exposed part and the unexposed part is excellent, and the pattern uniformity of the etched object is excellent. It preferably has an acid-decomposable group.
  • the Onishi parameter is the dry etching resistance expressed as N / (N C —N O ), where N is the total number of atoms in the acid-decomposable group, N C is the total number of carbons, and N O is the total number of oxygen. This is an index parameter. Generally, it is known that the smaller the Onishi parameter, the better the dry etching resistance.
  • the Onishi parameter of the acid-decomposable group is often 6.0 or less, and 4.0 or less is preferable, 3.5 or less is more preferable, and 3.0 or less is more preferable in that the above effect is more excellent.
  • the lower limit is not particularly limited, but is often 1.7 or more.
  • the content of the repeating unit (Q) is, for example, 90 mol% or less and 20 to 45 mol with respect to all the repeating units of the resin (A). % Is preferable, and 30 to 45 mol% is more preferable.
  • Resin (A) preferably has a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.
  • the lactone structure or sultone structure only needs to have a lactone structure or sultone structure, and a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable.
  • Those having other ring structures condensed to the sultone structure are more preferable.
  • the resin (A) is a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21), or any one of the following general formulas (SL1-1) to (SL1-3) It is more preferable to have a repeating unit having a sultone structure. A lactone structure or a sultone structure may be directly bonded to the main chain.
  • the lactone structure portion or the sultone structure portion may or may not have a substituent (Rb 2 ).
  • Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxy group.
  • An alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-decomposable group is preferable.
  • n 2 represents an integer of 0 to 4. When n 2 is 2 or more, the plurality of substituents (Rb 2 ) may be the same or different. A plurality of substituents (Rb 2 ) may be bonded to form a ring.
  • repeating unit having a lactone structure or a sultone structure a repeating unit represented by the following general formula (III) is preferable.
  • A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
  • n is the number of repetitions of the structure represented by —R 0 —Z—, and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, —R 0 —Z— does not exist and becomes a single bond.
  • R 0 represents an alkylene group, a cycloalkylene group, or a combination thereof. If R 0 is plural, R 0 each independently represents a alkylene group, a cycloalkylene group, or a combination thereof.
  • Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
  • each Z independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
  • R 8 represents a monovalent organic group having a lactone structure or a sultone structure.
  • R 7 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).
  • the alkylene group or cycloalkylene group of R 0 may have a substituent.
  • Z is preferably an ether bond or an ester bond, and more preferably an ester bond.
  • the resin (A) may have a repeating unit having a carbonate structure.
  • the carbonate structure is preferably a cyclic carbonate structure.
  • 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, a halogen atom or a monovalent organic group (preferably a methyl group).
  • n represents an integer of 0 or more.
  • R A 2 represents a substituent. When n is 2 or more, each R A 2 independently represents a substituent.
  • A represents a single bond or a divalent linking group.
  • Z represents an atomic group that forms a monocyclic structure or a polycyclic structure together with a group represented by —O—C ( ⁇ O) —O— in the formula.
  • the resin (A) is a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, and paragraphs ⁇ 0370> to ⁇ 0414> of US Patent Application Publication No. 2016 / 0070167A1. It is also preferable to have the repeating unit described in 1.
  • Resin (A) may have one or more repeating units having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, and may have two or more in combination. It may be.
  • the following monomers are also suitably used as the raw material for the resin (A).
  • the total number of repeating units having at least one kind is preferably 5 to 70 mol%, more preferably 10 to 65 mol%, more preferably 20 to 60 mol% is more preferable.
  • the resin (A) preferably has a repeating unit having a polar group.
  • the polar group include a hydroxyl group, a cyano group, a carboxy group, and a fluorinated alcohol group.
  • the repeating unit having a polar group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Moreover, it is preferable that the repeating unit which has a polar group does not have an acid-decomposable group.
  • the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group or a norbornane group.
  • Resin (A) may have the repeating unit which has a polar group individually by 1 type, and may have 2 or more types together.
  • the content of the repeating unit having a polar group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (A).
  • Resin (A) may further have a repeating unit having neither an acid-decomposable group nor a polar group.
  • the repeating unit having neither an acid-decomposable group nor a polar group preferably has an alicyclic hydrocarbon structure.
  • Examples of the repeating unit having neither an acid-decomposable group nor a polar group include the repeating units described in paragraphs ⁇ 0236> to ⁇ 0237> of US Patent Application Publication No. 2016 / 0026083A1.
  • Preferred examples of the monomer corresponding to the repeating unit having neither an acid-decomposable group nor a polar group are shown below.
  • the resin (A) may have one type of repeating unit that has neither an acid-decomposable group nor a polar group, or may have two or more types in combination.
  • the content of the repeating unit having neither an acid-decomposable group nor a polar group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, based on all repeating units in the resin (A). 5 to 25 mol% is more preferable.
  • Resin (A) is, other than the above repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or further, general required characteristics of resist, resolving power, heat resistance, sensitivity, etc.
  • Various repeating structural units may be included for the purpose of adjusting the above. Examples of such a repeating structural unit include, but are not limited to, a repeating structural unit corresponding to a predetermined monomer.
  • the predetermined monomer has one addition polymerizable unsaturated bond selected from, for example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Compounds and the like.
