WO2008068971A1 - Composition de résist positif pour une exposition à une immersion dans un liquide et procédé de formation de motif de résist - Google Patents

Composition de résist positif pour une exposition à une immersion dans un liquide et procédé de formation de motif de résist Download PDF

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Publication number
WO2008068971A1
WO2008068971A1 PCT/JP2007/070749 JP2007070749W WO2008068971A1 WO 2008068971 A1 WO2008068971 A1 WO 2008068971A1 JP 2007070749 W JP2007070749 W JP 2007070749W WO 2008068971 A1 WO2008068971 A1 WO 2008068971A1
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Prior art keywords
group
alkyl group
resin
structural unit
acid
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PCT/JP2007/070749
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English (en)
Japanese (ja)
Inventor
Yoshiyuki Utsumi
Yasuhiro Yoshii
Tsuyoshi Nakamura
Makiko Irie
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Tokyo Ohka Kogyo Co., Ltd.
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Publication of WO2008068971A1 publication Critical patent/WO2008068971A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means

Definitions

  • the present invention relates to a positive resist composition for immersion exposure and a method for forming a resist pattern.
  • the present invention relates to a positive resist composition for immersion exposure and a resist pattern forming method used for immersion exposure (Liquid Immersion Lithography).
  • a resist film made of a resist material is formed on a substrate, and the resist film is exposed to radiation such as light and electron beams through a mask on which a predetermined pattern is formed.
  • a step of forming a resist pattern having a predetermined shape on the resist film is performed by performing selective exposure and developing.
  • the exposure light source has become shorter in wavelength and the projection lens has a higher numerical aperture (high ⁇ ⁇ ).
  • an ArF excimer laser having a wavelength of 193 nm is used as the light source.
  • An exposure machine has been developed.
  • the resist material is required to have improved lithographic characteristics such as sensitivity to the exposure light source and resolution capable of reproducing a pattern with fine dimensions.
  • a chemically amplified resist containing a base resin whose alkali solubility is changed by the action of an acid and an acid generator that generates an acid upon exposure is used.
  • (meth) acrylic acid means one or both of acrylic acid having a hydrogen atom bonded to the ⁇ -position and methacrylic acid having a methyl group bonded to the a-position.
  • (Meth) acrylic acid ester means either an acrylic acid ester with a hydrogen atom bonded to the ⁇ -position or a methacrylate ester with a methyl group bonded to the a-position!
  • (Meth) atalylate” means one or both of an acrylate with a hydrogen atom bonded to the ⁇ -position and a meta-acrylate with a methyl group bonded to the ⁇ -position.
  • immersion exposure As one of the methods for further improving the resolution, exposure is performed by interposing a liquid (immersion medium) having a refractive index higher than that of air between the objective lens of the exposure machine and the sample.
  • a lithography method for performing immersion exposure so-called “Liquid Immersion Lithography”, hereinafter referred to as “immersion exposure”.
  • immersion exposure With immersion exposure, the same high resolution can be achieved with a light source with the same exposure wavelength as when using a light source with a shorter wavelength or with a high NA lens. It is said that there is no decrease in depth. Moreover, immersion exposure can be performed using an existing exposure apparatus. Therefore, immersion exposure is expected to be able to form resist patterns with low cost, high resolution, and excellent depth of focus, so manufacturing semiconductor devices that require large capital investment
  • cost and lithography characteristics such as resolution
  • the semiconductor industry is attracting a great deal of attention.
  • Immersion exposure is effective in the formation of all pattern shapes, and can be combined with super-resolution techniques such as the phase shift method and the modified illumination method, which are currently under investigation!
  • super-resolution techniques such as the phase shift method and the modified illumination method, which are currently under investigation!
  • an immersion exposure technique a technique mainly using an ArF excimer laser as a light source is being actively researched.
  • water is mainly studied as an immersion medium.
  • Non-Patent Document 2 Proceedings of SPIE, Vol. 5754, 119-128 (2005).
  • Non-Patent Document 2 Proceedings oi 3 ⁇ 4PIE— The International Society lor Optical Engineering (2002), 4690, 76— 83.
  • the immersion medium comes into contact with the resist film and the lens during immersion exposure, the resist film changes in quality due to elution of substances contained in the resist into the immersion medium, and the performance is reduced. It is conceivable that the refractive index of the immersion medium may be locally changed by the applied material, or the dissolved material may contaminate the lens surface and adversely affect the lithography characteristics.
