WO2010119910A1 - Composition de résine sensible au rayonnement, polymère utilisé dans la composition et composé utilisé dans la composition - Google Patents

Composition de résine sensible au rayonnement, polymère utilisé dans la composition et composé utilisé dans la composition Download PDF

Info

Publication number
WO2010119910A1
WO2010119910A1 PCT/JP2010/056718 JP2010056718W WO2010119910A1 WO 2010119910 A1 WO2010119910 A1 WO 2010119910A1 JP 2010056718 W JP2010056718 W JP 2010056718W WO 2010119910 A1 WO2010119910 A1 WO 2010119910A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
polymer
formula
repeating unit
Prior art date
Application number
PCT/JP2010/056718
Other languages
English (en)
Japanese (ja)
Inventor
信司 松村
幸生 西村
晃雅 征矢野
龍一 芹澤
昇 大塚
寛 冨岡
Original Assignee
Jsr株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2009129665A external-priority patent/JP5126163B2/ja
Priority claimed from JP2009191426A external-priority patent/JP5126182B2/ja
Priority claimed from JP2010028339A external-priority patent/JP5655320B2/ja
Application filed by Jsr株式会社 filed Critical Jsr株式会社
Priority to KR1020117024136A priority Critical patent/KR20120012792A/ko
Publication of WO2010119910A1 publication Critical patent/WO2010119910A1/fr
Priority to US13/272,523 priority patent/US8507575B2/en

Links

Classifications

    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/38—Esters containing sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain

