WO2017188297A1 - Composition de résist et procédé de production d'un dispositif l'utilisant - Google Patents

Composition de résist et procédé de production d'un dispositif l'utilisant Download PDF

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WO2017188297A1
WO2017188297A1 PCT/JP2017/016486 JP2017016486W WO2017188297A1 WO 2017188297 A1 WO2017188297 A1 WO 2017188297A1 JP 2017016486 W JP2017016486 W JP 2017016486W WO 2017188297 A1 WO2017188297 A1 WO 2017188297A1
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group
substituent
acid
resist composition
carbon
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PCT/JP2017/016486
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English (en)
Japanese (ja)
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智至 榎本
優介 菅
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東洋合成工業株式会社
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Priority to KR1020187033395A priority Critical patent/KR20190004300A/ko
Priority to JP2018514653A priority patent/JP6827037B2/ja
Publication of WO2017188297A1 publication Critical patent/WO2017188297A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/06—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G03F7/20—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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • 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
    • 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
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking

Definitions

  • Some embodiments of the present invention relate to a composition that can be used for forming a resist pattern and a method for producing a device using the composition.
  • Chemically-amplified photoresists have been proposed as photoresists suitable for short wavelengths (Patent Documents 1 to 3).
  • a feature of the chemically amplified photoresist is that an acid is generated from a photoacid generator as a component upon exposure to exposure light, and this acid causes an acid-catalyzed reaction with a resist compound or the like by heat treatment after exposure.
  • EUV Extreme Ultra Violet
  • EUV Extra Violet
  • the biggest drawback of EUV lithography is the lack of output of the EUV light source. For this reason, a highly sensitive photoresist is required, but there is a trade-off relationship among sensitivity, resolution, and LWR (Line Width Roughness). Therefore, there is a problem that increasing the sensitivity lowers resolution and increases roughness.
  • One object of some embodiments of the present invention is to provide a resist composition that can improve the efficiency of acid generation.
  • Another object of some aspects of the present invention is to provide a device manufacturing method using the resist composition that is suitably used as a photoresist composition that satisfies high sensitivity, high resolution, and high LWR characteristics. is there.
  • a photosensitizer precursor that can be dissociated by an acid to become a photosensitizer, a photoacid generator, a hydroxy group-containing compound
  • the acid generation efficiency can be improved by using a resist composition containing an acid-reactive compound as a chemically amplified resist composition. More specifically, in pattern formation using a chemically amplified photoresist containing a photoacid generator, a chemical composition comprising a photosensitizer precursor, a photoacid generator, a hydroxy group-containing compound, and an acid-reactive compound is chemically treated.
  • the photosensitizer precursor is acid-dissociated with an acid generated from the photoacid generator by irradiation with a first active energy ray such as EUV light or electron beam (EB), and photosensitized. It was found that, when the photosensitizer is further irradiated with UV light or the like second, electron transfer to the photoacid generator occurs and the acid generation efficiency is improved.
  • a first active energy ray such as EUV light or electron beam (EB)
  • One aspect of the present invention is a resist composition
  • a photosensitizer precursor represented by the following general formula (1) a photoacid generator, a hydroxy group-containing compound, and an acid-reactive compound. is there.
  • Ar 1 and Ar 2 are each independently a phenylene group optionally having a substituent
  • R 1 is any one selected from the group consisting of an optionally substituted thioalkoxy group, arylthio group, and thioalkoxyphenyl group
  • X is any selected from the group consisting of a sulfur atom, an oxygen atom and a direct bond
  • R 2 is either an alkyl group or an aryl group which may have a substituent
  • Y is each independently one of an oxygen atom and a sulfur atom
  • R 3 and R 4 are each independently a linear, branched or cyclic alkyl group which may have a substituent
  • R 3 and R 4 are bonded to each other to form a compound It may form a ring structure with two Y in the inside, At least one of the carbon-carbon single bonds in the alkyl group of R 1 , R 2 , R 3 and R 4 may be replaced with a carbon-carbon double bond or a carbon-carbon triple bond
  • the resist composition according to one embodiment of the present invention improves the acid generation efficiency of the photoacid generator and has high sensitivity, high resolution, and high LWR characteristics.
  • Photosensitizer precursor in one embodiment of the present invention is represented by the following general formula (1).
  • Ar 1 and Ar 2 are each independently a phenylene group optionally having a substituent
  • R 1 is any one selected from the group consisting of an optionally substituted thioalkoxy group, arylthio group, and thioalkoxyphenyl group
  • X is any selected from the group consisting of a sulfur atom, an oxygen atom and a direct bond
  • R 2 is either an alkyl group or an aryl group which may have a substituent
  • Y is each independently one of an oxygen atom and a sulfur atom
  • R 3 and R 4 are each independently a linear, branched or cyclic alkyl group that may have a substituent, R 3 and R 4 may be bonded to each other to form a ring structure with two Ys in the formula, At least one of the carbon-carbon single bonds in the alkyl group of R 1 , R 2 , R 3 and R 4 may be replaced with a carbon-carbon double bond or a carbon-carbon triple bond; At least one of the
  • the sum of Hammett substituent constants ⁇ is preferably 0.2 or less.
  • the sum of Hammett substituent constants ⁇ refers to each Ar 1 , based on a group in which two quaternary carbons bonded to Y, Ar 1 and Ar 2 are bonded in the general formula (1).
  • Hammett substituent constant [sigma] is used in 1935 to discuss the effect of substituents on the reaction or equilibrium of benzene derivatives quantitatively. P.
  • the total sum of Hammett substituent constants ⁇ of the photosensitizer precursor is preferably 0.2 or less, and more preferably ⁇ 0.01 or less. Further, it is preferably ⁇ 3.00 or more.
  • the Hammett substituent constant ⁇ of the substituent of Ar 1 in the general formula (1) is preferably 1 or less.
  • the Hammett substituent constant ⁇ of the substituent of Ar 2 in the general formula (1) is preferably 1 or less.
  • the sum of Hammett substituent constant ⁇ of the substituent of Ar 1 and Hammett substituent constant ⁇ of the substituent of Ar 2 is 0.2 or less, so that the Hammett substituent constant ⁇ of the photosensitizer precursor is reduced. Is less than 0.2.
  • the photoacid becomes when the photosensitizer precursor is acid-dissociated and becomes a photosensitizer.
  • the acid generation efficiency of the generator can be improved.
  • an electron-donating group or an electron-withdrawing substituent is appropriately selected for Ar 1 and Ar 2.
  • the Hammett substituent constant ⁇ may be adjusted by introducing an electron donating group at an appropriate position.
  • Ar 1 and Ar 2 in the above formula (1) are each a phenylene group, and each of them is a substituent other than R 1 or —X—R 2 (hereinafter, the substituents of Ar 1 and Ar 2 are referred to as “first It may be referred to as a “substituent”.
  • Ar 1 and Ar 2 are preferably bonded directly or indirectly to form a ring from the viewpoint of synthesis.
  • the first substituent include an electron donating group.