  • addition polymerizable unsaturated compounds that can be copolymerized with monomers corresponding to the above various repeating structural units may be used.
  • the content molar ratio of each repeating structural unit is appropriately set in order to adjust various performances.
  • the resin (A) preferably has substantially no aromatic group from the viewpoint of ArF light transmittance. More specifically, the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less with respect to all repeating units in the resin (A). More preferably, 0 mol%, that is, it does not have a repeating unit having an aromatic group.
  • all of the repeating units are composed of (meth) acrylate-based 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 50 mol% or less with respect to all the repeating units of the resin (A).
  • the resin (A) When the composition of the present invention is for KrF exposure, EB exposure, or EUV exposure, the resin (A) preferably has a repeating unit having an aromatic hydrocarbon ring group. It is more preferable that the resin (A) has a repeating unit containing a phenolic hydroxyl group. Examples of the repeating unit containing a phenolic hydroxyl group include a hydroxystyrene repeating unit or a hydroxystyrene (meth) acrylate repeating unit.
  • the resin (A) is protected with a group (leaving group) from which the hydrogen atom of the phenolic hydroxyl group is eliminated by the action of an acid.
  • the content of the repeating unit having an aromatic hydrocarbon ring group contained in the resin (A) is preferably from 30 to 100 mol%, more preferably from 40 to 100 mol%, based on all repeating units in the resin (A). 50 to 100 mol% is more preferable.
  • the weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3,000 to 15,000, and more preferably 3,000 to 11,000. Particularly preferred.
  • the degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and even more preferably 1.1 to 2.2. preferable.
  • Resin (A) may be used individually by 1 type, and may use 2 or more types together.
  • the content of the resin (A) is generally 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, based on the total solid content. 70 mass% or more is more preferable, and 80 mass% or more is particularly preferable. Although an upper limit in particular is not restrict
  • the composition of the present invention contains a photoacid generator (hereinafter also referred to as “photoacid generator (C)”).
  • a photoacid generator hereinafter also referred to as “photoacid generator (C)”.
  • the compound which has group represented by General formula (1B) used as an acid diffusion controlling agent (D) mentioned later is not contained in a photo-acid generator (C).
  • the photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation.
  • a compound capable of generating an organic acid upon irradiation with actinic rays or radiation is preferable.
  • Examples include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzyl sulfonate compounds.
  • photoacid generator known compounds that generate an acid upon irradiation with actinic rays or radiation can be appropriately selected and used alone or as a mixture thereof.
  • paragraphs ⁇ 0125> to ⁇ 0319> of US Patent Application Publication No. 2016 / 0070167A1 paragraphs ⁇ 0086> to ⁇ 0094> of US Patent Application Publication No. 2015 / 0004544A1
  • US Patent Application Publication No. 2016 / Known compounds disclosed in paragraphs ⁇ 0323> to ⁇ 0402> of the specification of 0237190A1 can be suitably used as the photoacid generator (C).
  • photoacid generator (C) for example, compounds represented by the following general formula (ZI), general formula (ZII) or general formula (ZIII) are preferable.
  • 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) and —CH 2 —CH 2 —O—CH 2 —CH 2 —.
  • Z ⁇ represents an anion.
  • the photoacid generator (C) may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of R 201 ⁇ R 203 of the compound represented by formula (ZI), and at least one of R 201 ⁇ R 203 of another compound represented by formula (ZI), a single bond Alternatively, it may be a compound having a structure bonded through a linking group.
  • Compound (ZI-1) is an arylsulfonium compound in which at least one of R 201 to R 203 in formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.
  • R 201 to R 203 may be an aryl group
  • a part of R 201 to R 203 may be an aryl group
  • the rest may be an alkyl group or a cycloalkyl group.
  • arylsulfonium compound examples include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.
  • the aryl group contained in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.
  • the two or more aryl groups may be the same or different.
  • the alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms.
  • the cycloalkyl group is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.
  • the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 are each independently an alkyl group (eg, having 1 to 15 carbon atoms), a cycloalkyl group (eg, having 3 to 15 carbon atoms), an aryl group (eg, carbon (Chem. 6-14), an alkoxy group (for example, C 1-15), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted.
  • Compound (ZI-2) is a compound in which R 201 to R 203 in formula (ZI) each independently represents an organic group having no aromatic ring.
  • the aromatic ring includes an aromatic ring containing a hetero atom.
  • the organic group having no aromatic ring as R 201 to R 203 generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
  • R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocyclo An alkyl group or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.
  • the alkyl group and cycloalkyl group represented by R 201 to R 203 are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, Propyl group, butyl group, and pentyl group) and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
  • R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
  • the compound (ZI-3) is a compound represented by the following general formula (ZI-3) and having a phenacylsulfonium salt structure.
  • R 1c to R 5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cyclo Represents an alkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group; R 6c and R 7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
  • R x and R y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
  • R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to form a ring structure.
  • the ring structure may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
  • Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic fused ring formed by combining two or more of these rings.
  • Examples of the ring structure include a 3- to 10-membered ring, a 4- to 8-membered ring is preferable, and a 5- or 6-membered ring is more preferable.
  • Examples of the group formed by combining any two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y include a butylene group and a pentylene group.