Definitions

  • the present invention relates to a radiation-sensitive resin composition used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and other photolithography processes, a polymer suitably used for the composition, and the polymer. It relates to the compound used for.
  • the chemically amplified radiation-sensitive resin composition generates an acid in an exposed area by irradiation with far ultraviolet light or the like typified by a KrF excimer laser or an ArF excimer laser, and reacts with the acid as a catalyst to react with the exposed area. It is a composition that changes the dissolution rate of the unexposed portion with respect to the developer to form a resist pattern on the substrate.
  • the chemically amplified resist not only has excellent resolution performance but also resist pattern line. It has become important that LWR (Line Width Roughness), which is an index of variation in width, is small and the pattern shape is rectangular.
  • LWR Line Width Roughness
  • an acid diffusion controller that loses acid diffusion controllability by being dissociated by an acid is attracting attention in terms of excellent contrast between an exposed area and an unexposed area, but the LWR characteristics and pattern shape are still insufficient. .
  • An object of the present invention is to provide a radiation-sensitive resin composition capable of forming a resist pattern having a small LWR and an excellent pattern shape.
  • R 1 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R 2 and R 4 are each independently a single bond, a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, or a divalent having a cyclic or cyclic partial structure having 3 to 20 carbon atoms.
  • R 3 is a single bond, —O—, —C ( ⁇ O) — group, —O—C ( ⁇ O) — group, —C ( ⁇ O) —O— group or sulfinyl group.
  • a ⁇ is —N ⁇ —SO 2 —R D , —COO ⁇ , —O 2 — or SO 3 — .
  • RD is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a monovalent hydrocarbon group having a cyclic or cyclic partial structure having 3 to 20 carbon atoms, or one of these hydrogen atoms.
  • X + is an onium cation.
  • a is 0 or 1; However, when A is SO 3 — , the end of R 4 on the SO 3 ⁇ side may not be —CF 2 —.
  • a - is -COO - when, not if all of R 2, R 3 and R 4 is a single bond. When a is 1, A ⁇ is not —O 2 — . )
  • the polymer (A) of the radiation-sensitive resin composition acts as a base with respect to the acid generated by exposure when it contains a radiation-sensitive acid generator, but decomposes upon irradiation with actinic rays or radiation and becomes basic. Disappear.
  • acid is diffused in the exposed area, while acid diffusion in the unexposed area is controlled, and a good contrast is obtained.
  • a structure having acid diffusion controllability is present in the polymer, uniform acid diffusion controllability in the unexposed area is expressed, so that good LWR characteristics and pattern shapes can be obtained.
  • X + in the above formula (I) is at least one selected from the group consisting of onium cations represented by the following formula (1-1) and the following formula (1-2), respectively.
  • R 5 to R 9 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, or a substituent having 1 to 10 carbon atoms.
  • the radiation-sensitive resin composition can exhibit good radiation sensitivity.
  • the radiation-sensitive resin composition is (B1) a polymer (hereinafter referred to as “polymer (B1)” having a repeating unit represented by the following formula (3) (hereinafter also referred to as “repeating unit (3)”). It is preferable to further contain.
  • polymer (B1) having a repeating unit represented by the following formula (3) (hereinafter also referred to as “repeating unit (3)”).
  • R 1 , R 2 and X + are as defined in the above formula (1).
  • N is an integer of 1 to 4.
  • the polymer (B1) is a polymer having a function as a radiation-sensitive acid generator that generates an acid upon irradiation with radiation, whereby uniform acid diffusion in an exposed area is achieved and good pattern formation is achieved. Can demonstrate its sexuality.
  • X + in the above formula (3) is preferably at least one selected from the group consisting of onium cations represented by the following formula (1-1) and the following formula (1-2).
  • R 5 to R 9 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, or a substituent having 1 to 10 carbon atoms.
  • the polymer (B1) When the polymer (B1) has the specific onium cation, the polymer (B1) exhibits good radiation sensitivity and can efficiently generate an acid.
  • the polymer (B1) preferably further has a repeating unit represented by the following formula (2) (hereinafter also referred to as “repeating unit (2)”).
  • R 10 is an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms.
  • R 11 is each independently an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or two R 11 's are bonded to each other so that both are bonded.
  • a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms is formed together with the carbon atoms.
  • the repeating unit (2) has a protecting group (acid-dissociable group) that can be removed by the action of an acid, the protecting group is removed by the action of an acid to cause the polymer (B1) to exhibit alkali solubility. And developability can be improved.
  • a protecting group acid-dissociable group
  • the radiation-sensitive resin composition comprises (B2) a radiation-sensitive acid generator (hereinafter also referred to as “acid generator (B2)”) instead of the polymer (B1) or together with the polymer (B1). Furthermore, you may contain.
  • B2 a radiation-sensitive acid generator
  • the polymer (A) is also referred to as a repeating unit represented by the following formula (1) as the repeating unit (I) (hereinafter also referred to as “repeating unit (1)”).
  • the polymer having the repeating unit (1) is also referred to as “polymer (A1)”).
  • R 1 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R 2 represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, a divalent hydrocarbon group having a cyclic or cyclic partial structure having 3 to 20 carbon atoms, or a hydrogen atom thereof.
  • R 3 is a single bond, —C ( ⁇ O) — group, —O—C ( ⁇ O) — group or sulfinyl group.
  • R D is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a monovalent hydrocarbon group having a cyclic or cyclic partial structure having 3 to 20 carbon atoms, or a hydrogen atom thereof. It is a group partially or entirely substituted with a fluorine atom.
  • X + is an onium cation.
  • the polymer (A) further has at least one selected from the group consisting of the repeating unit (2) and the repeating unit (3) (hereinafter, A polymer having the repeating unit (I) and the repeating unit (3) is also referred to as “polymer (A11)”).
  • this polymer (A11) is a polymer having a function as a radiation-sensitive acid generator that generates an acid upon irradiation with radiation, thereby achieving uniform acid diffusion in the exposed area, which is favorable. Pattern forming ability can be exhibited.
  • the polymer of the present invention has the above repeating unit (I). For this reason, although it acts as a base for the acid generated by exposure, it decomposes itself upon irradiation with actinic rays or radiation and loses basicity. Thereby, when the said polymer is used for a radiation sensitive resin composition, while an acid diffuses in an exposed part, the acid diffusion in an unexposed part will be controlled and favorable contrast will be obtained. Furthermore, since a structure having acid diffusion controllability is present in the polymer, uniform acid diffusion controllability in the unexposed area is expressed, so that good LWR characteristics and pattern shapes can be obtained. Therefore, the polymer of the present invention is suitable for the radiation sensitive resin composition.
  • the polymer of the present invention preferably contains the above repeating unit (1) as the repeating unit (I).
  • the polymer of the present invention preferably further has the repeating unit (2). Since it has a protecting group (acid dissociable group) that can be removed by the action of an acid, the protecting group is removed by the action of an acid, and the polymer can exhibit alkali solubility.
  • a protecting group acid dissociable group
  • X + in the above formula (I) is at least one selected from the group consisting of onium cations represented by the above formula (1-1) and the above formula (1-2), respectively. Is preferred. Thereby, the radiation sensitivity of the said polymer can be improved.
  • the polymer of the present invention can function as a radiation-sensitive acid generator that generates an acid upon irradiation with radiation by further including the repeating unit (3).
  • X + in formula (3) is preferably at least one selected from the group consisting of onium cations represented by formula (1-1) and formula (1-2), respectively. Also by this, the radiation sensitivity for acid generation from the polymer can be improved.
  • the compound of the present invention is a compound represented by the following formula (i) (hereinafter also referred to as “compound (i)”) or a compound represented by the following formula (ii) (hereinafter also referred to as “compound (ii)”). ).
  • R 1 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R 2 represents a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, a divalent hydrocarbon group having a cyclic or cyclic partial structure having 3 to 20 carbon atoms, or a hydrogen atom thereof. It is a group partially or entirely substituted with a fluorine atom.
  • R 3 is a single bond, —C ( ⁇ O) — group, —O—C ( ⁇ O) — group or sulfinyl group.
  • R D is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a monovalent hydrocarbon group having a cyclic or cyclic partial structure having 3 to 20 carbon atoms, or a hydrogen atom thereof. It is a group partially or entirely substituted with a fluorine atom.
  • X + is an onium cation.
  • R 1 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R 2 and R 4 are each independently a single bond, a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, or a divalent having a cyclic or cyclic partial structure having 3 to 20 carbon atoms. Or a group in which some or all of these hydrogen atoms are substituted with fluorine atoms.
  • R 3 is a single bond, —O—, —C ( ⁇ O) —, —C ( ⁇ O) —O— or —O—C ( ⁇ O) — group, provided that R 2 , R 3 and R Not all 4 are single bonds).
  • X + is an onium cation.
  • the sulfonamide structure or carboxylic acid anion structure of the compound decomposes when irradiated with radiation and loses basicity, and maintains basicity when not irradiated.
  • a polymer formed of such a compound is used in the radiation-sensitive resin composition, the acid diffuses in the exposed area, while the acid diffusion in the unexposed area is controlled. Contrast can be obtained.
  • a structure having acid diffusion controllability is present in the polymer, homogeneous acid diffusion controllability in unexposed areas is expressed, and good LWR characteristics and pattern shapes are obtained. Therefore, the compound of this invention is suitable for manufacture of the said polymer.
  • the radiation sensitive resin composition of the present invention has an effect that a resist pattern having a small LWR and an excellent pattern shape can be formed.
  • the polymer and compound of the present invention are suitably used as a raw material for the radiation-sensitive resin composition of the present invention.
  • the radiation sensitive resin composition of the present invention contains a polymer (A) having a repeating unit (I), and preferably a polymer (B1) having a repeating unit (3) and an acid generator (B2). At least one selected from the group consisting of:
  • the repeating unit (3) has a function similar to that of the acid generator (B2) that generates an acid upon irradiation with radiation.
  • Preferred embodiments of the polymer (A) include a polymer (A1) having the repeating unit (1) as the repeating unit (I), and a copolymer having the repeating unit (I) and the repeating unit (3).
  • a polymer (A11) is mentioned.
  • the radiation-sensitive resin composition of the present invention includes a radiation-sensitive resin composition containing the polymer (A1) and the polymer (A11) in addition to the composition containing these polymers. It is.
  • polymer (A), polymer (B1) as acid generator and acid generator (B2), polymer (A11) which is a preferred embodiment of polymer (A), and other suitable polymers Will be described.
  • the polymer (A) constituting the radiation-sensitive resin composition of the present invention has the repeating unit (I) and corresponds to the polymer of the present invention.
  • the repeating unit (I) has a sulfonamide structure, a carboxylate anion structure and a sulfonate anion structure each having an onium salt as a cation.
  • the radiation-sensitive resin composition contains at least one selected from the group consisting of the polymer (B1) and the acid generator (B)
  • it is a base for the acid generated in the exposure step. However, it decomposes upon irradiation with actinic rays or radiation, and loses basicity.
  • the radiation sensitive resin composition containing a polymer (A) an acid diffuses in an exposed part, acid diffusion in an unexposed part is controlled, and favorable contrast is obtained. Furthermore, since the structure having acid diffusion controllability is present in the polymer, homogeneous acid diffusion controllability in the unexposed area is expressed, so that particularly excellent LWR characteristics and pattern shapes can be obtained. The effect is obtained.
  • the polymer (A) is preferably a polymer that exhibits alkali insolubility or alkali insolubility, but has a protecting group (acid dissociable group) that can be removed by the action of an acid, and the protection by the action of an acid.