  • Specific examples of the electron donating group include an alkyl group, an alkoxy group, an alkoxyphenyl group, a thioalkoxy group, an arylthio group, and a thioalkoxyphenyl group. Can be mentioned.
  • Examples of the first substituent include a long-chain alkoxy group having a polyethylene glycol chain (— (CH 2 CH 2 O) n —). Further, when the first substituent is bonded to the para position of Ar 1 or Ar 2 , it may have a hydroxy group as the first substituent.
  • the substitution position such as “para-position” of Ar 1 or Ar 2 is the position relative to the group to which the two quaternary carbons bonded to Ar 1 and Ar 2 in the above formula (1) are bonded.
  • the criterion for the substitution position such as “para-position” is the position with respect to the group bonded to the quaternary carbon.
  • the alkyl group as the first substituent is not particularly limited, but includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, t-butyl group, cyclohexyl group, adamantyl group, etc.
  • Examples thereof include linear, branched and cyclic alkyl groups having 1 to 20 carbon atoms.
  • the alkoxy group as the first substituent is not particularly limited, and examples thereof include an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • Examples of the thioalkoxy group, arylthio group and thioalkoxyphenyl group as the first substituent include the same thioalkoxy groups, arylthio groups and thioalkoxyphenyl groups of R 1 described later.
  • the first substituent is an alkoxy group, an alkoxyphenyl group, a thioalkoxy group, an arylthio group, or a thioalkoxyphenyl group
  • the first substituent is bonded to the ortho position and / or the para position of the phenylene group that is Ar 1 and Ar 2.
  • the total number of the first substituent group of the Ar 1 and Ar 2 is 3 or less.
  • R 1 in the above formula (1) is any selected from the group consisting of a thioalkoxy group, an arylthio group and a thioalkoxyphenyl group which may have a substituent.
  • the thioalkoxy group for R 1 is preferably a thioalkoxy group having 1 to 20 carbon atoms such as a thiomethoxy group, a thioethoxy group, a thio n-propoxy group, or a thio n-butoxy group, and a thioalkoxy group having 1 to 12 carbon atoms.
  • An alkoxy group is more preferable.
  • Specific examples of the arylthio group for R 1 include a phenylthio group and a naphthylthio group.
  • thioalkoxyphenyl group represented by R 1 include a phenyl group to which a thioalkoxy group having 1 to 20 carbon atoms such as a thiomethoxyphenyl group, a thioethoxyphenyl group, a thiopropoxyphenyl group, or a thiobutoxyphenyl is bonded. More preferred is a phenyl group to which a thioalkoxy group having 1 to 12 carbon atoms is bonded. No particular restriction on the substitution position of thioalkoxy group attached to the phenylene group in R 1, but it is the para position is preferred from the viewpoint of increasing the molar extinction coefficient of the electron-donating and 365 nm. R 1 is preferably bonded to the ortho or para position of the phenylene group that is Ar 1 .
  • R 2 in the above formula (1) is either an alkyl group or an aryl group which may have a substituent.
  • the alkyl group for R 2 include a straight chain or branched chain having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a t-butyl group, and a cyclohexyl group.
  • cyclic alkyl groups examples of the aryl group for R 2 include a phenyl group and a naphthyl group.
  • R 1 and R 2 in the above formula (1) may have a substituent, and as the substituent (hereinafter, the substituents of R 1 and R 2 are referred to as “second substituent”), although it does not restrict
  • a polymerized group introduced into R 1 or R 2 and polymerized therefrom may be used as a polymer imparted with a sensitizing action. That is, a polymer including a unit having a function of a photosensitizer precursor as a unit is also a photosensitizer precursor in one embodiment of the present invention, and the second substituent includes a polymer main chain. Also good.
  • the polymerizable group include a (meth) acryloyloxy group, an epoxy group, and a vinyl group. Note that “(meth) acryloyl” represents acryloyl and methacryloyl.
  • X in the formula (1) is an oxygen atom or a sulfur atom, it is preferable that the X is an ortho position or a para position of Ar 2 .
  • X is a direct bond, it is preferable that X is an ortho or para position of Ar 2 .
  • At least one of the carbon-carbon single bonds in R 1 , R 2 , the alkyl group of the first substituent and the second substituent is replaced with a carbon-carbon double bond or a carbon-carbon triple bond. Also good.
  • at least one of the methylene groups in the alkyl group of R 1 , R 2 , the first substituent and the second substituent may be replaced with a divalent heteroatom-containing group. Examples of the divalent heteroatom-containing group include —O—, —CO—, —COO—, —OCO—, —O—CO—O—, —NHCO—, —CONH—, and —NH—CO—O—.
  • R 1 , R 2 , the first substituent, and the second substituent do not have a continuous connection of heteroatoms such as —O—O— and —SS—.
  • R may be the same as the alkyl group exemplified as the first substituent.
  • Ar is the same as the aryl group for R 2 .
  • the total number of carbon atoms of R 1 in the above formula (1) is not particularly limited, and is preferably 1 to 20 carbon atoms regardless of the presence or absence of the substituent of R 1 .
  • the total carbon number of R 2 in the above formula (1) is not particularly limited, and is preferably 1 to 20 in total, regardless of the presence or absence of the substituent of R 2 .
  • the photosensitizer precursor is a polymer
  • the total carbon number of R 1 and R 2 excluding the portion containing the polymer main chain that becomes the second substituent is preferably 1-20.
  • R 1 , R 2 , the first substituent and the second substituent may have an acid dissociable group.
  • the acid-dissociable group may be any protecting group that is deprotected by the action of an acid, such as t-butoxycarbonyloxy group, methoxymethoxy group, ethoxymethoxy group, trimethylsilyloxy group, tetrahydropyranyloxy group, and 1- An ethoxyethoxy group etc. are mentioned.
  • the photosensitizer precursor has an acid-dissociable group, so that the solubility is changed by the action of an acid, and a solubility contrast is obtained in the exposed and unexposed areas. It is preferable because it is easily formed.
  • Y is each independently either an oxygen atom or a sulfur atom.
  • R 3 and R 4 are each independently a linear, branched or cyclic alkyl group which may have a substituent.
  • the alkyl group of R 3 and R 4 a straight chain having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, t-butyl group, cyclohexyl group, etc. Examples include branched and cyclic alkyl groups. From the viewpoint of synthesis, R 3 and R 4 are preferably the same. In the present invention, when R 3 and R 4 are the groups shown above, the photosensitizer precursor may be deprotected with an acid to have a carbonyl group.
  • R 3 and R 4 may be bonded to each other to form a ring structure with two Ys in the formula. That is, the photosensitizer precursor in one embodiment of the present invention is preferably a cyclic acetal compound having a cyclic acetal protecting group represented by the following formula (2).
  • —R 5 —R 6 — is preferably — (CH 2 ) n —, and n is an integer of 2 or more.
  • n is not particularly limited as long as it is 2 or more, it is preferably 8 or less for ease of synthesis.
  • R 5 and R 6 correspond to those in which R 3 and R 4 in the above formula (1) are bonded to each other to form a ring.