  • the group formed by combining R 5c and R 6c , and R 5c and R x is preferably a single bond or an alkylene group.
  • Examples of the alkylene group include a methylene group and an ethylene group.
  • Zc - represents an anion.
  • the compound (ZI-4) is represented by the following general formula (ZI-4).
  • l represents an integer of 0 to 2.
  • r represents an integer of 0 to 8.
  • R 13 represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group. These groups may have a substituent.
  • R 14 represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. These groups may have a substituent. When a plurality of R 14 are present, they each independently represent the above group such as a hydroxyl group. R 15 each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. Two R 15 may be bonded to each other to form a ring.
  • the ring skeleton may contain an oxygen atom or a heteroatom such as a nitrogen atom.
  • Z ⁇ represents an anion.
  • the alkyl groups of R 13 , R 14, and R 15 are linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms.
  • a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like is more preferable.
  • R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
  • the aryl group for R 204 to R 207 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • the aryl group represented by R 204 to R 207 may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
  • Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
  • Examples of the alkyl group and cycloalkyl group represented by R 204 to R 207 include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, A butyl group and a pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group).
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may each independently have a substituent.
  • substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have include an alkyl group (eg, having 1 to 15 carbon atoms) and a cycloalkyl group (eg, having 3 to 3 carbon atoms). 15), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
  • Z ⁇ represents an anion.
  • the anion represented is preferred.
  • o represents an integer of 1 to 3.
  • p represents an integer of 0 to 10.
  • q represents an integer of 0 to 10.
  • Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
  • Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF 3 . In particular, it is more preferable that both Xf are fluorine atoms.
  • R 4 and R 5 each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R 4 and R 5 are present, R 4 and R 5 may be the same as or different from each other.
  • the alkyl group represented by R 4 and R 5 may have a substituent, and preferably has 1 to 4 carbon atoms.
  • R 4 and R 5 are preferably a hydrogen atom.
  • Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in formula (3).
  • L represents a divalent linking group.
  • L may be the same or different.
  • the divalent linking group include —COO — (— C ( ⁇ O) —O—), —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, — SO—, —SO 2 —, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and combinations thereof And divalent linking groups.
  • —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —SO 2 —, —COO-alkylene group—, —OCO-alkylene group—, —CONH— alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.
  • W represents an organic group containing a cyclic structure.
  • a cyclic organic group is preferable.
  • the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
  • the alicyclic group may be monocyclic or polycyclic.
  • the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • polycyclic alicyclic group examples include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • the aryl group may be monocyclic or polycyclic.
  • Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
  • the heterocyclic group may be monocyclic or polycyclic.
  • the polycyclic type can suppress acid diffusion more.
  • the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
  • heterocyclic ring examples include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
  • lactone ring and sultone ring examples include the lactone structure and sultone structure exemplified in the aforementioned resin.
  • a heterocyclic ring in the heterocyclic group a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.
  • the cyclic organic group may have a substituent.
  • substituents include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), a cycloalkyl group (monocyclic, polycyclic and spirocyclic). Any of them, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide Groups, and sulfonate groups.
  • the carbon constituting the cyclic organic group may be a carbonyl carbon.
  • Examples of the anion represented by the general formula (3) include SO 3 ⁇ —CF 2 —CH 2 —OCO— (L) q′—W, SO 3 ⁇ —CF 2 —CHF—CH 2 —OCO— (L).
  • q'-W, SO 3 - -CF 2 -COO- (L) q'-W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 - (L) q-W, SO 3 - -CF 2- CH (CF 3 ) —OCO— (L) q′—W is preferred.
  • L, q, and W are the same as those in the general formula (3).
  • q ′ represents an integer of 0 to 10.
  • X B1 and X B2 each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom.
  • X B1 and X B2 are preferably hydrogen atoms.
  • X B3 and X B4 each independently represent a hydrogen atom or a monovalent organic group.
  • at least one of X B3 and X B4 is a fluorine atom or a monovalent organic group having a fluorine atom
  • both X B3 and X B4 are a monovalent organic group having a fluorine atom or a fluorine atom. Is more preferable.
  • both X B3 and X B4 are alkyl groups substituted with a fluorine atom.
  • L, q and W are the same as those in the general formula (3).
  • Z in the general formula (ZI) -, Z in the general formula (ZII) -, Zc in formula (ZI-3) -, and Z in the general formula (ZI-4) - may be a benzenesulfonic acid anion Often, a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group is preferred.
  • Ar represents an aryl group, and may further have a substituent other than the sulfonate anion and the — (DB) group.
  • substituents include a fluorine atom and a hydroxyl group.
  • N represents an integer of 0 or more.
  • n is preferably 1 to 4, more preferably 2 to 3, and still more preferably 3.
  • D represents a single bond or a divalent linking group.
  • the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonic acid ester group, an ester group, and a group composed of a combination of two or more thereof.
  • B represents a hydrocarbon group
  • D is a single bond and B is an aliphatic hydrocarbon structure.
  • B is more preferably an isopropyl group or a cyclohexyl group.
  • Any combination of the above cations and anions can be used as a photoacid generator.
  • the photoacid generator may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
  • the photoacid generator is preferably in the form of a low molecular compound.
  • the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.
  • the photoacid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above or may be incorporated in a resin different from the resin (A). .