  • a polymer in which a group is eliminated and exhibits alkali solubility hereinafter also referred to as “acid-dissociable polymer”.
  • Preferred examples of the repeating unit having an acid dissociable group include the repeating unit (2).
  • the repeating unit (1) in the polymer (A) preferably generates a weak acid having a pKa of 3 to 8 by exposure, and the acid dissociable group in the polymer (A), preferably the acid in the repeating unit (2).
  • the dissociable group has a structure in which the protecting group is not dissociated by such a weak acid.
  • the acid generated by exposure of the above-described acid generator (B2) and repeating unit (3) preferably has a pKa2 or less, and when the acid diffuses, in the undecomposed polymer (A) Diffusion is suppressed by ion exchange with the repeating unit (1).
  • the repeating unit (I) in the polymer (A) is decomposed so that the basicity against the acid generated from the acid generator (B2) or the repeating unit (3) although it loses, it has a diffusion suppressing function with respect to the acid generated from the acid generator (B2) or the repeating unit (3) by ion exchange in the non-irradiated part, and as a result, it is good in the irradiated part and non-irradiated part Contrast is obtained.
  • R 1 is a hydrogen atom, a methyl group or a trifluoromethyl group, preferably a hydrogen atom or a methyl group.
  • R 2 and R 4 include a methylene group, an ethylene group, an i-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, and an n-octylene group.
  • a divalent hydrocarbon group having two or more hydrogen atoms and having a cyclic or cyclic partial structure having 3 to 20 carbon atoms, and part or all of the hydrogen atoms in these groups are substituted with fluorine atoms Group.
  • R 3 is a single bond, —C ( ⁇ O) — group, —O—C ( ⁇ O) — group or sulfinyl group.
  • Examples of the group represented by R 4 include a methyl group, an ethyl group, an i-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.
  • a hydrogen atom from a hydrocarbon such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, dicyclopentane, norbornane, tricyclodecane, tetracyclododecane, adamantane, etc.
  • a fluorinated alkyl group particularly a perfluoroalkyl group such as a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group, is preferably used.
  • repeating unit (I) examples include a repeating unit (1), a repeating unit (21) and a repeating unit (31) described later, and among them, the repeating unit (1) is particularly preferable.
  • R 1 is a hydrogen atom, a methyl group or a trifluoromethyl group, preferably a hydrogen atom or a methyl group.
  • R 2 examples include a methylene group, an ethylene group, an i-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, and an n-octylene group.
  • R 3 is a single bond, —C ( ⁇ O) — group, —O—C ( ⁇ O) — group or sulfinyl group.
  • Examples of the group represented by R 4 include a methyl group, an ethyl group, an i-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.
  • a hydrogen atom from a hydrocarbon such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, dicyclopentane, norbornane, tricyclodecane, tetracyclododecane, adamantane, etc.
  • a fluorinated alkyl group particularly a perfluoroalkyl group such as a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group, is preferably used.
  • the compound of the present invention represented by the above formula (i) is used as the monomer used for obtaining the repeating unit (1).
  • the compound of the present invention represented by the above formula (i) is used.
  • the compound include compounds represented by the following formulas (i-1) to (i-14). Of these, compounds in which R 1 is a hydrogen atom or a methyl group are preferably used.
  • the onium cation represented by X + is preferably at least one selected from the above formula (1-1) and the above formula (1-2).
  • Examples of the sulfonium cation represented by the above formula (1-1) include cations represented by the following formulas (j-1) to (j-22).
  • Examples of the iodonium cation represented by the above formula (1-2) include cations represented by the following formulas (k-1) to (k-25).
  • the monovalent onium cation represented by X + in the above formula (1) is described in, for example, Advances in Polymer Science, Vol. 62, p. 1-48 (1984).
  • the compound of the present invention can be synthesized generally by exchanging the active proton of the sulfonamide compound with an onium cation by ion exchange.
  • the polymer (A) includes a repeating unit represented by the following formula (21-1) (hereinafter also referred to as “repeating unit (21-1)”) and a repeating unit represented by the above formula (I) and At least one selected from the group consisting of repeating units represented by the formula (21-2) (hereinafter also referred to as “repeating units (21-2)”) (hereinafter referred to as repeating units (21-1) and (21- 2) may be collectively referred to as “repeating unit (21)” (hereinafter, the polymer having the repeating unit (21) is also referred to as “polymer (A21)”).
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R 2 and R 4 are each independently a single bond, a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, or a divalent having a cyclic or cyclic partial structure having 3 to 20 carbon atoms. Or a group in which some or all of these hydrogen atoms are substituted with fluorine atoms.
  • R 3 is a single bond, —O—, —C ( ⁇ O) —, —C ( ⁇ O) —O— or —O—C ( ⁇ O) — group, provided that R 2 , R 3 and R Not all 4 are single bonds).
  • X + is an onium cation.
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group, preferably a hydrogen atom or a methyl group.
  • the groups represented by R 2 and R 4 in the formula (21-1) include a single bond; a methylene group, an ethylene group, an i-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, n A linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms such as a heptylene group or an n-octylene group; cyclopropane, cyclobutane, cyclopentane, cyclohexane, dicyclopentane, norbornane, tricyclodecane, A divalent hydrocarbon group having a cyclic or cyclic partial structure of 3 to 20 carbon atoms in the form of removing two hydrogen atoms from a hydro
  • R 3 in the above formula (1-1) represents a single bond, —O—, —C ( ⁇ O) —, —C ( ⁇ O) —O— or —O—C ( ⁇ O) — group.
  • R 2 , R 3 and R 4 are all single bonds is excluded.
  • the compound of the present invention represented by the following formula (ii) is used, and the monomer used for obtaining the repeating unit (21-1) is used.
  • the monomer acrylic acid is used.
  • the compound (ii) include, for example, compounds represented by the following formulas (ii-1) to (ii-17). Of these, compounds in which R 1 is a hydrogen atom or a methyl group are preferably used.
  • the onium cation represented by X + is preferably at least one selected from the above formula (1-1) and the above formula (1-2).
  • sulfonium cation represented by the above formula (1-1) cations represented by the above formulas (j-1) to (j-22) can be preferably used.
  • iodonium cation represented by the above formula (1-2) cations represented by the above formulas (k-1) to (k-25) can be preferably used.
  • the compound (ii) can be generally synthesized by exchanging the active proton at the carboxylic acid site with an onium cation by ion exchange.
  • the polymer (A21) usually has other repeating units.
  • a repeating unit (2) described later and other repeating units can be mentioned as suitable ones.
  • the ratio of the repeating unit (21) in the polymer (A21) is preferably 0.1 to 20 mol%, particularly preferably 0.1 to 10 mol%, based on all repeating units.
  • the ratio of the repeating unit (21) is less than 0.1 mol%, the effect of reducing the pattern shape or LWR may be insufficient.
  • it exceeds 20 mol% there exists a possibility that the problem of the shape defect by low sensitivity or the deterioration of the transmittance
  • the ratio when the polymer (A21) has the repeating unit (2) is preferably 20 to 80 mol%, particularly preferably 25 to 75 mol% in all repeating units. If this ratio is less than 20 mol%, sufficient solubility may not be obtained and resolution may deteriorate. Moreover, when it exceeds 80 mol%, there exists a possibility that adhesiveness with a board
  • substrate may deteriorate.
  • At least one polymer selected from the group consisting of the polymer (A1), the polymer (A11) and the polymer (B1) is a repeating unit. (21) may be further included, and the polymer (A21) is used together with at least one polymer selected from the group consisting of the polymer (A1), the polymer (A11) and the polymer (B1). May be.
  • the polymer (A) may have a repeating unit represented by the following formula (31) (hereinafter also referred to as “repeating unit (31)”) as the repeating unit represented by the above formula (I).
  • Good hereinafter, the polymer having the repeating unit (31) is also referred to as “polymer (A31)”).
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R 2 represents a single bond, a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, a divalent hydrocarbon group having a cyclic or cyclic partial structure having 3 to 20 carbon atoms, or these A group in which part or all of the hydrogen atoms are substituted with fluorine atoms.
  • R 3 is a single bond or a divalent group represented by —O—, —C ( ⁇ O) —, —C ( ⁇ O) —O— or —O—C ( ⁇ O) —.
  • R 4 is a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having a cyclic or cyclic partial structure having 3 to 20 carbon atoms.
  • X + is an onium cation.
  • R 1 is a hydrogen atom, a methyl group or a trifluoromethyl group, among them preferably a hydrogen atom or a methyl group.
  • Examples of the linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms represented by R 2 and R 4 in the above formula (1) include, for example, a methylene group, an ethylene group, an i-propylene group, Examples thereof include an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, and an n-octylene group.
  • Is for example, a group in which two hydrogen atoms are removed from an alicyclic hydrocarbon such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, dicyclopentane, norbornane, tricyclodecane, tetracyclododecane, adamantane and the like.
  • an alicyclic hydrocarbon such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, dicyclopentane, norbornane, tricyclodecane, tetracyclododecane, adamantane and the like.
  • a linear alkylene group having 1 to 4 carbon atoms and a cyclic hydrocarbon group in which two hydrogen atoms are removed from cyclohexane, norbornane or adamantane are preferred.
  • the group represented by R 2 may be a group in which some or all
  • the compound include compounds represented by the following formulas (iii-1) to (iii-11). Of these, compounds in which R 1 is a hydrogen atom or a methyl group are preferably used.
  • the onium cation represented by X + is preferably at least one selected from the above formula (1-1) and the above formula (1-2).
  • sulfonium cation represented by the above formula (1-1) cations represented by the above formulas (j-1) to (j-22) can be preferably used.
  • iodonium cation represented by the above formula (1-2) cations represented by the above formulas (k-1) to (k-25) can be preferably used.
  • the compound of the present invention can be generally synthesized by exchanging an active proton at a carboxylic acid site to an onium cation by ion exchange.
  • the ratio of the repeating unit (31) in the polymer (A31) is preferably from 0.1 to 20 mol%, particularly preferably from 0.1 to 10 mol%, based on all repeating units.
  • the ratio of the repeating unit (31) is less than 0.1 mol%, the effect of reducing the pattern shape or LWR may be insufficient.
  • the ratio when it exceeds 20 mol% there exists a possibility that the problem of the shape defect by low sensitivity or the deterioration of the transmittance
  • the ratio when the polymer (A31) has the repeating unit (2) is preferably 20 to 80 mol%, particularly preferably 25 to 75 mol% in all repeating units. If this ratio is less than 20 mol%, sufficient solubility may not be obtained and resolution may deteriorate. Moreover, when it exceeds 80 mol%, there exists a possibility that adhesiveness with a board
  • At least one polymer selected from the group consisting of the polymer (A1), the polymer (A11) and the polymer (B1) is a repeating unit. (31) may be further included, and the polymer (A31) is used in combination with at least one polymer selected from the group consisting of the polymer (A1), the polymer (A11) and the polymer (B1). May be.
  • the polymer (A11) is a copolymer having the repeating unit (I) and the repeating unit (3). That is, the polymer of the present invention is a polymer having both an acid diffusion suppressing function by the repeating unit (I) and a radiation-sensitive acid generating function by the repeating unit (3). Therefore, the polymer (B1) and the acid generator (B2) are not essential components in the radiation-sensitive resin composition containing the polymer (A11).
  • the ratio of the repeating unit (3) in the polymer (A11) is preferably 0.1 to 20 mol%, particularly preferably 0.1%, based on all repeating units in the acid dissociable polymer contained in the radiation-sensitive resin composition. 1 to 10 mol%. If this ratio is less than 0.1 mol%, effects such as pattern shape and LWR reduction may be insufficient. Moreover, when the said ratio exceeds 20 mol%, there exists a possibility that the problem of the shape defect by the exposure amount margin insufficient (EL margin shortage) or the deterioration of the transmittance
  • the polymer (A11) usually has other repeating units.
  • a repeating unit (2) described later and other repeating units can be mentioned as suitable ones.