  • the present invention has been made in view of the above circumstances, and is the membrane surface highly hydrophobic? It is an object of the present invention to provide a positive resist composition for immersion exposure and a method for forming a resist pattern, which can form a resist film with good lithography characteristics.
  • the first aspect of the present invention for solving the above-mentioned problems is that a resin component (A) whose alkali solubility is increased by the action of an acid, an acid generator component (B) that generates an acid upon exposure, and a fluorine atom And an acid-dissociable group! /, A positive resist composition for immersion exposure containing a resin component (C), wherein the resin component (A) is derived from acrylic acid A resin (A1) having a structural unit (a) and containing no fluorine atom is contained, and the resin component (C) is a non-main chain cyclic resin (C1) and a main chain cyclic resin ( And a positive resist composition for immersion exposure containing C2).
  • the second aspect of the present invention includes a step of forming a resist film on a support using the positive resist composition for immersion exposure according to the first aspect of the present invention, and the resist A resist pattern forming method including a step of immersing and exposing a film and a step of developing the resist film to form a resist pattern.
  • alkyl group includes straight chain, branched chain and cyclic monovalent saturated hydrocarbon groups, unless otherwise specified.
  • a “lower alkyl group” is an alkyl group having 1 to 5 carbon atoms.
  • a “halogenated lower alkyl group” is a halogenated alkyl group having 1 to 5 carbon atoms.
  • alkylene group includes straight-chain, branched-chain and cyclic divalent saturated hydrocarbon groups unless otherwise specified.
  • the “structural unit” means a monomer unit (monomer unit) constituting a polymer compound (polymer, copolymer).
  • Exposure is a concept that includes general irradiation of radiation.
  • the present invention can provide a positive resist composition for immersion exposure and a method for forming a resist pattern, which can form a resist film excellent in hydrophobicity and lithographic properties of the film surface.
  • FIG. 1 is a diagram illustrating an advancing angle ( ⁇ ), a receding angle ( ⁇ ), and a falling angle ( ⁇ ).
  • the positive resist composition for immersion exposure of the present invention comprises a resin component (A) whose alkali solubility is increased by the action of an acid (hereinafter referred to as component (A)), and an acid generator that generates an acid upon exposure.
  • component (A) a resin component whose alkali solubility is increased by the action of an acid (hereinafter referred to as component (A)), and an acid generator that generates an acid upon exposure.
  • Ingredient (B) hereinafter referred to as component (B)
  • resin component (C) hereinafter referred to as component (C)
  • the component (A) is insoluble in alkali before exposure, and when acid is generated from the component (B) by exposure, the acid increases the alkali solubility of the component (A). Therefore, when a resist film obtained using the positive resist composition is selectively exposed in the formation of a resist pattern, the exposed area turns alkali-soluble while the unexposed area remains insoluble in alkali. Therefore, a resist pattern can be formed by performing alkali development.
  • Resin component (A) contains resin (A1).
  • the resin (A1) has a structural unit (a) derived from acrylic acid and does not contain a fluorine atom.
  • the resin (A1) is not particularly limited, and one or more resins that have been proposed as base resins for chemically amplified positive resists can be used.
  • the structural unit (a) derived from acrylic acid does not contain a fluorine atom.
  • the concept includes a derivative partially or wholly substituted with another group or atom.
  • Derivatives of acrylic acid include, for example, a substitution group (atom or group other than a hydrogen atom) bonded to the ⁇ -position carbon atom of narrowly defined acrylic acid! /, A substituted acrylic acid, and these acrylic acids And acrylic acid esters in which the hydrogen atom of the carboxy group is substituted with an organic group.
  • the “organic group” is a group containing a carbon atom, and the organic group in the acrylate ester is not particularly limited.
  • Each of the structural units (al) to (a4) is a kind of the structural unit (a).
  • a carbonyl group is bonded to the ⁇ -position of the acrylic acid (the ⁇ -position carbon atom)! /, The carbon atom.
  • Examples of the substituent of the ⁇ -substituted acrylic acid include a lower alkyl group, a halogenated lower alkyl group (however, the structural unit (a) excludes a fluorinated lower alkyl group).