  • a photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
  • the content of the photoacid generator (when there are a plurality of types) is preferably 0.1 to 35% by mass, based on the total solid content of the composition, preferably 0.5 to More preferred is 25% by mass, and further more preferred is 1 to 22% by mass.
  • the photoacid generator contains a compound represented by the above general formula (ZI-3) or (ZI-4)
  • the total is preferably 1 to 35% by mass, more preferably 1 to 30% by mass, based on the total solid content of the composition.
  • the composition of the present invention preferably contains an acid diffusion controller (D).
  • the acid diffusion controller (D) acts as a quencher that traps the acid generated from the photoacid generator and the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid.
  • DD low molecular compound
  • DE onium salt compound
  • a known acid diffusion controller can be used as appropriate.
  • R 200 , R 201 and R 202 may be the same or different and each independently represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), or a cycloalkyl group. (Preferably having 3 to 20 carbon atoms) or an aryl group (6 to 20 carbon atoms).
  • R 201 and R 202 may combine with each other to form a ring.
  • R 203 , R 204 , R 205 and R 206 may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group in the general formulas (A) and (E) may have a substituent or may be unsubstituted.
  • the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
  • the alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.
  • guanidine As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like are preferable, imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, A compound having a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, or the like is more preferable.
  • a basic compound (DB) whose basicity decreases or disappears upon irradiation with actinic rays or radiation (hereinafter also referred to as “compound (DB)”) has a proton acceptor functional group, and has an actinic ray or It is a compound that decomposes upon irradiation with radiation and whose proton acceptor property is lowered, disappears, or changes from proton acceptor property to acidity.
  • the proton acceptor functional group is a functional group having electrons or a group capable of electrostatically interacting with protons, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a ⁇ conjugate. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute to.
  • the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.
  • Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.
  • the compound (DB) is decomposed by irradiation with actinic rays or radiation to generate a compound in which the proton acceptor property is reduced or lost, or the proton acceptor property is changed to acidic.
  • the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid property is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group.
  • the acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) upon irradiation with actinic rays or radiation preferably satisfies pKa ⁇ 1, more preferably ⁇ 13 ⁇ pKa ⁇ 1, More preferably, 13 ⁇ pKa ⁇ -3 is satisfied.
  • the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined in, for example, Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.). It shows that acid strength is so large that the value of acid dissociation constant pKa is low.
  • the acid dissociation constant pKa in the aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution.
  • the following software package 1 can be used to calculate a value based on a Hammett substituent constant and a database of known literature values.
  • the values of pKa described in this specification all indicate values obtained by calculation using this software package.
  • an onium salt (DC) that is a weak acid relative to the photoacid generator can be used as an acid diffusion controller.
  • DC onium salt
  • the photoacid generator is generated by irradiation with actinic rays or radiation.
  • the acid generated from the acid collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to produce an onium salt having a strong acid anion.
  • the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.
  • onium salt that is a weak acid relative to the photoacid generator compounds represented by the following general formulas (d1-1) to (d1-3) are preferable.
  • R 51 represents a hydrocarbon group which may have a substituent
  • Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon adjacent to S).
  • R 52 is an organic group
  • Y 3 is a linear, branched or cyclic alkylene group or an arylene group
  • Rf is a fluorine atom.
  • Each of the M + is independently an ammonium cation, a sulfonium cation or an iodonium cation.
  • sulfonium cation or the iodonium cation represented by M + include the sulfonium cation exemplified by the general formula (ZI) and the iodonium cation exemplified by the general formula (ZII).
  • a low molecular compound (DD) having a nitrogen atom and a group capable of leaving by the action of an acid has a group leaving on the nitrogen atom by the action of an acid. It is preferable that it is an amine derivative having.
  • the group capable of leaving by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and more preferably a carbamate group or a hemiaminal ether group.
  • the molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and still more preferably 100 to 500.
  • Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom.
  • the protecting group constituting the carbamate group is represented by the following general formula (d-1).
  • each Rb independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably a carbon atom).
  • Rb may be connected to each other to form a ring.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are each independently a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, an alkoxy group, or a halogen atom. It may be substituted with an atom. The same applies to the alkoxyalkyl group represented by Rb.
  • Rb is preferably a linear or branched alkyl group, a cycloalkyl group, or an aryl group, and more preferably a linear or branched alkyl group or a cycloalkyl group.
  • Examples of the ring formed by connecting two Rb to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
  • Specific examples of the structure represented by the general formula (d-1) include, but are not limited to, the structure disclosed in paragraph ⁇ 0466> of US Patent Publication US2012 / 0135348A1.
  • the compound (DD) preferably has a structure represented by the following general formula (6).
  • l represents an integer of 0 to 2
  • m represents an integer of 1 to 3
  • Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • l 2
  • two Ras may be the same or different, and two Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula.
  • This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
  • Rb has the same meaning as Rb in formula (d-1), and preferred examples are also the same.
  • the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra are each independently substituted with the alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb.
  • a good group may be substituted with the same group as described above.
  • Ra alkyl group, cycloalkyl group, aryl group, and aralkyl group examples include the same groups as those described above for Rb. It is done.