  • an acyclic acetal has a lower activation energy than a cyclic acetal, and a cyclic acetal compound has a high hydrolysis rate.
  • a 5-membered ring structure such as 1,3-dioxolane has high activation energy and is stable, whereas a 6-membered ring such as 1,3-dioxane structure and 1,3-dioxepane. Those having the above structure have low activation energy.
  • the relative comparison value of the hydrolysis rate due to the difference in the structure of the cyclic acetal compound is described in, for example, Non-patent Document Green's PROTECTIVE GROUPS in ORGANIC SYNTHESIS Fourth Edition, A John Wiley & Sons, Inc. , Publication, p 448-449.
  • the photosensitizer precursor in one embodiment of the present invention preferably has a low activation energy of the acetal protecting group. This is because the photosensitizer precursor is easily converted into a photosensitizer by the deprotection reaction of acetal.
  • R 3 and R 4 are preferably a linear, branched or cyclic alkyl group, and more preferably a linear alkyl group.
  • —R 5 —R 6 — is a group in which n is 3 or more. (CH 2 ) n- is preferred.
  • R 3 and R 4 in the above formula (1) may have a substituent, and as the substituent (hereinafter, the substituents of R 3 and R 4 are referred to as “third substituent”), although it does not restrict
  • aryl groups such as a phenyl group and a naphthyl group, etc. are mentioned.
  • At least one of the carbon-carbon single bonds in the alkyl group of R 3 , R 4 and the third substituent may be replaced with a carbon-carbon double bond or a carbon-carbon triple bond.
  • at least one of methylene groups in the alkyl group of R 3 , R 4 and the third substituent may be replaced with the above divalent hetero atom-containing group.
  • the total carbon number of R 3 and R 4 in the above formula (1) is not particularly limited, and the photosensitizer precursor may be a constituent component of a polymer.
  • R 3 or R 4 preferably has a total carbon number of 1 to 20 regardless of the presence or absence of substituents.
  • R 5 and R 6 may have the same third substituent as R 3 and R 4 .
  • a polymer obtained by introducing a polymerizable group into R 3 or R 4 and polymerizing it may be used as a polymer imparted with a sensitizing action. That is, when the photosensitizer precursor in one embodiment of the present invention is a polymer including a unit having a photosensitizer precursor function as a unit, the third substituent is replaced with the third substituent.
  • the substituent may contain a polymer main chain.
  • the total carbon number of R 3 and R 4 is preferably 1-20.
  • the photosensitizer precursor is a polymer
  • the total number of carbon atoms of R 3 and R 4 excluding the portion containing the polymer main chain serving as the third substituent is preferably 1-20.
  • the photosensitizer after acid treatment of the photosensitizer precursor that is, the photosensitizer having a carbonyl group generated when the photosensitizer precursor is deprotected with an acid has a molar extinction coefficient at 365 nm of 1. It is preferable that it is 0.0 ⁇ 10 5 cm 2 / mol or more. A higher molar extinction coefficient at 365 nm is preferable, but a practical value is 1.0 ⁇ 10 10 cm 2 / mol or less.
  • the photosensitizer precursor has, for example, at least one selected from the group consisting of a thioalkoxy group, an arylthio group, and a thioalkoxyphenyl group, or an alkoxy group and A configuration having two or more aryloxy groups may be mentioned.
  • the molar extinction coefficient is at 365 nm in a chloroform solvent or acetonitrile solvent measured with a UV-VIS spectrophotometer using chloroform or acetonitrile as a solvent.
  • the molar extinction coefficient of the photosensitizer having a carbonyl group in some embodiments of the present invention can be within the above range in either a chloroform solvent or an acetonitrile solvent.
  • the photosensitizer precursor in one embodiment of the present invention is composed of -YR 3 and -YR 4 in the entire photosensitizer precursor from the viewpoint of ease of synthesis and light absorption characteristics.
  • the photosensitizer precursor represented by the above formula (1) for example, the following photosensitizer precursor can be exemplified. In the following examples, those shown in parentheses represent polymer units.
  • the photosensitizer precursor in some embodiments of the present invention is not limited to this.
  • the photosensitizer precursor in one embodiment of the present invention has a structure represented by the following formula (4)
  • the derivative represented by the above formula (3) and 1,3-propanediol obtained above are It can be obtained by reacting at 0 to 100 ° C. for 1 to 120 hours in the presence of an acid such as camphorsulfonic acid.
  • the photosensitizer precursor in one embodiment of the present invention has a structure represented by the following formula (5)
  • the derivative represented by the above formula (3) obtained above and methanethiol are combined with boron trichloride or the like. It can be obtained by reacting at -78 ° C to 0 ° C for 1 to 120 hours in the presence of a Lewis acid.
  • the photosensitizer precursor in one embodiment of the present invention has a structure represented by the following formula (6), the derivative represented by the above formula (3) obtained above and 3-mercapto-1-propanol It can be obtained by reacting at 0 to 100 ° C. for 1 to 120 hours in the presence of a Lewis acid such as zirconium chloride (IV).
  • a Lewis acid such as zirconium chloride (IV).
  • the photosensitizer precursor in one embodiment of the present invention has a structure represented by the following formula (7)
  • the derivative represented by the above formula (3) obtained above and methanethiol are combined with boron trichloride or the like. It can be obtained by reacting at 0 to 100 ° C. for 1 to 120 hours in the presence of a Lewis acid.
  • the photosensitizer precursor in one embodiment of the present invention has a structure represented by the following formula (8)
  • the derivative represented by the above formula (3) obtained above and 1,3-propanedithiol are obtained. It can be obtained by reacting at 0 to 100 ° C. for 1 to 120 hours in the presence of a Lewis acid such as boron trichloride.
  • the photosensitizer precursor in one embodiment of the present invention has a specific structure, the acetalization reaction can be efficiently advanced. It is preferable that Ar 1 and Ar 2 do not have a ring structure through a divalent group and the quaternary carbon. The reason is that when Ar 1 and Ar 2 have a ring structure via a divalent group and the quaternary carbon, for example, when having a skeleton such as thioxanthone, it is difficult to efficiently advance the acetalization reaction. There is a case. Therefore, it is preferable in the synthesis that Ar 1 and Ar 2 do not have a ring structure directly or via a divalent group and the quaternary carbon.
  • Photoacid generator in one embodiment of the present invention is not particularly limited as long as it is usually used in a chemically amplified resist composition, and examples thereof include onium salt compounds, N-sulfonyloxyimides. Examples thereof include compounds, halogen-containing compounds, diazoketone compounds and the like.
  • a photo-acid generator can be used individually by 1 type or in combination of 2 or more types.
  • the electron acceptability is preferably high, and the molar extinction coefficient with respect to 365 nm is preferably 1.0 ⁇ 10 4 cm 2 / mol or less.
  • onium salt compounds examples include sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.
  • examples of the sulfonium salt and iodonium salt include those described in WO2011 / 093139. Specific examples include photoacid generators represented by the following formula (9) or (10), but are not limited thereto.