  • specific examples of the lower alkyl group as a substituent at the ⁇ -position include a methyl group, an ethyl group, a propyl group, an isopropyl group, a ⁇ -butyl group, an isobutyl group, a tert-butyl group, and a pentyl group.
  • Lower linear or branched alkyl groups such as isopentyl group and neopentyl group.
  • halogenated lower alkyl group as a substituent at the a-position, part or all of the hydrogen atoms of the lower alkyl group are substituted with halogen atoms other than fluorine atoms, for example, chlorine atoms, bromine atoms, iodine atoms, etc. Groups.
  • the structural unit (a) has a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group (but not a fluorinated lower group) bonded to the ⁇ -position of acrylic acid! /
  • a hydrogen atom or a methyl group is the most preferred because of the ease of industrial availability in which a hydrogen atom or a lower alkyl group is preferred.
  • examples of the structural unit ( a ) include structural units represented by the following general formula (a).
  • R is a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group (excluding a fluorinated lower alkyl group), and X is a hydrogen atom or does not contain a fluorine atom. It is a monovalent organic group.
  • the lower alkyl group or halogenated lower alkyl group of R (excluding the fluorinated lower alkyl group) is the lower alkyl group or halogenated lower alkyl group (provided that the fluorinated lower alkyl group is substituted as the ⁇ -position substituent). Except for an alkyl group, the same as in) can be mentioned.
  • Examples of the organic group for X include the same as the above-mentioned “organic group in acrylic ester”.
  • the resin (A1) preferably contains the structural unit (a) in a ratio of 50 to 100 mol% with respect to the total of all the structural units constituting the resin (A1). ⁇ ; Containing 100 mol% is preferable.
  • the resin (A1) is preferably composed only of the structural unit (a) that also induces acrylic acid power! /.
  • the resin (A1) preferably has a structural unit (al) that does not have a fluorine atom and is derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group.
  • structural unit derived from an acrylate ester force means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
  • the acid dissociable, dissolution inhibiting group in the structural unit (al) has an alkali dissolution inhibiting property that makes the entire resin (A1) insoluble in alkali before dissociation, and the entire resin (A1) after dissociation. As long as it can be changed to alkali-soluble, those that have been proposed as acid dissociable, dissolution inhibiting groups for base resins for chemically amplified resists can be used.
  • an acid-releasing dissolution inhibiting group generally, a group that forms a cyclic or chain tertiary alkyl ester with a carboxy group in (meth) acrylic acid or the like; an acetal-type acid dissociation such as an alkoxyalkyl group or the like
  • the soluble dissolution inhibiting group is widely known.
  • the “(meth) acrylic acid ester” means one or both of an acrylic acid ester having a hydrogen atom bonded to the ⁇ -position and a methacrylic acid ester having a methyl group bonded to the ⁇ -position.
  • the "tertiary alkyl ester” is an ester formed by replacing a hydrogen atom of a carboxy group with a chain or cyclic alkyl group, and the carboxoxy group.
  • a structure in which the tertiary carbon atom of the chain or cyclic alkyl group is bonded to the oxygen atom at the terminal of (1 c (o) —o—)! When an acid acts on this tertiary alkyl ester, the bond is broken between the oxygen atom and the tertiary carbon atom.
  • the chain or cyclic alkyl group may have a substituent.
  • a group that becomes acid dissociable by constituting a carboxy group and a tertiary alkyl ester will be referred to as a “tertiary alkyl ester type acid dissociable, dissolution inhibiting group” for convenience.
  • the tertiary alkyl ester type acid dissociable, dissolution inhibiting group include aliphatic branched acid dissociable, dissolution inhibiting groups, and acid dissociable, dissolution inhibiting groups containing aliphatic cyclic groups.
  • aliphatic in the claims and specification of the present application is a relative concept to aromatics, and is defined as meaning a group, compound, etc. that does not have aromaticity. To do.
  • “Aliphatic branched” means that it has no aromaticity and has a branched structure.
  • the structure of the “aliphatic branched acid dissociable, dissolution inhibiting group” is not limited to a group consisting of carbon and hydrogen (a hydrocarbon group), but is preferably a hydrocarbon group. Further, the “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated.
  • aliphatic branched, acid dissociable, dissolution inhibiting group a tertiary alkyl group force s preferably 4 to 8 carbon atoms, in particular tert- butyl group, tert- pentyl group, heptyl group and the like to tert- is Can be mentioned.