  • the polymer (A) usually has other repeating units.
  • the repeating unit (2) in the polymer (B1) described later and other repeating units can be mentioned as suitable ones.
  • the radiation sensitive resin composition of this invention may contain 2 or more types of polymers (A) from which a copolymerization ratio and molecular weight differ, a polymer (B1), or another acid dissociable polymer. May be contained.
  • Examples of the repeating unit constituting the other acid dissociable polymer include the repeating unit (2) described later and other repeating units.
  • the ratio of the repeating unit (1) in the polymer (A) is preferably from 0.1 to 20 mol%, particularly preferably from 0.1 to 20 mol% in all repeating units in the acid dissociable polymer contained in the radiation-sensitive resin composition. 1 to 10 mol%. If this ratio is less than 0.1 mol%, effects such as pattern shape and LWR reduction may be insufficient. Moreover, when the said ratio exceeds 20 mol%, there exists a possibility that the problem of the shape defect by low sensitivity or the deterioration of the transmittance
  • the proportion of the polymer (A) having the repeating unit (2) is preferably 20 to 80 mol%, particularly preferably in all repeating units in the acid dissociable polymer contained in the radiation sensitive resin composition. Is 25 to 75 mol%. If this ratio is less than 20 mol%, sufficient solubility may not be obtained and resolution may deteriorate. Moreover, when it exceeds 80 mol%, there exists a possibility that adhesiveness with a board
  • the polymer (B1) is a polymer having a repeating unit (3).
  • the polymer (B1) is a polymer having a function as a radiation-sensitive acid generator that generates an acid upon irradiation with radiation. Therefore, when the radiation-sensitive resin composition contains the polymer (B1), The acid generator (B2) is not an essential component.
  • R 1 , R 2 and X + are the same as in the above formula (1).
  • X + is the same as in the repeating unit (1), and the above formula (1-1) and It is preferably at least one selected from the formula (1-2).
  • N is an integer of 1 to 4, and is preferably 2.
  • Preferred examples of the monomer used for obtaining the repeating unit (3) include the following formulas (3-1) to (3-7). Of these, compounds in which R 1 is a hydrogen atom or a methyl group are preferably used.
  • the polymer (B1) preferably further contains a repeating unit (2).
  • the repeating unit (2) has a protecting group (acid-dissociable group) that can be removed by the action of an acid, and the protecting group is released by the action of an acid to cause the polymer (B1) to exhibit alkali solubility.
  • the alkyl group having 1 to 4 carbon atoms in R 10 and R 11 is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group. , 1-methylpropyl group, t-butyl group and the like.
  • Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms in R 10 and R 11 include cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; Examples include a group having a bridged alicyclic skeleton such as a pentanyl group, a dicyclopentenyl group, a tricyclodecyl group, a tetracyclododecyl group, and an adamantyl group.
  • the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms formed by bonding two R 11 together with the carbon atom to which both are bonded includes the above-described monovalent alicyclic hydrocarbon group.
  • a group obtained by removing one hydrogen atom from a hydrocarbon group can be exemplified.
  • Preferred examples of the repeating unit (2) include the following formulas (2-1) to (2-9).
  • R 1 has the same definition as the above formula (1).
  • the polymer (B1) may further have other repeating units. Preferably, it further contains at least one selected from the group consisting of a repeating unit having a lactone skeleton and a repeating unit having a cyclic carbonate structure.
  • repeating unit having a lactone skeleton examples include (meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1.0 3,7 ] non-2-yl ester, (meth) acrylic acid. -9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 3,7 ] non-2-yl ester, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [ 5.2.1.0 3,8 ] dec-2-yl ester, (meth) acrylic acid-10-methoxycarbonyl-5-oxo-4-oxa-tricyclo [5.2.1.0 3,8 ] Non-2-yl ester, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] oct-2-yl ester, (meth) acrylic acid-4-methoxycarbonyl-6-oxo -7- Oxa-bicyclo [3.2.1] oct-2-yl ester
  • repeating unit having a cyclic carbonate structure examples include a repeating unit represented by the following formula.
  • R 1 has the same definition as the above formula (1).
  • repeating units include other repeating units derived from (meth) acrylic acid esters, such as hydroxyl group-containing (meth) acrylic acid esters and carboxyl group-containing (meth) acrylic acid esters.
  • the ratio of the repeating unit (3) in the polymer (B1) is preferably 0.1 to 20 mol%, particularly preferably 0.1%, based on all repeating units in the acid dissociable polymer contained in the radiation-sensitive resin composition. 1 to 10 mol%. If this ratio is less than 0.1 mol%, effects such as pattern shape and LWR reduction may be insufficient. On the other hand, if it exceeds 20 mol%, there is a possibility that a problem of shape defect due to insufficient exposure margin (EL margin shortage) or deterioration of transmittance may occur.
  • EL margin shortage insufficient exposure margin
  • the content ratio when the polymer (B1) contains the repeating unit (2) is preferably 20 to 80 mol%, particularly in all repeating units in the acid dissociable polymer contained in the radiation-sensitive resin composition. Preferably, it is 25 to 75 mol%. If this ratio is less than 20 mol%, sufficient solubility may not be obtained and resolution may deteriorate. Moreover, when it exceeds 80 mol%, there exists a possibility that adhesiveness with a board
  • the acid generator (B2) include onium salts such as sulfonium salts and iodonium salts, organic halogen compounds, sulfone compounds such as disulfones and diazomethane sulfones, and dicarboximide compounds.
  • the acid generator (B2) include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] Triphenylsulfonium salt compounds such as hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium camphorsulfonate;
  • 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2.
  • 4-cyclohexylphenyldiphenylsulfonium salt compounds such as hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate and 4-cyclohexylphenyldiphenylsulfonium camphorsulfonate;
  • 4-methanesulfonylphenyldiphenylsulfonium trifluoromethanesulfonate 4-methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium 2- 4-methanesulfonylphenyl diphenylsulfonium salt compounds such as bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate and 4-methanesulfonylphenyldiphenylsulfonium camphorsulfonate;
  • the acid generator (B2) can be used alone or in admixture of two or more.
  • the blending amount of the acid generator (B2) is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer (A) from the viewpoint of ensuring the sensitivity and developability as a resist. More preferably, it is 1 to 20 parts by mass. In this case, if the blending amount of the acid generator is less than 0.1 parts by mass, the sensitivity and developability tend to decrease. On the other hand, if it exceeds 30 parts by mass, the transparency to radiation decreases and a rectangular resist is produced. It tends to be difficult to obtain a pattern.
  • the acid generator (B2) is not an essential component of the radiation sensitive resin composition, but may be used as an optional component.
  • the method for producing each polymer of the present invention and the polymer (A) and polymer (B1) used in the radiation-sensitive resin composition is not particularly limited.
  • the polymer has a desired molecular composition.
  • the polymerizable unsaturated monomer corresponding to each repeating unit can be produced by polymerizing in a suitable solvent in the presence of a radical polymerization initiator, a chain transfer agent or the like.
  • the radical polymerization initiator is preferably added so as to have a sufficiently high concentration in order to realize a sufficient polymerization rate.
  • the ratio of the amount of radical polymerization initiator to the amount of chain transfer agent is too high, a radical-radical coupling reaction occurs and an undesirable non-living radical polymer is formed. Therefore, the obtained polymer has a molecular weight and molecular weight.
  • the part which has the characteristic which is not controlled in polymer characteristics, such as distribution, will be contained.
  • the molar ratio between the amount of radical polymerization initiator and the amount of chain transfer agent is preferably (1: 1) to (0.005: 1).
  • radical polymerization initiator A thermal polymerization initiator, a redox polymerization initiator, and a photoinitiator are mentioned.
  • Specific examples include polymerization initiators such as peroxides and azo compounds. More specific radical polymerization initiators include t-butyl hydroperoxide, t-butyl perbenzoate, benzoyl peroxide, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azo.
  • Examples thereof include bisisobutyronitrile (AIBN), 1,1′-azobis (cyclohexanecarbonitrile), dimethyl-2,2′-azobisisobutyrate (MAIB), dimethylazobisisobutyronitrile and the like.
  • Examples of the chain transfer agent include pyrazole derivatives and alkylthiols.
  • Polymerization can be carried out by a method such as ordinary batch polymerization or dropping polymerization.
  • a method such as ordinary batch polymerization or dropping polymerization.
  • the monomers that form each of the above repeating units (1), (2) and other repeating units necessary types and amounts are dissolved in an organic solvent, and in the presence of a radical polymerization initiator and a chain transfer agent.
  • the polymer (A1) is obtained by polymerizing with.
  • the polymerization solvent an organic solvent capable of dissolving the monomer, radical polymerization initiator and chain transfer agent is generally used.
  • the organic solvent include ketone solvents, ether solvents, aprotic polar solvents, ester solvents, aromatic solvents, and chain or cyclic aliphatic solvents.
  • Examples of ketone solvents include methyl ethyl ketone and acetone.
  • Examples of ether solvents include alkoxyalkyl ethers such as methoxymethyl ether, ethyl ether, tetrahydrofuran, 1,4-dioxane and the like.
  • Examples of the aprotic polar solvent include dimethylformamide and dimethylsulfoxide.
  • Examples of ester solvents include alkyl acetates such as ethyl acetate and methyl acetate.
  • Aromatic solvents include alkylaryl solvents such as toluene, xylene, and halogenated aromatic solvents such as chlorobenzene.
  • Examples of the aliphatic solvent include hexane and cyclohexane.
  • the polymerization temperature is generally 20 to 120 ° C., preferably 50 to 110 ° C., more preferably 60 to 100 ° C. Although polymerization may be performed even in a normal air atmosphere, polymerization in an inert gas atmosphere such as nitrogen or argon is preferable.
  • the molecular weight of the polymer (A) can be adjusted by controlling the ratio between the monomer amount and the chain transfer agent amount.
  • the polymerization time is generally 0.5 to 144 hours, preferably 1 to 72 hours, more preferably 2 to 24 hours.
  • the polymer (A) and the polymer (B1) may have a residue derived from a chain transfer agent at the molecular chain end, and may not have a residue derived from the chain transfer agent at the molecular chain end. Moreover, the state which a part of residue derived from a chain transfer agent remains in the molecular chain terminal may be sufficient.
  • the polymer used in the radiation-sensitive resin composition of the present invention is naturally low in impurities such as halogen and metal, and the residual monomer and oligomer components are below the predetermined values, for example, 0. It is preferable that it is 1 mass% or less. As a result, not only can the sensitivity, resolution, process stability, pattern shape, etc. as a resist be further improved, but also a radiation-sensitive resin composition that can be used as a resist with little change over time such as foreign matter in liquid or sensitivity can be obtained. .
  • Examples of the polymer purification method include the following methods. (1) As a method for removing impurities such as metal, a metal is adsorbed by using a zeta potential filter or by washing the polymer solution with an acidic aqueous solution such as oxalic acid or sulfonic acid. For example, a method of removing in a chelated state can be mentioned.
  • (2) methods for removing residual monomers and oligomer components below specified values include liquid-liquid extraction methods that remove residual monomers and oligomer components by combining water washing and an appropriate solvent, and specific molecular weights.
  • the poor solvent used in the reprecipitation method depends on the physical properties of the polymer to be purified and cannot be generally exemplified. However, those skilled in the art can appropriately select the poor solvent according to the physical properties of the polymer. it can.
  • the weight average molecular weight (hereinafter abbreviated as “Mw”) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer of the present invention and the polymer used in the radiation sensitive resin composition of the present invention is usually 1, 000 to 300,000, preferably 2,000 to 300,000, more preferably 2,000 to 12,000. If the Mw of the polymer is less than 1,000, the heat resistance as a resist tends to decrease, while if it exceeds 300,000, the developability as a resist tends to decrease.