  • R a COOR b SO 3 ⁇ M + (9)
  • R a represents a monovalent organic group having 1 to 200 carbon atoms which may have a substituent
  • R b represents that some hydrogen atoms are substituted with fluorine atoms. Or a good hydrocarbon group.
  • M + represents a counter cation.
  • R a COOCH 2 CH 2 CFHCF 2 SO 3 ⁇ M + (10)
  • R a represents a monovalent organic group having 1 to 200 carbon atoms which may have a substituent.
  • M + represents a counter cation.
  • the photo acid generator may be added to the resist composition as a low molecular weight component, or may be contained as a polymer unit. That is, the aspect contained in the polymer as a unit so that it may couple
  • the photoacid generator is a sulfonium salt
  • the hydroxy group-containing compound according to one embodiment of the present invention is not particularly limited as long as hydrogen of a hydroxy group can be a hydrogen supply source when the photoacid generator is decomposed.
  • the acid generation efficiency from the photoacid generator is improved, and further, the ionization potential is increased as compared with the case where the hydroxy group is added to have no hydroxy group. Can be lowered.
  • hydroxy group-containing compounds include units derived from hydroxystyrene, hydroxyvinylnaphthalene, hydroxyphenyl acrylate, hydroxyphenyl methacrylate, hydroxy naphthyl acrylate, hydroxy norbornene acrylate, hydroxy norbornene methacrylate, hydroxy naphthyl methacrylate, hydroxy adamantane acrylate, hydroxy adamantane methacrylate, and the like.
  • Polymers including: polyphenol compounds such as bisphenol and TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) calixarene; and the like.
  • polymers containing units derived from hydroxystyrene, hydroxyvinylnaphthalene, hydroxyphenyl acrylate, hydroxyphenyl methacrylate, hydroxy naphthyl acrylate, hydroxy naphthyl methacrylate and the like are preferable.
  • the hydroxyaryl group-containing compound include a polymer having a unit represented by the following formula (11).
  • Ar 3 represents an arylene group
  • R 7 represents a hydrogen atom or a hydrocarbon group
  • L represents a carbonyloxy group or a direct bond.
  • the Ar 3 arylene group may further have a hydroxy group in addition to the hydroxy group disclosed in formula (11).
  • the Ar 3 arylene group is preferably an arylene group having 6 to 14 carbon atoms which may have a substituent other than a hydroxy group, more preferably a phenylene group or a naphthylene group which may have a substituent.
  • a phenylene group which may have a group is more preferable.
  • the hydrocarbon group for R 7 is preferably an alkyl group having 1 to 12 carbon atoms.
  • R 7 is more preferably a hydrogen atom or a methyl group.
  • hydroxyaryl group-containing compound examples include polymers having units represented by the following formula, but are not limited thereto.
  • Examples of the acid reaction compound include a compound having a protecting group that is deprotected by an acid, a compound having a polymerizable group that is polymerized by an acid, and a crosslinking agent having a crosslinking action by an acid.
  • a compound having a protecting group that is deprotected by an acid is, for example, a compound in which the solubility in a developer is changed when a protective group is deprotected by an acid to form a polar group when the composition is used as a resist composition. It is.
  • aqueous development using an alkaline developer or the like it is insoluble in an alkaline developer, but the protective group is deprotected in the exposed area by an acid generated from the photoacid generator upon exposure, whereby an alkaline developer It is a compound that becomes soluble in.
  • the developer is not limited to an alkali developer, and may be a neutral developer or an organic solvent development. Therefore, when an organic solvent developer is used, the compound having a protecting group that is deprotected by an acid is deprotected in the exposed area by the acid generated from the photoacid generator upon exposure, and the organic solvent developer Is a compound whose solubility is reduced.
  • the polar group examples include a hydroxy group, a carboxy group, an amino group, and a sulfo group.
  • Specific examples of the protecting group to be deprotected with an acid include an ester group, an acetal group, a tetrahydropyranyl group, a siloxy group, and a benzyloxy group.
  • the compound having the protecting group a compound having a styrene skeleton, a methacrylate or an acrylate skeleton pendant with these protecting groups is preferably used.
  • the compound having a protecting group to be deprotected with an acid may be a protecting group-containing low molecular weight compound or a protecting group-containing polymer.
  • the low molecular weight compound has a weight average molecular weight of less than 1000, and the polymer has a weight average molecular weight of 1000 or more.
  • the compound having a polymerizable group that is polymerized with an acid is a compound whose solubility in a developer is changed by polymerization of the polymerizable group with an acid.
  • aqueous development it is soluble in an aqueous developer, but the polymerizable group is polymerized in the exposed area by the acid generated from the photoacid generator upon exposure, and is soluble in the aqueous developer. It is a compound that decreases.
  • an organic solvent developer may be used instead of the aqueous developer.
  • Examples of the polymerizable group that is polymerized with an acid include an epoxy group, a vinyloxy group, and an oxetanyl group.
  • the compound having a polymerizable group a compound having a styrene skeleton, a methacrylate or an acrylate skeleton having these polymerizable groups is preferably used.
  • the compound having a polymerizable group that is polymerized with an acid may be a polymerizable low-molecular compound or a polymer.
  • the crosslinking agent having a crosslinking action with an acid is a compound that changes the solubility in a developer by crosslinking with an acid.
  • aqueous development aqueous development It acts on a compound that is soluble in a liquid and reduces the solubility of the compound in an aqueous developer after crosslinking.
  • methylated melamine such as 2,4,6-tris [bis (methoxymethyl) amino] -1,3,5-triazine, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, etc.
  • examples of the cross-linking partner compound include compounds having a phenolic hydroxyl group or a carboxy group.
  • the compound having a crosslinking action with an acid may be a polymerizable low molecular compound or a polymer.
  • composition Containing Photosensitizer Precursor One aspect of the present invention is the photosensitizer precursor, the photoacid generator, the hydroxy group-containing compound, and the acid-reactive compound.
  • the photosensitizer precursor is a photosensitizer in the above composition, wherein the photoacid generator generates an acid upon irradiation with active energy rays or the like, and is deprotected by the acid. obtain.
  • the photoacid generator generates an acid by the first irradiation using the first active energy ray, the photosensitizer precursor is deprotected by the acid to become a photosensitizer, and By performing the second irradiation using the second active energy having a wavelength at which the photosensitizer absorbs light, the photoacid generator is again applied only to the portion subjected to the first irradiation by the action of the photosensitizer. It is preferable that an acid can be generated. Thereby, while the said acid generates a photosensitizer further, the acid reaction compound which reacts with an acid can be made to react.
  • a resist composition comprising the photosensitizer precursor, a compound having a protecting group that is deprotected by the acid, and a photoacid generator; a compound having a polymerizable group that is polymerized by the photosensitizer precursor and the acid.
  • a resist composition comprising: and a photoacid generator; a photosensitizer precursor; a crosslinking agent having a crosslinking action with an acid; a compound that reacts with the crosslinking agent to change solubility in a developer; And a resist composition containing a photoacid generator.
  • the photosensitizer precursor in one embodiment of the present invention can be preferably used as a sensitizer for positive and negative resist compositions.