  • the “aliphatic cyclic group” refers to a monocyclic group or a polycyclic group that does not have aromaticity! /.
  • the “aliphatic cyclic group” preferably has 4 to 20 carbon atoms.
  • the “aliphatic cyclic group” in the structural unit (al) may or may not have a substituent.
  • the basic ring structure excluding the substituent of the “aliphatic cyclic group” is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but a hydrocarbon group is preferred.
  • the “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated.
  • the “aliphatic cyclic group” is preferably a polycyclic group.
  • aliphatic cyclic group may be substituted with a lower alkyl group, a halogen atom other than a fluorine atom, or a halogenated alkyl group (excluding a fluorinated alkyl group).
  • a halogen atom other than a fluorine atom
  • a halogenated alkyl group excluding a fluorinated alkyl group.
  • examples thereof include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane, which may not be present.
  • monocycloalkanes such as cyclopentane and cyclohexane
  • groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. I can get lost.
  • Examples of the acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group include a group having a tertiary carbon atom on the ring skeleton of a cyclic alkyl group.
  • 2-methyl-2 Examples include —adamantyl group and 2-ethyl-2-adamantyl group.
  • an aliphatic cyclic group such as an adamantyl group such as a group bonded to an oxygen atom of a carbonyloxy group (one C (O) -0-)
  • R is the same as described above, and R 1 and R 2 represent an alkyl group (both linear and branched, preferably 1 to 5 carbon atoms). ]
  • the “acetal type acid dissociable, dissolution inhibiting group” is generally bonded to an oxygen atom by substituting a hydrogen atom at the terminal of an alkali-soluble group such as a carboxy group or a hydroxyl group. When an acid is generated by exposure, this acid acts to break the bond between the acetal type acid dissociable, dissolution inhibiting group and the oxygen atom to which the acetal type acid dissociable, dissolution inhibiting group is bonded.
  • Examples of the acetal type acid dissociable, dissolution inhibiting group include a group (pi) represented by the following general formula (pi).
  • R 1 ′ and R 2 ′ each independently represents a hydrogen atom or a lower alkyl group, n represents an integer of 0 to 3, and Y represents a lower alkyl group or an aliphatic cyclic group.
  • n is preferably an integer of 0 to 2, 0 or 1 is more preferable, and 0 is most preferable.
  • Examples of the lower alkyl group for R 1 ′ and R 2 ′ include the same lower alkyl groups as those described above for R, and a methyl group that is preferably a methyl group or an ethyl group is most preferable.
  • Examples of the lower alkyl group of ⁇ ⁇ include the same lower alkyl groups as those described above for R.
  • alicyclic group a monocyclic or polycyclic aliphatic group that has been proposed in large numbers in ArF resists and the like can be appropriately selected and used.
  • those similar to the above “aliphatic cyclic group” can be exemplified.
  • examples of the acetal type acid dissociable, dissolution inhibiting group include a group (p2) represented by the following general formula (p2).
  • R 17 and R 18 each independently represent a linear or branched alkyl group or a hydrogen atom
  • R 19 represents a linear, branched or cyclic alkyl group.
  • R 17 and R 19 are each independently a linear or branched alkylene group, and the end of R 17 and the end of R 19 may combine to form a ring! / ! / ]
  • the alkyl group preferably has 1 to 15 carbon atoms, and a straight chain or branched chain ethyl group or a methyl group is preferred. preferable.
  • one of R 17 and R 18 is preferably a hydrogen atom and the other is preferably a methyl group.
  • R 19 is a linear, branched or cyclic alkyl group, preferably having carbon number;! ⁇ 1 5, which may be linear, branched or cyclic.
  • R 19 When R 19 is linear or branched, it preferably has 1 to 5 carbon atoms, more preferably a methyl group, and most preferably an ethyl group.
  • R 19 When R 19 is cyclic, the number of carbons is 4 to; 15 is the preferred number of carbons 4 to 12 is the more preferred number of carbons 5 to 10; Specifically, it may be substituted with a halogen atom other than a fluorine atom or a halogenated alkyl group (excluding a fluorinated alkyl group), or may be unsubstituted monocycloalkane, bicycloalkane, trimethyl. Examples include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as cycloalkane or tetracycloalkane.