  • Specific examples of the particularly preferred compound (DD) in the present invention include, but are not limited to, compounds disclosed in paragraph ⁇ 0475> of US Patent Application Publication No. 2012 / 0135348A1.
  • the onium salt compound (DE) having a nitrogen atom in the cation part is preferably a compound having a basic site containing a nitrogen atom in the cation part.
  • the basic moiety is preferably an amino group, and more preferably an aliphatic amino group. More preferably, all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. From the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is not directly connected to the nitrogen atom.
  • an electron-withdrawing functional group such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom
  • the compound (DE) include, but are not limited to, compounds disclosed in paragraph ⁇ 0203> of US Patent Application Publication No. 2015 / 03009408
  • composition of the present invention may contain a compound having a group represented by the following general formula (1B) as the acid diffusion controller (D).
  • a ⁇ represents —N ⁇ —SO 2 —R D , —COO ⁇ , —O ⁇ , or —SO 3 — .
  • R D represents a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms or a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms.
  • X + represents an onium cation.
  • Examples of the linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms represented by RD include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • Examples of the cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms represented by RD include a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.
  • a ⁇ is preferably bonded to a carbon atom, and the carbon atom preferably has no electron withdrawing group (atom).
  • Examples of the onium cation represented by X + include a triphenylsulfonium cation, a 4-cyclohexylphenyldiphenylsulfonium cation, a 4-methanesulfonylphenyldiphenylsulfonium cation, and a sulfone group-containing triphenylsulfonium cation represented by the following general formula (2B).
  • a sulfonium cation of Iodonium cations such as diphenyliodonium cation and bis (4-t-butylphenyl) iodonium cation; 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium cation, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium cation, and 1- (3,5-dimethyl- And tetrahydrothiophenium cations such as 4-hydroxyphenyl) tetrahydrothiophenium cation.
  • a sulfonium cation is preferable, and a triphenylsulfonium cation and a sulfone group-containing triphenylsulfonium cation represented by the above formula (2B) are more preferable.
  • R 6 to R 8 each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a carbon number 1 to 10 alkoxy groups.
  • R 6 to R 8 may have a substituent (for example, substituent group T).
  • Examples of the halogen atom represented by R 6 to R 8 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkyl group having 1 to 10 carbon atoms represented by R 6 to R 8 include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • Examples of the cycloalkyl group having 3 to 12 carbon atoms represented by R 6 to R 8 include a cyclopentyl group, a cyclohexyl group, and a norbornyl group.
  • Examples of the alkoxy group having 1 to 10 carbon atoms represented by R 6 to R 8 include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • the compound having a group represented by the general formula (1B) may be a low molecular compound or a polymer, and among them, a compound represented by the following general formula (3B). It is preferable.
  • R 1 is a hydrogen atom or a monovalent organic group.
  • a ⁇ and X + are as defined in the above formula (1B).
  • Examples of the monovalent organic group represented by R 1 include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, and 7 to 30 carbon atoms. Examples thereof include an aralkyl group and a heterocyclic group having 3 to 30 carbon atoms. In these groups, some or all of the hydrogen atoms may be substituted.
  • the atom bonded to A ⁇ is preferably a carbon atom, and the carbon atom preferably has no electron withdrawing group (atom).
  • alkyl group, cycloalkyl group, aryl group, aralkyl group, and heterocyclic group have include a hydroxy group, a halogen atom, an alkoxy group, a lactone group, and an alkylcarbonyl group.
  • the acid diffusion controller (D) may be used alone or in combination of two or more.
  • the content of the acid diffusion controller (D) (the total when there are a plurality of types) is preferably 0.1 to 10% by mass, based on the total solid content of the composition, preferably 0.1 to 5 mass% is more preferable.
  • composition of the present invention is a basic compound or the above general formula (D) as the acid diffusion controller (D) in that it is superior in contrast between an exposed area and an unexposed area, and more excellent in pattern uniformity of an object to be etched. It is preferable to contain a compound having a group represented by 1B).
  • the composition of the present invention may contain a hydrophobic resin (E).
  • the hydrophobic resin (E) is preferably a resin different from the resin (A) and the resin (B).
  • the composition of the present invention contains the hydrophobic resin (E)
  • the static / dynamic contact angle on the surface of the actinic ray-sensitive or radiation-sensitive film can be controlled. This makes it possible to improve development characteristics, suppress outgassing, improve immersion liquid follow-up in immersion exposure, reduce immersion defects, and the like.
  • the hydrophobic resin (E) is preferably designed to be unevenly distributed on the surface of the resist film. However, unlike the surfactant, the hydrophobic resin (E) is not necessarily required to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.
  • the hydrophobic resin (E) is selected from the group consisting of “fluorine atom”, “silicon atom”, and “CH 3 partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the membrane surface layer. It is preferable that the resin has a repeating unit having at least one kind.
  • the hydrophobic resin (E) contains a fluorine atom and / or a silicon atom
  • the fluorine atom and / or silicon atom in the hydrophobic resin (E) may be contained in the main chain of the resin, It may be contained in the chain.
  • the hydrophobic resin (E) contains a fluorine atom
  • it may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. preferable.
  • the hydrophobic resin (E) preferably has at least one group selected from the following groups (x) to (z).
  • Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (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, and tris (alkylsulfonyl) ) And a methylene group.