  • the content of the photosensitizer precursor in the composition of one embodiment of the present invention is preferably 0.1 to 5 molar equivalents, and preferably 0.5 to 2.0 molar equivalents with respect to the photoacid generator. It is more preferable.
  • the mass is based on the polymer main chain.
  • the content of the photoacid generator in the resist composition of one embodiment of the present invention is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resist composition component excluding the photoacid generator. The amount is more preferably 30 parts by mass, and further preferably 1 to 15 parts by mass.
  • the photoacid generator in the composition within the above range, for example, even when the composition is used as a permanent film such as an insulating film such as a display body, the light transmittance can be increased.
  • the solvent is not included in 100 parts by mass of the resist composition component.
  • the photosensitizer precursor is included as a unit of the same polymer together with at least one selected from the group consisting of the photoacid generator, the hydroxy group-containing compound and the acid-reactive compound.
  • the unit acting as an agent precursor is preferably 1 to 40 mol%, more preferably 10 to 35 mol%, and still more preferably 10 to 30 mol% in the total polymer unit.
  • the photoacid generator When the photoacid generator is included as a unit of the same polymer together with at least one selected from the group consisting of the photosensitizer precursor, the hydroxy group-containing compound, and the acid-reactive compound, the photoacid generator
  • the unit acting as an agent is preferably 1 to 40% by mole, more preferably 5 to 35% by mole, and still more preferably 5 to 30% by mole based on all units of the polymer.
  • the hydroxy group-containing compound When the hydroxy group-containing compound is contained as a unit of the same polymer together with at least one selected from the group consisting of the photosensitizer precursor, the photoacid generator and the acid-reactive compound, the hydroxy group-containing compound
  • the unit acting as a compound is preferably from 3 to 90 mol%, more preferably from 5 to 80 mol%, more preferably from 7 to 70 mol% in the whole polymer unit for a positive resist composition for aqueous development. More preferably.
  • a negative resist composition for aqueous development it is preferably 60 to 99 mol%, more preferably 70 to 98 mol%, and still more preferably 75 to 98 mol% in the total unit of the polymer.
  • the acid-reactive compound is included as a unit of the same polymer together with at least one selected from the group consisting of the photosensitizer precursor, the photoacid generator, and the hydroxy group-containing compound, the photosensitization
  • the unit acting as the agent precursor is preferably 3 to 40 mol%, more preferably 5 to 35 mol%, and still more preferably 7 to 30 mol% in the total polymer unit.
  • the polymer in one embodiment of the present invention preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 2,000 to 50,000, and even more preferably 2,000 to 15,000.
  • the polymer preferably has a dispersity (molecular weight distribution) (Mw / Mn) of 1.0 to 1.7, more preferably 1.0 to 1.2 from the viewpoint of sensitivity.
  • the weight average molecular weight and dispersity of the polymer are defined as polystyrene converted values by GPC measurement.
  • an acid diffusion controller in addition to the above components, as an optional component, an acid diffusion controller, a surfactant, an organic carboxylic acid, a solvent, a dissolution inhibitor, which are used in an ordinary resist composition, A stabilizer, a dye, and other sensitizers other than the photosensitizer precursor may be included in combination.
  • the acid diffusion control agent controls the diffusion phenomenon of the acid generated from the photoacid generator in the resist film, and has an effect of controlling an undesirable chemical reaction in the non-exposed region. Therefore, the storage stability of the resulting resist composition is improved, and the resolution as a resist is improved.
  • the acid diffusion controller examples include compounds having one, two, or three nitrogen atoms in the same molecule, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.
  • the acid diffusion controlling agent a photodegradable base that is sensitized by exposure to generate a weak acid can also be used.
  • the photodegradable base include onium salt compounds and iodonium salt compounds that lose acid diffusion controllability by being decomposed by exposure. Specifically, Japanese Patent Nos.
  • the content of the acid diffusion controller is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the resist composition component. More preferably, it is 3 parts by mass.
  • the surfactant is preferably used for improving the coating property.
  • surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. Agents, fluorosurfactants, organosiloxane polymers, and the like.
  • the content of the surfactant is preferably 0.0001 to 2 parts by mass, more preferably 0.0005 to 1 part by mass with respect to 100 parts by mass of the resist composition component.
  • organic carboxylic acid examples include aliphatic carboxylic acid, alicyclic carboxylic acid, unsaturated aliphatic carboxylic acid, oxycarboxylic acid, alkoxycarboxylic acid, ketocarboxylic acid, benzoic acid derivative, phthalic acid, terephthalic acid, isophthalic acid, 2 -Naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid and the like.
  • Aromatic organic carboxylic acids, such as benzoic acid and 1-hydroxy-2-naphthoic acid, among them, are less likely to volatilize from the resist film surface and contaminate the drawing chamber when the electron beam exposure is performed in vacuum.
  • 2-hydroxy-3-naphthoic acid is preferred as the organic carboxylic acid.
  • the content of the organic carboxylic acid is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the resist composition component. It is.
  • solvent examples include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate.
  • PGME propylene glycol monomethyl ether
  • PGMEA propylene glycol monomethyl ether propionate
  • propylene glycol monoethyl ether acetate examples include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate.
  • the resist composition component is preferably dissolved in the solvent so that the solid content concentration is 1 to 40% by mass. More preferably, it is 1 to 30% by mass, and further preferably 3 to 20% by mass. By setting the solid content concentration in such a range, the above film thickness can be achieved.
  • the resist composition of one embodiment of the present invention may contain a fluorine-containing water-repellent polymer.
  • a fluorine-containing water-repellent polymer The thing normally used for the immersion exposure process is mentioned, The one where a fluorine atom content rate is larger than the said polymer is preferable. Accordingly, when the resist film is formed using the resist composition, the fluorine-containing water-repellent polymer can be unevenly distributed on the resist film surface due to the water-repellent property of the fluorine-containing water-repellent polymer. .
  • the composition of one aspect of the present invention is obtained by mixing the components of the above composition, and the mixing method is not particularly limited.
  • the resist composition of one embodiment of the present invention may contain a ketone derivative represented by the following general formula (12) instead of the sensitizer precursor.
  • the ketone derivative corresponds to one produced by hydrolysis of the sensitizer precursor by acid treatment.
  • Each substituent in the following general formula (12) is the same as the substituent in the above general formula (1).
  • it can be used as a photosensitizer having a large absorption with a molar extinction coefficient at 365 nm of 1.0 ⁇ 10 5 cm 2 / mol or more without requiring a deprotection reaction with an acid. Therefore, it can be suitably used as a chemically amplified resist composition for UV, and can be suitably used for optical device applications that require particularly high visible light transmittance.
  • the acid generation efficiency can be improved by including the ketone derivative.
  • One embodiment of the present invention includes a step of applying the composition on a substrate to form a resist film (hereinafter also referred to as a “resist film forming step”), and a first step in the resist film.
  • a step of irradiating active energy rays hereinafter also referred to as “first irradiation step” and a step of irradiating the resist film irradiated with the first active energy rays with second active energy rays (hereinafter referred to as “second irradiation”).