  • a group in which one or more hydrogen atoms are removed from adamantane is preferable.
  • R 17 and R 19 are each independently a linear or branched alkylene group (preferably an alkylene group having 1 to 5 carbon atoms), and the end of R 19 and the end of R 17 The end may be bonded.
  • a cyclic group is formed by R 17 and R 19 , the oxygen atom to which R 19 is bonded, and the carbon atom to which the oxygen atom and R 17 are bonded.
  • the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring.
  • Specific examples of the cyclic group include a tetrahydrovinyl group and a tetrahydrofuranyl group.
  • the structural unit (al) is selected from the group consisting of structural units represented by the following general formula (al—0—1) and structural units represented by the following general formula (al—0—2). It is preferable to use one or more.
  • R represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group (excluding a fluorinated lower alkyl group);
  • X 1 represents an acid dissociable, dissolution inhibiting group having 4 to 20 carbon atoms; Indicates.
  • R represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group (excluding a fluorinated lower alkyl group);
  • X 2 represents an acid dissociable, dissolution inhibiting group;
  • Y 2 represents An alkylene group or an aliphatic cyclic group is shown.
  • the lower alkyl group or halogenated lower alkyl group of R is a lower alkyl group or halogenated lower alkyl group which may be bonded to the ⁇ -position of the acrylate ester. It is the same.
  • X 1 is not particularly limited as long as it is an acid dissociable, dissolution inhibiting group, and examples thereof include the above-described tertiary alkyl ester type acid dissociable, dissolution inhibiting group and acetal type acid dissociable, dissolution inhibiting group.
  • Tertiary alkyl ester type acid dissociable, dissolution inhibiting groups are preferred! /.
  • R is the same as described above.
  • X 2 is the same as X 1 in the formula (al—0—1).
  • Y 2 is preferably an alkylene group having 1 to 4 carbon atoms or a divalent aliphatic cyclic group.
  • aliphatic cyclic group a group in which two or more hydrogen atoms are removed is used. The thing similar to what was demonstrated to the "aliphatic cyclic group" can be used.
  • X represents a tertiary alkyl ester type acid dissociable, dissolution inhibiting group
  • Y represents a lower alkyl group having 1 to 5 carbon atoms, or an aliphatic cyclic group
  • n represents 0 to 3
  • M represents 0 or 1
  • R is the same as defined above
  • R 1 ′ and R 2 ′ each independently represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms.
  • At least one of R 1 'and R 2 ' is preferably a hydrogen atom, and more preferably a hydrogen atom.
  • n is preferably 0 or 1.
  • X is the same as the tertiary alkyl ester type acid dissociable, dissolution inhibiting group exemplified in X 1 above.
  • Examples of the aliphatic cyclic group of Y include those similar to those exemplified in the description of the “aliphatic cyclic group” above.
  • one type may be used alone, or two or more types may be used in combination.
  • Structural unit (a General structural unit represented by the general formula (al-1) The general formula (a 1— 1 01 ) And the following general formula (a 1) including the structural units of formulas (al-35) to (al-1 41) -1 -02) is more preferred!
  • those represented by the general formula (al-1 101) are particularly preferred, and are selected from the structural units represented by (al-1 1 ;!) to (al-1 14). It is particularly preferable to use at least one selected from the above.
  • R is as defined above, and R 11 represents a lower alkyl group.
  • R is the same as above, represents a lower alkyl group, h represents an integer of 13 o]
  • the lower alkyl group for R 11 is the same as the lower alkyl group for R, and is preferably a methyl group or an ethyl group.
  • the lower alkyl group for R 12 is the same as the lower alkyl group for R, and is most preferably a methyl group or an ethyl group, preferably an ethyl group.
  • the amount of the structural unit (al) is based on all the structural units that constitute the resin (A1), 10 to 80 Monore 0/0 Ca Preferably, 20-70 Monore 0/0 Kayori preferably, 25-50 Monore 0/0 Ca further favorable preferable.
  • the lower limit value or more it is possible to easily obtain a pattern when a resist composition is obtained.
  • the value below the upper limit it is possible to balance with other structural units.
  • the resin (Al) preferably further has a structural unit (a2) that does not have a fluorine atom and is derived from an acrylate ester containing a latathone-containing cyclic group.