  • the ratio (Mw / Mn) of the polymer Mw to the polystyrene-equivalent number average molecular weight (hereinafter abbreviated as “Mn”) by gel permeation chromatography (GPC) is preferably 1 to 5, more preferably 1 To 3, particularly preferably 1 to 1.6.
  • ⁇ Other ingredients> In the radiation sensitive resin composition of the present invention, various additives such as an acid diffusion controller, an alicyclic additive, a surfactant, and a sensitizer can be blended as necessary. Since the polymer (A) used in the present invention itself has acid diffusion controllability, good resolution, pattern shape, and LWR characteristics can be obtained without using any other acid diffusion control agent. , You may use together. As other acid diffusion control agents, nitrogen-containing organic compounds excluding the polymer (A) are preferably used.
  • nitrogen-containing organic compound examples include a compound represented by the following formula (4) (hereinafter sometimes referred to as “nitrogen-containing compound (I)”), a compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (I)”). “Nitrogen-containing compound (II)”), polyamino compounds having three or more nitrogen atoms in the same molecule and polymers thereof (hereinafter sometimes collectively referred to as “nitrogen-containing compound (III)”) And amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.
  • R 12 are independently of each other a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, aryl group, or aralkyl group.
  • nitrogen-containing compound (I) examples include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; di-n- Butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc.
  • mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; di-n- Butylamine, di-n-pentylamine
  • Di (cyclo) alkylamines such as dimethylamine, methyldicyclohexylamine, tricyclohexylamine; substituted alkylamines such as 2,2 ′, 2 ′′ -nitrotriethanol; aniline, N-methylaniline, N, N— Dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,4,6-tri-tert-butyl-N-methylaniline, N- Aromatic amines such as phenyldiethanolamine
  • nitrogen-containing compound (II) examples include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodiphenyl ether.
  • nitrogen-containing compound (III) examples include polymers of polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide, and the like.
  • Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, and Nt-butoxy.
  • N N′-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxycarbonyl- 1,9-diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N′-di -T-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole, N In addition to Nt-butoxycarbonyl group-containing amino compounds such as -t-butoxycarbon
  • urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea. Etc.
  • nitrogen-containing heterocyclic compound examples include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-methyl.
  • Imidazoles such as -1H-imidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, Pyridines such as nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, 2,2 ′: 6 ′, 2 ′′ -terpyridine; piperazine, 1- (2-hydroxyethyl )
  • piperazines such as piperazine, Razine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidine ethanol, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3 -(N-morpholino) -1
  • the compounding amount of the nitrogen-containing organic compound is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less with respect to 100 parts by mass of the polymer. If the amount is more than 15 parts by mass, the sensitivity as a resist and the developability of the exposed area may be reduced. If the amount of the nitrogen-containing organic compound is less than 0.001 part by mass, the pattern shape and dimensional fidelity as a resist may be lowered depending on the process conditions.
  • the alicyclic additive may have an acid-dissociable group, and is a component that exhibits an action of further improving dry etching resistance, pattern shape, adhesion to the substrate, and the like.
  • Examples of the alicyclic additive include 1-adamantanecarboxylic acid t-butyl, 1-adamantanecarboxylic acid t-butoxycarbonylmethyl, 1-adamantanecarboxylic acid ⁇ -butyrolactone ester, 1,3-adamantane dicarboxylic acid di-t- Butyl, 1-adamantane acetate t-butyl, 1-adamantane acetate t-butoxycarbonylmethyl, 1,3-adamantanediacetate di-t-butyl, 2,5-dimethyl-2,5-di (adamantylcarbonyloxy) hexane Adamantane derivatives such as;
  • the said alicyclic additive can be used individually by 1 type or 2 or more types.
  • Surfactant is a component having an action of improving coatability, striation, developability and the like.
  • the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene
  • nonionic surfactants such as glycol distearate, the following are all trade names: KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no.
  • the said surfactant can be used individually by 1 type or 2 types or more. It is preferable that the compounding quantity of surfactant is 2 mass parts or less with respect to 100 mass parts of polymers (A).
  • the sensitizer absorbs radiation energy and transmits the energy to the photoacid generator, for example, in the form of radicals or electrons, thereby increasing the amount of acid produced. It has the effect of improving sensitivity.
  • the sensitizer include carbazoles, benzophenones, rose bengals, anthracenes, phenols and the like.
  • the said sensitizer can be used individually by 1 type or 2 types or more. It is preferable that the compounding quantity of a sensitizer is 50 mass parts or less with respect to 100 mass parts of polymers (A).
  • the radiation-sensitive resin composition of the present invention is usually dissolved in a solvent so that the total solid concentration is 1 to 50% by mass, preferably 3 to 25% by mass. It is filtered through a filter of about 2 ⁇ m and prepared as a radiation sensitive resin composition solution.
  • Examples of the solvent used for the preparation of the radiation sensitive resin composition solution include linear or branched ketones such as 2-pentanone, 2-hexanone, 2-heptanone, and 2-octanone; cyclopentanone, Cyclic ketones such as cyclohexanone; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; 2-hydroxypropionic acids such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate Alkyls: 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.
  • linear or branched ketones such as 2-pentanone, 2-hexanone, 2-heptanone, and 2-octanone
  • Cyclic ketones such as
  • Coal monomethyl ether ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, n-butyl acetate, methyl pyruvate, Examples include ethyl pyruvate, N-methylpyrrolidone, and ⁇ -butyrolactone.
  • solvents can be used alone or in admixture of two or more.
  • the radiation sensitive resin composition of the present invention is useful as a chemically amplified resist.
  • a resin component mainly an acid dissociable group in the polymer (A) is dissociated by the action of an acid generated from an acid generator by exposure, and is represented by a carboxyl group. This produces a polar group.
  • the solubility of the exposed portion of the resist in the alkaline developer is increased, and the exposed portion is dissolved and removed by the alkaline developer to obtain a positive photoresist pattern.
  • the crosslinking reaction between the alkali-soluble resin component and the crosslinking agent easily occurs by the action of the acid generated from the acid generator by exposure by containing a crosslinking agent or the like.
  • the solubility of the exposed portion of the resist in the alkaline developer is lowered, and the undeposed rear portion is dissolved and removed by the alkaline developer to obtain a resist pattern.
  • the photoresist pattern forming method is generally performed according to the following procedure, for example. (1) After forming a photoresist film on the substrate using the radiation-sensitive resin composition (step (1)), (2) the formed photoresist film (with an immersion medium if necessary) ), Exposing by exposure to radiation through a mask having a predetermined pattern (step (2)), heating the substrate (exposed photoresist film) (step (3)), and then (4) developing ( Step (4)), a photoresist pattern can be formed.
  • a radiation sensitive resin composition or a composition solution obtained by dissolving it in a solvent is applied to a substrate (silicon wafer) by an appropriate application means such as spin coating, cast coating, roll coating or the like. , Silicon dioxide, a wafer coated with an antireflection film, etc.) to form a photoresist film.
  • the solvent in the coating film is vaporized by pre-baking (PB) to form a resist film.
  • step (2) the photoresist film formed in step (1) is irradiated with radiation (possibly through an immersion medium such as water) and exposed.
  • radiation is irradiated through a mask having a predetermined pattern.
  • irradiation is performed by appropriately selecting from visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like according to the line width of the target pattern.
  • far ultraviolet rays represented by ArF excimer laser (wavelength 193 nm) and KrF excimer laser (wavelength 248 nm) are preferable, and ArF excimer laser is particularly preferable.
  • Step (3) is called post-exposure bake (PEB), and is a step in which the acid generated from the acid generator deprotects the polymer in the exposed portion of the photoresist film in step (2). There is a difference in the solubility of the exposed portion (exposed portion) and the unexposed portion (unexposed portion) in the alkaline developer. PEB is usually carried out by appropriately selecting in the range of 50 ° C to 180 ° C.
  • the exposed photoresist film is developed with a developer to form a predetermined photoresist pattern. After development, it is common to wash with water and dry.
  • the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine , Ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3. [0]
  • An aqueous alkali solution in which at least one alkaline compound such as 5-nonene is dissolved is preferable.
  • an immersion liquid insoluble immersion protective film is formed on the resist film. It may be provided.
  • a solvent peeling type protective film see, for example, JP-A-2006-227632 which is peeled off by a solvent before the step (4), a development which is peeled off simultaneously with the development in the step (4)
  • Any of liquid-removable protective films see, for example, WO 2005-069096 and WO 2006-035790 may be used.
  • a developer peeling type immersion protective film is preferable to use.
  • the resist pattern obtained in this way has good rectangularity and LWR is suppressed, so that it is suitable for fine processing using a lithography technique.
  • the obtained polymer was measured for Mw, Mw / Mn (molecular weight dispersity), yield (mass%), and the ratio (mol%) of each repeating unit in the polymer.
  • the results are shown in Table 2.
  • the content rate of the low molecular weight component with a molecular weight of less than 1,000 of the obtained polymer was less than 0.1 mass% as a result of measuring by GPC.
  • a positive resist pattern was formed by developing with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, washing with water, and drying. .
  • an exposure amount such that a line and space pattern (1L / 1S) having a diameter of 0.090 ⁇ m in the mask has a diameter of 0.090 ⁇ m was set as the optimum exposure amount, and this optimum exposure amount was set as the sensitivity.
  • pattern shape The cross-sectional shape of the 0.075 ⁇ m line and space pattern in the sensitivity measurement as described above was observed with “S-4800” manufactured by Hitachi High-Technologies Corporation, and showed a T-top shape (ie, a shape other than a rectangle). The case was “bad”, and the case of a rectangular shape was “good”.
  • the radiation-sensitive resin compositions according to Examples 1 to 8 had sufficient sensitivity, and had a good shape and a low LWR pattern. On the other hand, the LWR was poor in the compositions of Comparative Examples 1 and 2, and the pattern shape was defective in the composition of Comparative Example 3.
  • pattern shape The cross-sectional shape of the 0.090 ⁇ m line and space pattern in the sensitivity measurement as described above was observed with SEM “S-4800” manufactured by Hitachi High-Technologies Corporation, and the T-top shape (ie, a shape other than a rectangle) was obtained. The case where it was shown was “bad”, and the case where it was a rectangular shape was “good”.
  • the radiation-sensitive resin compositions according to Examples 9 to 12 were able to form a pattern having a good shape and a low LWR while having sufficient sensitivity.
  • the LWR was poor in the composition of Comparative Example 4, and the pattern shape was defective in the composition of Comparative Example 5.
  • pattern shape As described above, the cross-sectional shape of the 0.090 ⁇ m line and space pattern in the sensitivity measurement is observed with SEM “S-4800” manufactured by Hitachi High-Technologies Corporation, and the T-top shape (ie, a shape other than a rectangle) is obtained. The case where it was shown was “bad”, and the case where it was a rectangular shape was “good”.
  • the radiation-sensitive resin compositions according to Examples 13 to 14 had sufficient sensitivity, and had a good shape and a low LWR pattern. On the other hand, the LWR was poor in the composition of Comparative Example 6, and the pattern shape was defective in the composition of Comparative Example 7.
  • the radiation-sensitive resin composition of the present invention has a sufficient radiation sensitivity, has a good pattern rectangularity, and can form a resist pattern in which LWR is suppressed, a KrF excimer laser or an ArF excimer laser is used. It can be suitably used as a lithography material for a light source.