  • a step of developing the resist film irradiated with the second active energy ray to obtain a pattern hereinafter also referred to as “pattern formation step”).
  • the photoacid generator by performing the first irradiation with the first active energy ray, the photoacid generator generates an acid, and the photosensitizer precursor is deprotected by the acid to cause photosensitization. Become a sensitizer. Then, by performing the second irradiation with the second active energy ray having a wavelength at which the photosensitizer absorbs light, the photoacid generator is again applied only to the portion subjected to the first irradiation by the action of the photosensitizer. Is preferably capable of generating an acid. Thereby, while the said acid generates a photosensitizer further, the acid reaction compound which reacts with an acid can be made to react.
  • the first active energy ray used in the first irradiation may be a particle beam or an electromagnetic wave that can generate an acid when the photoacid generator contained in the composition is activated, such as a KrF excimer laser beam or an ArF excimer laser.
  • a KrF excimer laser beam or an ArF excimer laser examples thereof include light, F 2 excimer laser light, electron beam, UV, visible light, X-ray, ion beam, g-line, h-line, i-line, and EUV. Of these, electron beam, X-ray, EUV and the like are preferable.
  • the second active energy rays used in the second irradiation photosensitizer that produces by R 3 and R 4 of the photosensitizer precursor represented by the formula (1) is deprotected to absorb Any electromagnetic wave may be used as long as it has a wavelength.
  • the electromagnetic wave include KrF excimer laser light, ArF excimer laser light, F 2 excimer laser light, UV, visible light, g-line, h-line, and i-line. Is mentioned.
  • the electromagnetic wave of the first active energy ray preferably has a shorter wavelength than the electromagnetic wave used as the second active energy ray.
  • One embodiment of the present invention includes a resist film formation step, a first irradiation step, a second irradiation step, and a pattern formation step using the above composition, and a substrate having a pattern before obtaining individualized chips. It may be a manufacturing method.
  • the resist film formed from the resist composition preferably has a thickness of 10 to 200 nm.
  • the resist composition is applied onto the substrate by an appropriate application method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, and the like, and is performed at 60 to 150 ° C. for 1 to 20 minutes, preferably 80 to Pre-bake at 120 ° C. for 1 to 10 minutes to form a thin film.
  • the thickness of this coating film is 10 to 200 nm, preferably 20 to 150 nm.
  • the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
  • the molar extinction coefficient after acid treatment of a compound that is, the molar extinction coefficient at 365 nm of a benzophenone compound derivative obtained by deprotecting the compound was measured with a UV-VIS spectrophotometer (Hitachi Co., Ltd.). (U-3300) manufactured by Seisakusho, using chloroform or acetonitrile as a solvent.
  • Synthesis Example 1 Synthesis of 2,4-methoxy-4′-methylthiobenzophenone (sensitizer compound A1) 8.0 g of 4-bromothioanisole was dissolved in 32 g of tetrahydrofuran, and 1 mol / L methylmagnesium bromide was dissolved therein. 39 ml of THF solution is added dropwise at 5 ° C. or lower. After dropping, the mixture is stirred at 5 ° C. or lower for 30 minutes to obtain a THF solution of 4-methylthiophenylmagnesium bromide.
  • the crude crystals are recrystallized using 120 g of ethanol to obtain 7.6 g of 2,4-dimethoxy-4′-methylthiobenzophenone.
  • the molar extinction coefficient at 365 nm in chloroform solvent is 1.1 ⁇ 10 6 cm 2 / mol.
  • the crude crystals are recrystallized using 40 g of ethanol to obtain 5.6 g of 4-methylthio-4′-phenylthiobenzophenone.
  • the molar extinction coefficient at 365 nm in chloroform solvent is 2.6 ⁇ 10 6 cm 2 / mol.
  • Synthesis Example 6 Synthesis of (4-methylthio) phenyl- (4′-phenylthio) phenyl-diethoxymethane (Precursor Compound B3) (4-Methylthio) phenyl- (4′-phenylthio) obtained in Synthesis Example 5 5.0 g of phenyl-dimethoxymethane, 300 mg of camphorsulfonic acid and 4.3 g of triethyl orthoformate are dissolved in 32.5 g of dehydrated ethanol, and the mixture is stirred at 70 ° C. for 5 hours while distilling off methanol in the solution together with ethanol. .
  • Synthesis Example 8 Synthesis of 2-methoxy-4′-methylthiobenzophenone (sensitizer compound A3) The same procedure as in Synthesis Example 1 except that 2-methoxybenzoyl chloride was used instead of 2,4-dimethoxybenzoyl chloride To give 2-methoxy-4′-methylthiobenzophenone.
  • the molar extinction coefficient at 365 nm in chloroform solvent is 1.0 ⁇ 10 5 cm 2 / mol or more.
  • Synthesis Example 10 Synthesis of 4- (4-methoxyphenyl) -4′-methylthiobenzophenone (sensitizer compound A4) 4- (4-methoxyphenyl) benzoyl chloride is used in place of 2,4-dimethoxybenzoyl chloride Except for the above, the same operation as in Synthesis Example 1 is carried out to obtain 5.2 g of 4- (4-methoxyphenyl) -4′-methylthiobenzophenone.
  • the molar extinction coefficient at 365 nm in chloroform solvent is 1.0 ⁇ 10 5 cm 2 / mol or more.
  • Synthesis Example 12 Synthesis of 2-methylthio-4,4′-dimethoxybenzophenone (sensitizer compound A5) 4.6 g of 3-methylthioanisole and 4.9 g of aluminum chloride are dissolved in 15 g of dichloromethane. 4-methoxybenzoyl chloride 5.0g is dripped at this at 5 degrees C or less over 30 minutes. Then, after stirring at 5 ° C. for 2 hours, 15 g of pure water is added so as to be 25 ° C. or less, and further stirred for 10 minutes.
  • the organic layer is separated and recovered and washed with pure water, dichloromethane is distilled off, and the resulting residue is produced by recrystallization using 70 g of ethanol, whereby 2-methylthio-4,4′-dimethoxybenzophenone. 6.5 g is obtained.
  • the molar extinction coefficient at 365 nm in chloroform solvent is 1.0 ⁇ 10 5 cm 2 / mol or more.
  • Synthesis Example 19 Synthesis of 4- (4-hydroxyphenylthio) -4′-methylthiobenzophenone (sensitizer Compound A7) Same as Synthesis Example 4 except that 4-hydroxybenzenethiol was used instead of thiophenol By performing the operation, 5.8 g of 4- (4-hydroxyphenylthio) -4′-methylthiobenzophenone is obtained.
  • the molar extinction coefficient at 365 nm in chloroform solvent is 3.01 ⁇ 10 6 cm 2 / mol.
  • the molar extinction coefficient of 365 nm with acetonitrile solvent is 1.73 ⁇ 10 6 cm 2 / mol.