  • a rataton-containing cyclic group is a ring containing a -o-c (o) structure (a rataton ring).
  • the rataton ring is counted as the first ring, and if it is only the rataton ring, it is called a monocyclic group, and if it has another ring structure, it is called a polycyclic group regardless of the structure.
  • the Rataton cyclic group in the structural unit (a2) increases the adhesion of the resist film to the substrate or has an affinity for a developer containing water. It is effective in raising the level.
  • any unit can be used without any particular limitation.
  • examples of the latatatone-containing monocyclic group include groups in which one hydrogen atom has been removed from ⁇ -petit-latatotone.
  • examples of the latathone-containing polycyclic group include groups in which one hydrogen atom has been removed from a bicycloalkane, tricycloalkane, or tetracycloalkane having a latathone ring.
  • examples of the structural unit (a2) include structural units represented by the following general formulas (a2— ;!) to (a2-5).
  • R is as defined above, R ′ is a hydrogen atom, a lower alkyl group, or an alkoxy group having 1 to 5 carbon atoms, m is an integer of 0 or 1, and A is 1 to 5 carbon atoms]
  • R in the general formulas (a2;;!) To (a2-5) is the same as R in the structural unit (al).
  • alkylene group of A to C having 5 to 5 carbon atoms include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group.
  • R ′ is preferably a hydrogen atom in view of industrial availability.
  • one type may be used alone, or two or more types may be used in combination.
  • the proportion of the structural units in the resin (A1) (a2), relative to the combined total of all the structural units that constitute the resin (A1), 5 to 70 Monore 0/0 Ca Preferably, 10 to 60 Monore 0/0 Kayori preferably, 20-50 Monore 0/0 force S more preferred.
  • the effect of containing the structural unit (a2) can be sufficiently obtained.
  • Balance with other structural units by setting the value below the upper limit.
  • the resin (A1) is an acrylic resin having no fluorine atom and containing a polar group-containing aliphatic hydrocarbon group. Acid Ester power It is preferred to contain the derived structural unit (a3)! /.
  • the hydrophilicity of the component (A) is increased, the affinity with the developer is increased, the alkali solubility in the exposed area is improved, and the resolution is improved. Contribute to improvement.
  • Examples of the polar group include a hydroxyl group, a cyano group, and a carboxy group, and a hydroxyl group is particularly preferable.
  • the aliphatic hydrocarbon group examples include a linear or branched hydrocarbon group (preferably an alkylene group) having a carbon number;! To 10 and a polycyclic aliphatic hydrocarbon group (polycyclic group). It is done.
  • a resin for resist composition for ArF excimer laser can be appropriately selected from among many proposed ones.
  • the carbon number of the polycyclic group is preferably 7-30! /.
  • a structural unit derived from an acrylate ester containing an aliphatic polycyclic group containing a hydroxyl group, a cyano group or a carboxy group is more preferred.
  • the polycyclic group include groups in which one or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane, or the like. Specific examples include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane. Among these polycyclic groups, two or more hydrogen atoms are removed from adamantane!
  • the structural unit (a3) when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, the hydroxy group of acrylic acid is used.
  • the structural unit derived from tilester is preferred When the hydrocarbon group is a polycyclic group, the structural unit represented by the following formula (a3-1), the structural unit represented by (a3-2) And so on.
  • R is the same as defined above, j is an integer of 1 to 3, and k is an integer of 1 to 3. ]
  • j is preferably 1 or 2, and more preferably 1.
  • j is 2, it is preferable that the hydroxyl group is bonded to the 3rd and 5th positions of the adamantyl group.
  • the hydroxyl group is bonded to the 3-position of the adamantyl group.
  • k is preferably 1.
  • the Ciano group is the 5-position of the norbornyl group or
  • one type may be used alone, or two or more types may be used in combination.
  • Resin (A1) the proportion of the structural unit (a3), against the total of all structural units that constitute the resin (A1), 5 to 50 mole 0/0 force S
  • Ri 5 to 40 mole 0/0 force preferably , and still more preferably 5 to 25 mol 0/0.
  • the resin (Al) includes other structural units (a4) other than the structural units (al) to (a3) as long as the effects of the present invention are not impaired.
  • the structural unit (a4) is not particularly limited as long as it does not contain a fluorine atom and is not classified as any of the structural units (al) to (a3) described above.