Landscapes

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

Abstract

L'invention concerne une composition de résine sensible au rayonnement qui est capable de former un motif résistant qui présente un faible LWR et une excellente forme de motif. La composition de résine sensible au rayonnement contient (A) un polymère qui comporte une unité répétitive représentée par la formule (I). Dans la formule (I), X+ est de préférence au moins un cation d'onium sélectionné parmi le groupe constitué des cations d'onium représentés par la formule (1-1) et la formule (1-2).
PCT/JP2010/056718 2009-04-15 2010-04-14 Composition de résine sensible au rayonnement, polymère utilisé dans la composition et composé utilisé dans la composition WO2010119910A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020117024136A KR20120012792A (ko) 2009-04-15 2010-04-14 감방사선성 수지 조성물, 이것에 이용하는 중합체 및 이것에 이용하는 화합물
US13/272,523 US8507575B2 (en) 2009-04-15 2011-10-13 Radiation-sensitive resin composition, polymer, and compound

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2009098982 2009-04-15
JP2009-098982 2009-04-15
JP2009-129665 2009-05-28
JP2009129665A JP5126163B2 (ja) 2009-05-28 2009-05-28 感放射線性樹脂組成物、それに用いる重合体およびそれに用いる化合物
JP2009191426A JP5126182B2 (ja) 2009-04-15 2009-08-20 感放射線性樹脂組成物、それに用いる重合体およびそれに用いる化合物
JP2009-191426 2009-08-20
JP2010028339A JP5655320B2 (ja) 2010-02-12 2010-02-12 感放射線性樹脂組成物およびそれに用いる重合体
JP2010-028339 2010-11-29

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/272,523 Continuation US8507575B2 (en) 2009-04-15 2011-10-13 Radiation-sensitive resin composition, polymer, and compound

Publications (1)

Publication Number Publication Date
WO2010119910A1 true WO2010119910A1 (fr) 2010-10-21

Family

ID=42982569

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/056718 WO2010119910A1 (fr) 2009-04-15 2010-04-14 Composition de résine sensible au rayonnement, polymère utilisé dans la composition et composé utilisé dans la composition

Country Status (1)