  • the acid group is preferably a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulf
  • Examples of the group (y) which is decomposed by the action of the alkali developer and increases the solubility in the alkali developer include a lactone group, a carboxylic acid ester group (—COO—), and an acid anhydride group (—C (O) OC. (O)-), acid imide group (—NHCONH—), carboxylic acid thioester group (—COS—), carbonate ester group (—OC (O) O—), sulfate ester group (—OSO 2 O—), and Examples thereof include a sulfonic acid ester group (—SO 2 O—), and a lactone group or a carboxylic acid ester group (—COO—) is preferable.
  • the repeating unit containing these groups is, for example, a repeating unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include a repeating unit of an acrylate ester and a methacrylate ester.
  • these groups may be bonded to the main chain of the resin via a linking group.
  • this repeating unit may be introduce
  • the repeating unit having a lactone group include those similar to the repeating unit having a lactone structure described above in the section of the resin (A).
  • the content of the repeating unit having a group (y) that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer is 1 to 100 mol% with respect to all the repeating units in the hydrophobic resin (E). 3 to 98 mol% is more preferable, and 5 to 95 mol% is still more preferable.
  • Examples of the repeating unit having a group (z) that is decomposed by the action of an acid in the hydrophobic resin (E) are the same as the repeating unit having an acid-decomposable group mentioned in the resin (A).
  • the repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom.
  • the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all repeating units in the hydrophobic resin (E). 20 to 60 mol% is more preferable.
  • the hydrophobic resin (E) may further have a repeating unit different from the above-described repeating unit.
  • the repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all repeating units in the hydrophobic resin (E).
  • the repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, based on all repeating units in the hydrophobic resin (E).
  • hydrophobic resin (E) contains a CH 3 partial structure in the side chain portion
  • a mode in which the hydrophobic resin (E) does not substantially contain a fluorine atom and a silicon atom is also preferable.
  • hydrophobic resin (E) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom.
  • the weight average molecular weight in terms of standard polystyrene of the hydrophobic resin (E) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
  • the total content of the residual monomer and / or oligomer component contained in the hydrophobic resin (E) is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass.
  • the dispersity (Mw / Mn) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3.
  • hydrophobic resin (E) publicly known resins can be appropriately selected and used alone or as a mixture thereof.
  • the repeating units disclosed in paragraphs ⁇ 0177> to ⁇ 0258> of US Patent Application Publication No. 2016 / 0237190A1 are also preferable as the repeating units constituting the hydrophobic resin (E).
  • Hydrophobic resin (E) may be used individually by 1 type, and may use 2 or more types together. It is preferable to use a mixture of two or more kinds of hydrophobic resins (E) having different surface energies from the viewpoint of compatibility between the immersion liquid followability and the development characteristics in the immersion exposure.
  • the content of the hydrophobic resin (E) is preferably from 0.01 to 10% by mass, more preferably from 0.05 to 8% by mass, based on the total solid content in the composition.
  • the composition of the present invention may contain a solvent.
  • a known resist solvent can be appropriately used.
  • paragraphs ⁇ 0665> to ⁇ 0670> of U.S. Patent Application Publication No. 2016 / 0070167A1 paragraphs ⁇ 0210> to ⁇ 0235> of U.S. Patent Application Publication No. 2015 / 0004544A1, and Patent Publication No. 2016 / 0237190A1.
  • Known solvents disclosed in paragraphs ⁇ 0424> to ⁇ 0426> of the specification and paragraphs ⁇ 0357> to ⁇ 0366> of U.S. Patent Application Publication No. 2016 / 0274458A1 can be preferably used.
  • Examples of the solvent that can be used in preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), Examples thereof include an organic solvent such as a monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.
  • a monoketone compound preferably having 4 to 10 carbon atoms
  • the mixed solvent which mixed the solvent which has a hydroxyl group in a structure may be used as an organic solvent, you may use the mixed solvent which mixed the solvent which has a hydroxyl group in a structure, and the solvent which does not have a hydroxyl group.
  • the solvent having a hydroxyl group and the solvent not having a hydroxyl group the above-described exemplary compounds can be selected as appropriate.
  • the solvent containing a hydroxyl group an alkylene glycol monoalkyl ether, an alkyl lactate or the like is preferable, and propylene glycol monomethyl ether ( PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred.
  • alkylene glycol monoalkyl ether acetate alkyl alkoxypropionate, monoketone compound which may have a ring, cyclic lactone, alkyl acetate, etc. are preferable.
  • propylene More preferred are glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, cyclopentanone or butyl acetate, propylene glycol monomethyl ether acetate, ⁇ -butyrolactone, ethyl ethoxypropionate, More preferred are cyclohexanone, cyclopentanone or 2-heptanone.
  • the solvent having no hydroxyl group propylene carbonate is also preferable.
  • the mixing ratio (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. preferable.
  • a mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable in terms of coating uniformity.
  • the solvent preferably contains propylene glycol monomethyl ether acetate, may be a propylene glycol monomethyl ether acetate single solvent, or may be two or more mixed solvents containing propylene glycol monomethyl ether acetate.
  • the composition of the present invention may contain a surfactant.
  • a surfactant When a surfactant is included, a fluorine-based and / or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom) Is preferred.