  • ArF excimer laser and KrF excimer laser Many known hitherto used as resist resins such as (preferably for ArF excimer laser) can be used.
  • As the structural unit (a4) for example, a structural unit derived from an acrylate ester force containing a non-acid-dissociable aliphatic polycyclic group is preferable. Examples of the polycyclic group include those similar to those exemplified in the case of the structural unit (al).
  • ArF excimer laser KrF excimer laser (preferably for ArF excimer laser) Etc.
  • a number of hitherto known materials can be used as the resin component of the resist composition.
  • At least one selected from a tricyclodecanyl group, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, and a norbornyl group is preferable in terms of industrial availability.
  • These polycyclic groups have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent! /, Or may be /.
  • structural unit (a4) include those having the following general formulas (a4— ;!) to (a4-5).
  • one type may be used alone, or two or more types may be used in combination.
  • the structural unit (a4) is contained in the resin (A1)
  • the structural unit (a4) is contained in an amount of 1 to 30 mol%, preferably 10%, based on the total of all structural units constituting the resin (A1). It is preferable to contain ⁇ 20 mol%.
  • the resin (A1) is preferably a copolymer having at least the structural units (al), (a2) and (a3).
  • a terpolymer comprising the above structural units (al), (a2) and (a3)
  • a quaternary copolymer comprising the above structural units (al), (a2), (a3) and (a4) Etc.
  • the resin (A1) is particularly preferably one containing three structural units represented by the following general formula (A1-11)!
  • R 4i , R 4d and R 44 are each independently a hydrogen atom, a lower alkyl group, or a lower alkyl group (halogenated lower alkyl group) in which a hydrogen atom is substituted with a halogen atom other than a fluorine atom.
  • R 42 is a lower alkyl group.
  • R 41 , R 43 , and R 44 is the same as the lower alkyl group for R above.
  • R 41 , R 43 and R 44 are preferably a hydrogen atom or a methyl group, preferably a hydrogen atom or a lower alkyl group! /.
  • the lower alkyl group for R 42 is the same as the lower alkyl group for R described above, and is most preferably a methyl group or a methyl group, preferably an ethyl group.
  • the resin (A1) is obtained by polymerizing a monomer that derives each structural unit by, for example, a known radical polymerization using a radical polymerization initiator such as azobisisoptyronitrile (AIBN). You can get power S.
  • a radical polymerization initiator such as azobisisoptyronitrile (AIBN).
  • the mass average molecular weight (Mw) of the whole component (A) is not particularly limited, but 2000 to 50000 is preferred ⁇ , 3000 to 30000 More preferred ⁇ , 5000-20000 most preferred. If it is less than the upper limit of this range, there is sufficient solubility in a resist solvent to be used as a resist. When it is at least the lower limit of this range, the dry etching resistance and resist pattern cross-sectional shape are good.
  • the dispersity (Mw / Mn) of the entire component (A) is preferably 1 ⁇ 0 to 5 ⁇ 0 force S, more preferably 1 ⁇ 0 to 3 ⁇ 0, and most preferably 1.2 to 2.5.
  • the content of the component (ii) may be adjusted according to the thickness of the resist film to be formed.
  • the resin (A1) may be used alone or in combination of two or more.
  • the content of the resin (Al) in the component (A) is preferably in the range of 50 to 100% by weight 75 to 75%; 100% by weight is more preferable 80 to 100% by weight. preferable.
  • the resin (A1) content is 50% by mass or more, the lithography properties are improved.
  • the content of the resin (A1) in the component (A) is most preferably 100% by mass.
  • the component (B) is not particularly limited, and those that have been proposed as acid generators for chemically amplified resists can be used.
  • acid generators hitherto salt generators such as iodine salts and sulfoyumate salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes,
  • diazomethane acid generators such as poly (bissulfonyl) diazomethanes, nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, and disulfone acid generators.
  • Examples of the onium salt-based acid generator include acid generators represented by the following general formula (b-0).
  • R 51 represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group
  • R 52 represents a hydrogen atom, a hydroxyl group, a halogen atom, a straight Chain or branched alkyl group, linear or branched alkyl halide group
  • R 51 represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group.
  • the linear or branched alkyl group is most preferably 1 to 4 carbon atoms, preferably 1 to 8 carbon atoms;!