Country Link
WO (1) WO2010119910A1 (fr)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2362268A1 (fr) * 2010-02-26 2011-08-31 Shin-Etsu Chemical Co., Ltd. Polymère, composition de réserve positive amplifiée chimiquement et procédé de formation de motifs
EP2362267A1 (fr) * 2010-02-26 2011-08-31 Shin-Etsu Chemical Co., Ltd. Composition de réserve négative amplifiée chimiquement et procédé de formation de motifs
JP2011173855A (ja) * 2010-02-26 2011-09-08 Central Glass Co Ltd 含フッ素不飽和カルボン酸オニウム塩類
WO2012053527A1 (fr) * 2010-10-22 2012-04-26 Jsr株式会社 Procédé de formation de motif et composition sensible au rayonnement
JP2013001715A (ja) * 2011-06-10 2013-01-07 Tokyo Ohka Kogyo Co Ltd 高分子化合物の製造方法、レジスト組成物及びレジストパターン形成方法
WO2013024756A1 (fr) * 2011-08-16 2013-02-21 Jsr株式会社 Composition de photorésist
JP2013095880A (ja) * 2011-11-02 2013-05-20 Tokyo Ohka Kogyo Co Ltd 高分子化合物の製造方法、レジスト組成物及びレジストパターン形成方法
JP2013173855A (ja) * 2012-02-27 2013-09-05 Shin-Etsu Chemical Co Ltd 高分子化合物の製造方法、該製造方法によって製造された高分子化合物及びそれを含んだレジスト材料並びにパターン形成方法
US8623590B2 (en) 2010-11-02 2014-01-07 Shin-Etsu Chemical Co., Ltd. Pattern forming process
US8691490B2 (en) 2010-02-02 2014-04-08 Shin-Etsu Chemical Co., Ltd. Sulfonium salt, polymer, method for producing the polymer, resist composition and patterning process
US8735046B2 (en) 2010-11-29 2014-05-27 Shin-Etsu Chemical Co., Ltd. Positive resist composition and patterning process
US8795954B2 (en) 2010-10-15 2014-08-05 Jsr Corporation Resist pattern-forming method, and radiation-sensitive resin composition
US8900793B2 (en) 2011-05-30 2014-12-02 Shin-Etsu Chemical Co., Ltd. Polymer, chemically amplified resist composition, and patterning process using said chemically amplified resist composition
US9017918B2 (en) 2010-06-01 2015-04-28 Shin-Etsu Chemical Co., Ltd. Monomer, polymer, chemically amplified positive resist composition, and patterning process
US9164387B2 (en) 2010-10-04 2015-10-20 Jsr Corporation Pattern-forming method, and radiation-sensitive resin composition
US9360753B2 (en) 2011-07-25 2016-06-07 Shin-Etsu Chemical Co., Ltd. Resist composition and patterning process
WO2019167737A1 (fr) * 2018-02-28 2019-09-06 富士フイルム株式会社 Composition de résine sensible aux rayons actifs ou au rayonnement, film de réserve, procédé de formation de motif et procédé de fabrication d'un dispositif électronique
WO2024080128A1 (fr) * 2022-10-12 2024-04-18 富士フイルム株式会社 Composition de résine sensible aux rayons actiniques ou au rayonnement, film de résine photosensible, procédé de formation de motif et procédé de production de dispositif électronique

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09325497A (ja) * 1996-06-04 1997-12-16 Fuji Photo Film Co Ltd 感光性組成物
JPH10221852A (ja) * 1997-02-06 1998-08-21 Fuji Photo Film Co Ltd ポジ型感光性組成物
JP2002107929A (ja) * 2000-10-03 2002-04-10 Fuji Photo Film Co Ltd 平版印刷版用原版
JP2004125832A (ja) * 2002-09-30 2004-04-22 Fuji Photo Film Co Ltd 光分解型画像形成材料および平版印刷版の製版方法
JP2004287338A (ja) * 2003-03-25 2004-10-14 Fuji Photo Film Co Ltd 画像形成材料
JP2005067041A (ja) * 2003-08-25 2005-03-17 Fuji Photo Film Co Ltd 平版印刷方法および機上現像用平版印刷原版
JP2006178317A (ja) * 2004-12-24 2006-07-06 Shin Etsu Chem Co Ltd レジスト材料及びこれを用いたパターン形成方法
JP2007192907A (ja) * 2006-01-17 2007-08-02 Fujifilm Corp ポジ型感光性組成物及びそれを用いたパターン形成方法
JP2007197718A (ja) * 2005-12-27 2007-08-09 Sumitomo Chemical Co Ltd 化学増幅型ポジ型レジスト組成物用酸発生樹脂
JP2007328060A (ja) * 2006-06-06 2007-12-20 Jsr Corp パターン形成方法並びにそれに用いられる感放射線性樹脂組成物及び感放射線性酸発生基含有樹脂
WO2008056796A1 (fr) * 2006-11-10 2008-05-15 Jsr Corporation Composition de résine sensible au rayonnement
WO2008056795A1 (fr) * 2006-11-10 2008-05-15 Jsr Corporation Sel d'onium d'acide sulfonique et résine polymérisables
WO2009019793A1 (fr) * 2007-08-09 2009-02-12 Jsr Corporation Procédé de formation de motif et composition de résine sensible aux rayonnements et résine ayant un groupe acidogène sensible aux rayonnements, destinées à être utilisées dans le procédé
JP2010002599A (ja) * 2008-06-19 2010-01-07 Shin-Etsu Chemical Co Ltd ポジ型レジスト材料並びにこれを用いたパターン形成方法
JP2010002593A (ja) * 2008-06-19 2010-01-07 Shin-Etsu Chemical Co Ltd ポジ型レジスト材料並びにこれを用いたパターン形成方法
JP2010013627A (ja) * 2008-06-03 2010-01-21 Shin-Etsu Chemical Co Ltd 重合性化合物、高分子化合物及びポジ型レジスト材料並びにこれを用いたパターン形成方法
JP2010085971A (ja) * 2008-09-05 2010-04-15 Fujifilm Corp ポジ型レジスト組成物、該組成物を用いたパターン形成方法及び該組成物に用いられる樹脂

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09325497A (ja) * 1996-06-04 1997-12-16 Fuji Photo Film Co Ltd 感光性組成物
JPH10221852A (ja) * 1997-02-06 1998-08-21 Fuji Photo Film Co Ltd ポジ型感光性組成物
JP2002107929A (ja) * 2000-10-03 2002-04-10 Fuji Photo Film Co Ltd 平版印刷版用原版
JP2004125832A (ja) * 2002-09-30 2004-04-22 Fuji Photo Film Co Ltd 光分解型画像形成材料および平版印刷版の製版方法
JP2004287338A (ja) * 2003-03-25 2004-10-14 Fuji Photo Film Co Ltd 画像形成材料
JP2005067041A (ja) * 2003-08-25 2005-03-17 Fuji Photo Film Co Ltd 平版印刷方法および機上現像用平版印刷原版
JP2006178317A (ja) * 2004-12-24 2006-07-06 Shin Etsu Chem Co Ltd レジスト材料及びこれを用いたパターン形成方法
JP2007197718A (ja) * 2005-12-27 2007-08-09 Sumitomo Chemical Co Ltd 化学増幅型ポジ型レジスト組成物用酸発生樹脂
JP2007192907A (ja) * 2006-01-17 2007-08-02 Fujifilm Corp ポジ型感光性組成物及びそれを用いたパターン形成方法
JP2007328060A (ja) * 2006-06-06 2007-12-20 Jsr Corp パターン形成方法並びにそれに用いられる感放射線性樹脂組成物及び感放射線性酸発生基含有樹脂
WO2008056796A1 (fr) * 2006-11-10 2008-05-15 Jsr Corporation Composition de résine sensible au rayonnement
WO2008056795A1 (fr) * 2006-11-10 2008-05-15 Jsr Corporation Sel d'onium d'acide sulfonique et résine polymérisables
WO2009019793A1 (fr) * 2007-08-09 2009-02-12 Jsr Corporation Procédé de formation de motif et composition de résine sensible aux rayonnements et résine ayant un groupe acidogène sensible aux rayonnements, destinées à être utilisées dans le procédé
JP2010013627A (ja) * 2008-06-03 2010-01-21 Shin-Etsu Chemical Co Ltd 重合性化合物、高分子化合物及びポジ型レジスト材料並びにこれを用いたパターン形成方法
JP2010002599A (ja) * 2008-06-19 2010-01-07 Shin-Etsu Chemical Co Ltd ポジ型レジスト材料並びにこれを用いたパターン形成方法
JP2010002593A (ja) * 2008-06-19 2010-01-07 Shin-Etsu Chemical Co Ltd ポジ型レジスト材料並びにこれを用いたパターン形成方法
JP2010085971A (ja) * 2008-09-05 2010-04-15 Fujifilm Corp ポジ型レジスト組成物、該組成物を用いたパターン形成方法及び該組成物に用いられる樹脂