  • composition of the present invention contains a surfactant
  • a surfactant when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less is used, a pattern having good adhesion and development defects with good sensitivity and resolution can be obtained.
  • the fluorine-based and / or silicon-based surfactant include surfactants described in paragraph ⁇ 0276> of US Patent Application Publication No. 2008/0248425.
  • surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph ⁇ 0280> of US Patent Application Publication No. 2008/0248425 can also be used.
  • surfactants may be used alone or in combination of two or more.
  • the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. preferable.
  • the content of the surfactant is 10 ppm or more based on the total solid content of the composition, the surface uneven distribution of the hydrophobic resin (E) is increased. Thereby, the surface of the actinic ray-sensitive or radiation-sensitive film can be made more hydrophobic, and water followability at the time of immersion exposure is improved.
  • composition of the present invention may further contain an acid proliferation agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, or a dissolution accelerator.
  • the solid content concentration of the composition of the present invention is usually preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and still more preferably 2.0 to 5.3% by mass. .
  • the solid content concentration is a mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.
  • the thickness of the resist film is preferably 300 nm or less from the viewpoint of improving the resolution.
  • Such 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 or film forming property.
  • the composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably the above 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 further preferably 0.03 ⁇ m or less.
  • This filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
  • a cyclic filtration may be performed, and a plurality of types of filters may be connected in series or in parallel. It may be connected to and filtered.
  • the composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and after filter filtration.
  • the present invention also relates to an electronic device manufacturing method including the pattern forming method described above.
  • the electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric / electronic device (for example, home appliances, OA (Office Automation) -related devices, media-related devices, optical devices, communication devices, etc.). Is done.
  • an electric / electronic device for example, home appliances, OA (Office Automation) -related devices, media-related devices, optical devices, communication devices, etc.
  • ⁇ Acid-decomposable resin> The resins shown below were used as the resins (P-1 to P-13) shown in Table 2.
  • Table 1 shows the composition ratio (molar ratio), weight average molecular weight (Mw) and dispersity (Mw / Mn) of the repeating units in the resins P-1 to P-13, and leaving groups containing Si atoms. And the molecular weight of the leaving group in the repeating unit having a structure in which the polar group is protected, and the content of the Si atom in the repeating unit having a structure in which the polar group is protected by the leaving group containing an Si atom ( Mass%).
  • Resins P-6 to P-9 have a repeating unit having a structure in which a polar group is protected by a leaving group containing Si atoms, and a structure in which the polar group is protected by a leaving group containing Si atoms It corresponds to a resin having “a repeating unit having another acid-decomposable group”.
  • Table 1 also shows the Onishi parameters of the above “repeating units having other acid-decomposable groups”.
  • the weight average molecular weights (Mw) and dispersities (Mw / Mn) of the resins P-1 to P-13 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene).
  • the composition ratio (mol% ratio) of the resin was measured by 13 C-NMR (nuclear magnetic resonance).
  • Etching was performed on the exposed resist film under the following etching conditions using Tactras Vegas (manufactured by Tokyo Electron). By etching, the exposed portion of the resist film and the SOC film (lower layer film) located in the opening formed by removing the exposed portion are removed. That is, the etching process also serves as a dry development process. The etching time was 60 seconds. As a result, an LS (line space) pattern having a line width of about 22 nm and a space width of 22 nm was obtained.
  • Etching conditions >> Etching gas: O 2 ⁇ Pressure: 20 mTorr Applied power: 100 mW / cm 2
  • a coating film containing a spin-on carbon material (manufactured by Brewer) is formed on a silicon wafer by coating and then baked at 240 ° C. for 60 seconds to form a 200 nm-thick SOC film (underlayer film) to be etched. did.
  • the prepared actinic ray-sensitive or radiation-sensitive resin composition (Ar-1) was applied to form a coating film, followed by baking at 100 ° C. for 60 seconds to obtain a film thickness. A 100 nm resist film was formed.
  • the object to be etched was etched by the same method as described above.
  • the SOC film (lower layer film) located in the opening (unexposed portion) is removed by etching using the exposed portion of the resist film as a mask.
  • the etching time was 60 seconds.
  • an LS (line space) pattern having a line width of about 22 nm and a space width of 22 nm was obtained.
  • Example 6 From the comparison with Example 7, when the Onishi parameter of the acid-decomposable group in the repeating unit having another acid-decomposable group is 4.0 or less (preferably 3.0 or less), the pattern uniformity of the object to be etched It was confirmed that the property is superior. Further, from the comparison of Examples 5, 7, 8, and 9, the acid-decomposable resin is other acid-decomposable group other than the repeating unit having a structure in which the polar group is protected with a leaving group containing Si atom. When the content of the repeating unit having a structure in which a polar group is protected by a leaving group containing Si atoms is 50% by mass or more based on the total repeating units, It was confirmed that the pattern uniformity was more excellent.
  • the pattern formation of Examples 1 ′ to 9 ′ was performed by the same method except that the exposure process was ArF exposure under the following conditions.