  • Synthesis Example 20 Synthesis of 4- (4-hydroxyphenylthio) phenyl-4′-methylthiophenyl-dimethoxymethane (Precursor Compound B9) 4- (4 instead of 2,4-dimethoxy-4′-methylthiobenzophenone Except for using -hydroxyphenylthio) -4'-methylthiobenzophenone, 3.3 g of 4- (4-hydroxyphenylthio) phenyl-4'-methylthiophenyl-dimethoxymethane was obtained by performing the same operation as in Synthesis Example 2 above. obtain. The sum total of Hammett substituent constants ⁇ is 0.2 or less.
  • Synthesis Example 21 Synthesis of 4,4′-di (4-hydroxyphenylthio) benzophenone (sensitizer Compound A8) 6.5 g of 4,4′-difluorobenzophenone was dissolved in 20 g of DMF, and 4-hydroxybenzene was dissolved therein. Add 11.3 g of thiol and 12.4 g of potassium carbonate and stir at 70 ° C. for 2 hours. After stirring, 90 g of pure water is added and the mixture is further stirred for 10 minutes to precipitate a solid. The precipitated solid is collected by filtration and vacuum dried to obtain crude crystals. The crude crystals are dispersed in 120 g of methylene chloride and stirred for 1 hour.
  • Synthesis Example 22 Synthesis of 4- [4- (methoxymethoxy) phenylthio] phenyl-4′-methylthiophenyl-dimethoxymethane (precursor compound B11) 4- (4-hydroxyphenylthio) phenyl obtained in Synthesis Example 20 Dissolve 2.0 g of -4'-methylthiophenyl-dimethoxymethane in 8.0 g of DMF, add 0.61 g of chloromethyl methyl ether and 1.1 g of potassium carbonate, and stir at 70 ° C. for 12 hours. After stirring, 16 g of pure water and 32 g of methylene chloride are added to recover the organic layer, which is further washed twice with pure water.
  • the solid obtained by separating this by filtration under reduced pressure was washed twice with 300 g of pure water and then vacuum-dried to obtain 9.2 g of copolymer A shown below as a white solid.
  • the monomer ratio of the copolymer unit in the present invention is not limited to the following.
  • Synthesis Example 25 Synthesis of Copolymer B 7.0 g acetoxystyrene, 3.4 g 2-methyladamantane-2-methacrylate, 0.022 g butyl mercaptan and 0.40 g dimethyl-2,2′-azobis (2-Methylpropionate) (AIBN) is dissolved in 35 g of tetrahydrofuran (THF) and deoxygenated. This is dripped over 4 hours in 20 g of THF which has been brought to a reflux temperature in advance by flowing nitrogen gas. After dropping, the mixture is stirred for 2 hours and then cooled to room temperature.
  • THF tetrahydrofuran
  • the mixture is stirred for 2 hours and then cooled to 25 ° C. After cooling, it is reprecipitated by dropping it into a mixed solvent consisting of 107 g of hexane and 11 g of tetrahydrofuran. This is filtered, then dispersed and washed twice with 37 g of hexane, filtered and vacuum dried to obtain 6.2 g of the target copolymer E as a white powder.
  • required by polystyrene conversion using the gel permeation chromatography is 8600.
  • Synthesis Example 29 Synthesis of Copolymer F 0.80 g of the above precursor compound B8, 3.9 g of ⁇ -methacryloyloxy- ⁇ -butyrolactone, 2.9 g of 2-methyladamantane-2-methacrylate, (4 -Hydroxy) phenyl methacrylate 2.3 g, 5-phenyldibenzothiophenium 1,1-difluoro-2- (2-methacryloyloxy) -ethanesulfonate 0.49 g, butyl mercaptan 0.13 g and (4-hydroxy) 2.9 g of phenyl methacrylate and 0.56 g of dimethyl-2,2′-azobis (2-methylpropionate) (product name V601, manufactured by Wako Pure Chemical Industries, Ltd.
  • V601 Each is weighed and dissolved in 12.2 g of tetrahydrofuran and degassed under reduced pressure. After deaeration, the solution is added dropwise over 4 hours to a flask in which 4 g of THF is refluxed by turning into a nitrogen stream. After dropping, the mixture is stirred for 2 hours and then cooled to 25 ° C. After cooling, it is reprecipitated by dropping it into a mixed solvent consisting of 107 g of hexane and 11 g of tetrahydrofuran.
  • Synthesis Example 30 Synthesis of Copolymer G ⁇ -Methacryloyloxy- ⁇ -butyrolactone 5.0 g, 2-methyladamantane-2-methacrylate 6.0 g, V601 0.51 g, and tetrahydrofuran 26 g were dissolved. Perform vacuum degassing. This is dripped over 4 hours in the flask which refluxed THF4g. After dropping, the mixture is stirred for 2 hours and then cooled to 25 ° C. This solution is reprecipitated by dropping it into a mixed solvent consisting of 160 g of hexane and 18 g of tetrahydrofuran. This is filtered, dispersed and washed twice with 37 g of hexane, and vacuum dried after filtration to obtain 7.4 g of the desired copolymer G as a white powder.
  • Evaluation samples 1 to 20 are prepared as follows. 7000 mg of cyclohexanone, 500 mg of copolymer A, C and G, 507 mg of copolymer E, 497 mg of copolymer F and 500 mg of copolymer H, and diphenyliodonium-nona as a photoacid generator (PAG) 0.043 mmol of fluorobutanesulfonate (DPI-Nf) or phenyldibenzothionium-nonafluorobutanesulfonate (PBpS-Nf), precursor compounds B1 to 3, B9 and B10 as photosensitizer precursors and 2 as comparative compounds , 2-diphenyl-1,3-dioxolane (compound C1) (the sum of Hammett substituent constants ⁇ is 0, the molar extinction coefficient at 365 nm in chloroform solvent is 6.3 ⁇ 10 4
  • Example evaluation 1 Each of the evaluation samples 1 to 20 is applied onto a Si wafer that has been subjected to hexamethyldisilazane (HMDS) treatment in advance, spin-coated, and heated at 110 ° C. to obtain a resist film having a thickness of 100 nm.
  • the evaluation sample resist film is exposed by changing the exposure amount so that a 1: 1 line and space pattern having a line width half pitch of 100 nm is formed by an EB drawing apparatus of 30 keV. Thereafter, the entire surface of the wafer is irradiated with ultraviolet rays using a UV light having an emission line of 365 nm. Subsequently, it heats at 110 degreeC on a hotplate for 1 minute.
  • HMDS hexamethyldisilazane
  • Examples 1 to 9 and 13 to 16 using the resist composition mixed with the photosensitizer precursor according to one embodiment of the present invention had a minimum EB by UV irradiation after EB irradiation. The exposure amount becomes small.
  • the acid generation is improved by the photosensitization of the photosensitizer generated from the photosensitizer precursor, and the sensitivity is improved. I understand.
  • the acid generation efficiency by EB is improved by including a compound having a hydroxy group in the resist as compared with the resist having no hydroxy group. It can be seen that the sensitivity is increased.
  • the effect of UV irradiation is greater than the comparison between Examples 4 and 5 in that the molar extinction coefficient of the photosensitizer produced from the photosensitizer precursor is large if the sum of the Hammett substituent constants ⁇ is 0.2 or less. There is a tendency toward higher sensitivity.