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8691490B2 (en) 2010-02-02 2014-04-08 Shin-Etsu Chemical Co., Ltd. Sulfonium salt, polymer, method for producing the polymer, resist composition and patterning process
EP2362268A1 (fr) * 2010-02-26 2011-08-31 Shin-Etsu Chemical Co., Ltd. Polymère, composition de réserve positive amplifiée chimiquement et procédé de formation de motifs
US20110212390A1 (en) * 2010-02-26 2011-09-01 Shin-Etsu Chemical Co., Ltd. Chemically amplified negative resist composition and patterning process
JP2011173855A (ja) * 2010-02-26 2011-09-08 Central Glass Co Ltd 含フッ素不飽和カルボン酸オニウム塩類
JP2011195812A (ja) * 2010-02-26 2011-10-06 Shin-Etsu Chemical Co Ltd 高分子化合物及びこれを用いた化学増幅ポジ型レジスト組成物並びにパターン形成方法
TWI501038B (zh) * 2010-02-26 2015-09-21 Shinetsu Chemical Co 高分子化合物及使用其之化學增幅正型光阻組成物以及圖型之形成方法
EP2362267A1 (fr) * 2010-02-26 2011-08-31 Shin-Etsu Chemical Co., Ltd. Composition de réserve négative amplifiée chimiquement et procédé de formation de motifs
US8859181B2 (en) 2010-02-26 2014-10-14 Shin-Etsu Chemical Co., Ltd. Chemically amplified negative resist composition and patterning process
US8632939B2 (en) 2010-02-26 2014-01-21 Shin-Etsu Chemical Co., Ltd. Polymer, chemically amplified positive resist composition and pattern forming process
US9017918B2 (en) 2010-06-01 2015-04-28 Shin-Etsu Chemical Co., Ltd. Monomer, polymer, chemically amplified positive resist composition, and patterning process
US9164387B2 (en) 2010-10-04 2015-10-20 Jsr Corporation Pattern-forming method, and radiation-sensitive resin composition
US9170488B2 (en) 2010-10-15 2015-10-27 Jsr Corporation Resist pattern-forming method, and radiation-sensitive resin composition
US8795954B2 (en) 2010-10-15 2014-08-05 Jsr Corporation Resist pattern-forming method, and radiation-sensitive resin composition
JPWO2012053527A1 (ja) * 2010-10-22 2014-02-24 Jsr株式会社 パターン形成方法及び感放射線性組成物
KR101907705B1 (ko) * 2010-10-22 2018-10-12 제이에스알 가부시끼가이샤 패턴 형성 방법 및 감방사선성 조성물
US9335630B2 (en) 2010-10-22 2016-05-10 Jsr Corporation Pattern-forming method, and radiation-sensitive composition
WO2012053527A1 (fr) * 2010-10-22 2012-04-26 Jsr株式会社 Procédé de formation de motif et composition sensible au rayonnement
JP2015172755A (ja) * 2010-10-22 2015-10-01 Jsr株式会社 パターン形成方法
US9034559B2 (en) 2010-10-22 2015-05-19 Jsr Corporation Pattern-forming method, and radiation-sensitive composition
US8623590B2 (en) 2010-11-02 2014-01-07 Shin-Etsu Chemical Co., Ltd. Pattern forming process
US8735046B2 (en) 2010-11-29 2014-05-27 Shin-Etsu Chemical Co., Ltd. Positive resist composition and patterning process
US8900793B2 (en) 2011-05-30 2014-12-02 Shin-Etsu Chemical Co., Ltd. Polymer, chemically amplified resist composition, and patterning process using said chemically amplified resist composition
KR101849787B1 (ko) * 2011-06-10 2018-04-17 도오꾜오까고오교 가부시끼가이샤 고분자 화합물의 제조 방법, 레지스트 조성물 및 레지스트 패턴 형성 방법
TWI501029B (zh) * 2011-06-10 2015-09-21 Tokyo Ohka Kogyo Co Ltd 高分子化合物之製造方法
US8987386B2 (en) 2011-06-10 2015-03-24 Tokyo Ohka Kogyo Co., Ltd. Method of producing polymeric compound, resist composition, and method of forming resist pattern
JP2013001715A (ja) * 2011-06-10 2013-01-07 Tokyo Ohka Kogyo Co Ltd 高分子化合物の製造方法、レジスト組成物及びレジストパターン形成方法
US9360753B2 (en) 2011-07-25 2016-06-07 Shin-Etsu Chemical Co., Ltd. Resist composition and patterning process
JPWO2013024756A1 (ja) * 2011-08-16 2015-03-05 Jsr株式会社 フォトレジスト組成物
WO2013024756A1 (fr) * 2011-08-16 2013-02-21 Jsr株式会社 Composition de photorésist
JP2013095880A (ja) * 2011-11-02 2013-05-20 Tokyo Ohka Kogyo Co Ltd 高分子化合物の製造方法、レジスト組成物及びレジストパターン形成方法
JP2013173855A (ja) * 2012-02-27 2013-09-05 Shin-Etsu Chemical Co Ltd 高分子化合物の製造方法、該製造方法によって製造された高分子化合物及びそれを含んだレジスト材料並びにパターン形成方法
WO2019167737A1 (fr) * 2018-02-28 2019-09-06 富士フイルム株式会社 Composition de résine sensible aux rayons actifs ou au rayonnement, film de réserve, procédé de formation de motif et procédé de fabrication d'un dispositif électronique
KR20200110439A (ko) * 2018-02-28 2020-09-23 후지필름 가부시키가이샤 감활성광선성 또는 감방사선성 수지 조성물, 레지스트막, 패턴 형성 방법, 전자 디바이스의 제조 방법
JPWO2019167737A1 (ja) * 2018-02-28 2021-02-12 富士フイルム株式会社 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法
KR102476090B1 (ko) * 2018-02-28 2022-12-09 후지필름 가부시키가이샤 감활성광선성 또는 감방사선성 수지 조성물, 레지스트막, 패턴 형성 방법, 전자 디바이스의 제조 방법
WO2024080128A1 (fr) * 2022-10-12 2024-04-18 富士フイルム株式会社 Composition de résine sensible aux rayons actiniques ou au rayonnement, film de résine photosensible, procédé de formation de motif et procédé de production de dispositif électronique

Similar Documents

Publication Publication Date Title
JP5126182B2 (ja) 感放射線性樹脂組成物、それに用いる重合体およびそれに用いる化合物
US8507575B2 (en) Radiation-sensitive resin composition, polymer, and compound
WO2010119910A1 (fr) Composition de résine sensible au rayonnement, polymère utilisé dans la composition et composé utilisé dans la composition
JP5088327B2 (ja) 感放射線性樹脂組成物
JP5713004B2 (ja) 感放射線性樹脂組成物
JP5660037B2 (ja) 感放射線性樹脂組成物
KR20130028032A (ko) 감방사선성 조성물 및 신규 화합물
JP5617339B2 (ja) 感放射線性樹脂組成物、重合体及び化合物
JP3952946B2 (ja) （メタ）アクリル系重合体および感放射線性樹脂組成物
TWI476212B (zh) Sensitive radiation linear resin composition, polymer and photoresist pattern formation method
JP4655886B2 (ja) ポジ型感放射線性樹脂組成物
JP2010271686A (ja) 感放射線性樹脂組成物
JP4076360B2 (ja) 感放射線性樹脂組成物
JP3975790B2 (ja) 感放射線性樹脂組成物
JP2004300403A (ja) （メタ）アクリル系重合体および感放射線性樹脂組成物
JP2005023234A (ja) アクリル系重合体および感放射線性樹脂組成物
JP5126163B2 (ja) 感放射線性樹脂組成物、それに用いる重合体およびそれに用いる化合物
JP3969135B2 (ja) 感放射線性樹脂組成物
JP2004176049A (ja) アクリル系共重合体および感放射線性樹脂組成物
JP5434709B2 (ja) 感放射線性樹脂組成物及び重合体
JP3968509B2 (ja) 感放射線性樹脂組成物
JP5655320B2 (ja) 感放射線性樹脂組成物およびそれに用いる重合体
JP2004203898A (ja) アクリル系重合体および感放射線性樹脂組成物
JP2004210910A (ja) （メタ）アクリル系重合体および感放射線性樹脂組成物
JP2004157199A (ja) 感放射線性樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10764494

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20117024136

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10764494

Country of ref document: EP

Kind code of ref document: A1