  • ArF exposure Using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, Dipole, outer sigma 0.980, inner sigma 0.89, Y deflection) with a resist film thickness of 500 nm, a pitch of 100 nm and a line width
  • a LS pattern having a line width of about 50 nm and a space width of 50 nm was obtained by performing the same operation except that pattern exposure was performed through a chromium halftone mask having a thickness of 50 nm.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé de formation de motif qui forme un motif pouvant fournir un objet à graver, qui a une excellente uniformité de motif. L'invention concerne également un procédé de production d'un dispositif électronique qui comprend le procédé de formation de motif décrit ci-dessus. Un procédé de formation de motif qui comprend : une étape de formation de film de réserve au cours de laquelle un film de réserve est formé à l'aide d'une composition de résine sensible à la lumière active amplifiée chimiquement ou sensible au rayonnement ; une étape d'exposition à la lumière au cours de laquelle le film de réserve est exposé à la lumière ; une étape de cuisson après exposition au cours de laquelle le film de réserve exposé à la lumière est chauffé ; et une étape de développement au cours de laquelle le film de réserve chauffé est développé à sec. La composition de résine sensible à la lumière active amplifiée chimiquement ou sensible au rayonnement contient une résine qui a un groupe qui est décomposé par l'action d'un acide et dont la polarité est augmentée, et un générateur de photoacide. Le groupe qui est décomposé par l'action d'un acide et dont la polarité est augmentée a une structure au sein de laquelle un groupe polaire est protégé par un groupe partant qui est séparé par l'action d'un acide ; et le groupe partant contient un atome de Si, tout en ayant un poids moléculaire de 500 ou moins.
PCT/JP2018/006602 2017-03-31 2018-02-23 Procédé de formation de motif et procédé de production de dispositif électronique WO2018180069A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020171006A1 (fr) * 2019-02-22 2020-08-27 Jsr株式会社 Procede de production de substrat a semi-conducteurs et composition
WO2021120106A1 (fr) * 2019-12-19 2021-06-24 Showa Denko Materials Co., Ltd. Résine soluble dans les alcalis, composition de résine photosensible, élément photosensible, procédé de formation d'un motif de résine photosensible, et procédé de formation d'un motif de câblage
US11372329B2 (en) * 2018-11-02 2022-06-28 Tokyo Ohka Kogyo Co., Ltd. Resist composition and method of forming resist pattern

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7653908B2 (ja) 2018-11-14 2025-03-31 ラム リサーチ コーポレーション 次世代リソグラフィにおいて有用なハードマスクを作製する方法
US12211691B2 (en) 2018-12-20 2025-01-28 Lam Research Corporation Dry development of resists
TWI869221B (zh) 2019-06-26 2025-01-01 美商蘭姆研究公司 利用鹵化物化學品的光阻顯影
KR20250007037A (ko) 2020-01-15 2025-01-13 램 리써치 코포레이션 포토레지스트 부착 및 선량 감소를 위한 하부층
US20230045336A1 (en) 2020-07-07 2023-02-09 Lam Research Corporation Integrated dry processes for patterning radiation photoresist patterning
JP2022059575A (ja) * 2020-10-01 2022-04-13 東京応化工業株式会社 レジスト組成物及びレジストパターン形成方法
JP7562696B2 (ja) 2020-11-13 2024-10-07 ラム リサーチ コーポレーション フォトレジストのドライ除去用プロセスツール

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02115853A (ja) * 1988-10-26 1990-04-27 Fujitsu Ltd 半導体装置の製造方法
JP2003147022A (ja) * 2001-11-08 2003-05-21 Nippon Steel Chem Co Ltd シンジオタクチック置換ヒドロキシスチレン系重合体及び感光性組成物
JP2015025879A (ja) * 2013-07-24 2015-02-05 Jsr株式会社 樹脂組成物、重合体及びレジストパターン形成方法
WO2017002430A1 (fr) * 2015-07-01 2017-01-05 富士フイルム株式会社 Composition de résine sensible aux rayons actiniques ou au rayonnement, film sensible aux rayons actiniques ou au rayonnement, procédé de moulage par motif et procédé de production d'un dispositif électronique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02115853A (ja) * 1988-10-26 1990-04-27 Fujitsu Ltd 半導体装置の製造方法
JP2003147022A (ja) * 2001-11-08 2003-05-21 Nippon Steel Chem Co Ltd シンジオタクチック置換ヒドロキシスチレン系重合体及び感光性組成物
JP2015025879A (ja) * 2013-07-24 2015-02-05 Jsr株式会社 樹脂組成物、重合体及びレジストパターン形成方法
WO2017002430A1 (fr) * 2015-07-01 2017-01-05 富士フイルム株式会社 Composition de résine sensible aux rayons actiniques ou au rayonnement, film sensible aux rayons actiniques ou au rayonnement, procédé de moulage par motif et procédé de production d'un dispositif électronique

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11372329B2 (en) * 2018-11-02 2022-06-28 Tokyo Ohka Kogyo Co., Ltd. Resist composition and method of forming resist pattern
WO2020171006A1 (fr) * 2019-02-22 2020-08-27 Jsr株式会社 Procede de production de substrat a semi-conducteurs et composition
WO2021120106A1 (fr) * 2019-12-19 2021-06-24 Showa Denko Materials Co., Ltd. Résine soluble dans les alcalis, composition de résine photosensible, élément photosensible, procédé de formation d'un motif de résine photosensible, et procédé de formation d'un motif de câblage

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