  • Examples 5, 13 and 14 are compared, when the precursor compound B9 or B10 is mixed in the resist, the sensitivity is higher than when the precursor compound B2 is mixed in the resist. This is because, like sensitizer compounds A7 and A8 produced from precursor compounds B9 and B10, an increase in the molar extinction coefficient of 365 nm by introducing a 4-hydroxyphenylthio group, and an electron donating property due to the phenolic hydroxyl group. This is thought to be due to the improvement. Furthermore, it is considered that the acid generation efficiency of the photosensitization occurring between the photosensitizer and the acid generator is improved by the phenolic hydroxyl group of the photosensitizer becoming a proton source.
  • the compound C1 added in Comparative Examples 3 and 4 has a sum of Hammett substituent constants ⁇ of 0 or more and a molar extinction coefficient at 365 nm of 6.3 ⁇ 10 4 cm 2 / mol, which is very low, so the sensitization efficiency in UV
  • UV irradiation at 200 mJ / cm 2 did not improve the amount of acid generated and did not increase the sensitivity. From the above, it is considered that a highly sensitive photosensitizer precursor can be obtained by adding an electron-donating group to the compound to increase the molar absorption coefficient at 365 nm.
  • Evaluation samples 16 to 25 are prepared as follows. To 7000 mg of cyclohexanone, 500 mg of the copolymer A or H, and diphenyliodonium-nonafluorobutanesulfonate (DPI-Nf), phenyldibenzothionium-nonafluorobutanesulfonate (PBpS-Nf) or (PAG) as a photoacid generator (PAG) 0.043 mmol of 4-phenylthio) phenyldiphenylsulfonium-nonafluorobutanesulfonate (PSDPS-Nf) and 0.043 mmol of any of sensitizer compounds A1, A2, A7 and A8 as photosensitizers, respectively, or A sample is prepared by adding no trioctylamine as a quencher at a ratio of 0.0043 mmol. Details of the prepared samples are shown in
  • the evaluation sample resist film is exposed by changing the exposure amount with a UV exposure apparatus having a bright line of 365 nm through a 1: 1 line having a line width half pitch of 2 ⁇ m and a space pattern mask. Subsequently, it heats at 110 degreeC on a hotplate for 1 minute.
  • PBpS-Nf does not generate acid because there is no UV absorption at 365 nm, but Examples 17, 18, and 21 using resist compositions mixed with photosensitizers in one embodiment of the present invention.
  • 24, and 25 can generate an acid when the added photosensitizer absorbs light during UV irradiation and sensitizes the acid generator.
  • each example has higher sensitivity than Comparative Examples 6 and 7 in which an acid generator having UV absorption at 365 nm is mixed.
  • the acid generation was improved and the sensitivity was improved.
  • the irradiation wavelength was improved. It can be seen that even an acid generator that absorbs UV has higher sensitivity due to the effect of the photosensitizer.
  • Examples 17, 18, 24 and 25 show that the greater the molar extinction coefficient of the added sensitizer compound, the higher the sensitivity.
  • Examples 24 and 25 are considered to be more sensitive because electron donating property is improved by introducing a hydroxy group into the thioaryl structure as in sensitizer compounds A7 and A8.
  • the effect of improving the acid generation efficiency in the sensitization reaction that occurs between the photosensitizer and the acid generator is also observed by using the phenolic hydroxyl group of the sensitizer compound as a proton source.
  • a resist composition including a photosensitizer precursor for improving acid generation efficiency and forming a photoresist having high sensitivity, high resolution, and high LWR characteristics can be provided. .

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

La présente invention concerne une composition de résist qui améliore l'efficacité de génération d'acide et est utilisée pour produire un photorésist ayant une sensibilité élevée, une haute résolution et des propriétés de LWR élevées. La présente invention concerne un composé représenté par une formule générale (1). (1) (Dans la formule (1) : Ar 1 et Ar 2 représentent indépendamment un groupe phénylène ayant facultativement un substituant ; R 1 représente un élément choisi dans le groupe constitué par un groupe thioalcoxy phényle, un groupe arylthio, et un groupe thioalcoxy ayant éventuellement un substituant ; X représente un élément choisi dans le groupe constitué par un atome de soufre, un atome d'oxygène et une liaison directe ; R 2 représente soit un groupe aryle soit un groupe alkyle ayant éventuellement un substituant ; chaque Y représente indépendamment un atome d'oxygène ou un atome de soufre ; R 3 et R 4 représentent indépendamment un groupe alkyle linéaire, ramifié ou cyclique ayant éventuellement un substituant ; R 3 et R 4 sont facultativement liés l'un à l'autre de façon à former une structure en anneau avec deux Y dans la formule ; au moins l'une des liaisons simples carbone-carbone dans le groupe alkyle compris dans R 1 , R 2 , R 3 , et R 4 est éventuellement substituée par une double liaison carbone-carbone ou une triple liaison carbone-carbone ; et au moins l'un des groupes méthylène dans le groupe alkyle compris dans R 1 , R 2 , R 3 , et R 4 éventuellement substitué par un groupe divalent contenant un hétéroatome.)
PCT/JP2017/016486 2016-04-28 2017-04-26 Composition de résist et procédé de production d'un dispositif l'utilisant WO2017188297A1 (fr)

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JP2019182813A (ja) * 2018-04-17 2019-10-24 東洋合成工業株式会社 組成物及びそれを用いたデバイスの製造方法
JP2020176096A (ja) * 2019-04-19 2020-10-29 東洋合成工業株式会社 オニウム塩、組成物及びそれを用いたデバイスの製造方法
WO2024038802A1 (fr) * 2022-08-15 2024-02-22 富士フイルム株式会社 Composition de résine sensible aux rayons actiniques ou au rayonnement, film de réserve, procédé de formation de motif, et procédé de fabrication de dispositif électronique
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WO2019151400A1 (fr) * 2018-01-31 2019-08-08 三菱瓦斯化学株式会社 Composé, résine, composition, procédé de formation de motif de photorésine, procédé de formation de motif de circuit, et procédé de purification de résine
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JP7079647B2 (ja) 2018-04-17 2022-06-02 東洋合成工業株式会社 組成物及びそれを用いたデバイスの製造方法
JP2020176096A (ja) * 2019-04-19 2020-10-29 東洋合成工業株式会社 オニウム塩、組成物及びそれを用いたデバイスの製造方法
JP7249198B2 (ja) 2019-04-19 2023-03-30 東洋合成工業株式会社 オニウム塩、組成物及びそれを用いたデバイスの製造方法
JP7478650B2 (ja) 2019-12-13 2024-05-07 住友化学株式会社 レジスト組成物及びレジストパターンの製造方法
WO2024038802A1 (fr) * 2022-08-15 2024-02-22 富士フイルム株式会社 Composition de résine sensible aux rayons actiniques ou au rayonnement, film de réserve, procédé de formation de motif, et procédé de fabrication de dispositif électronique

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