  • the cyclic alkyl group is most preferably 4 to 10 carbon atoms, preferably 5 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms.
  • the fluorinated alkyl group is most preferably 1 to 4 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the fluorination rate of the fluorinated alkyl group (ratio of the number of substituted fluorine atoms to the total number of hydrogen atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%. In particular, those in which all hydrogen atoms are substituted with fluorine atoms are preferable because the strength of the acid is increased.
  • R 51 is most preferably a linear alkyl group or a fluorinated alkyl group! /.
  • R 52 is a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group, a linear or branched alkyl halide group, or a linear or branched alkoxy group. .
  • examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group is linear or branched, and the carbon number thereof is preferably;!-5, in particular;!-4, and more preferably 1-3.
  • the halogenated alkyl group is a group in which part or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms.
  • the alkyl group here are the same as the “alkyl group” in R 51 .
  • the halogen atom to be substituted are the same as those described above for “no, log atom”.
  • the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly preferably !! to 4, and more preferably 1 to 3.
  • R 52 is preferably a hydrogen atom.
  • R 53 is an aryl group having 6 to 20 carbon atoms which may have a substituent, and the structure of the basic ring (matrix ring) excluding the substituent includes a naphthyl group, a phenyl group, and an anthracenyl group From the viewpoint of the effect of the present invention and the absorption of exposure light such as ArF excimer laser, a phenyl group is desirable.
  • the substituent include a hydroxyl group and a lower alkyl group (straight or branched chain, preferably having 1 to 5 carbon atoms, particularly preferably a methyl group).
  • the aryl group of R 53 has no substituent! /, More preferably! / ,.
  • u is an integer of 1 to 3, 2 or 3 is preferred, and 3 is particularly desirable.
  • Preferable examples of the acid generator represented by the general formula (b-O) include the following.
  • onium salt acid generators of the acid generator represented by the general formula (b-0) for example, a compound represented by the following general formula (b-1) or (b-2) Is mentioned.
  • R 5 “ ⁇ R 6 ” each independently represents an aryl group or an alkyl group; R 4 ”represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group; And at least one of “ ⁇ ” represents an aryl group, and at least one of R 5 “to R 6 ” represents an aryl group.
  • the aryl group of Ri "to" is not particularly limited, for example, an aryl group having 6 to 20 carbon atoms, and in the aryl group, part or all of the hydrogen atoms are alkyl groups, alkoxy groups, halogen atoms. It does not need to be substituted with an atom or the like.
  • the aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at low cost. Specific examples include a phenyl group and a naphthyl group.
  • alkoxy group a methoxy group and an ethoxy group are preferred, and an alkoxy group having! To 5 carbon atoms is preferred.
  • the halogen atom is preferably a fluorine atom.
  • R1 as alkyl group "to R 3", Nag particularly limited for example, the number of carbon atoms;! A ⁇ 10 linear
  • the number of carbon atoms is preferably 1 to 5.
  • methyl group, ethyl group, n-propyl group, isopyl pill group, n butyl group, isobutyl group, n pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nonyl group, decanyl group It is preferable because it is excellent in resolution and can be synthesized at a low cost.
  • 1 " ⁇ ! ⁇ " Is most preferably a phenyl group or a naphthyl group, respectively.
  • R 4 ′′ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group.
  • the linear or branched alkyl group preferably has 1 to 10 carbon atoms, preferably 10 carbon atoms;
  • the cyclic alkyl group is a cyclic group, and is most preferably 4 to 10 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.
  • the fluorinated alkyl group is most preferably 1 to 4 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the fluorination rate of the fluorinated alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%. What is substituted with an atom is preferred because the strength of the acid increases.
  • R 4 ′′ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.
  • R 5 ′′ to R 6 ′′ each independently represents an aryl group or an alkyl group. At least one of R 5 “to R 6 " represents an aryl group. All of R 5 “to R 6 " are preferably aryl groups.
  • R 5 " ⁇ R 6 " arele groups are the same as those for 1 " ⁇ ! ⁇ "
  • R 5 " ⁇ R 6" 1 " ⁇ ! ⁇ "
  • R 5 " ⁇ R 6" is a phenyl group preferable.
  • R 4 in the formula (b-1) Formula (b-2) R 4 in the same groups as those described above for.
  • onion salt-based acid generators represented by the formulas (b-1) and (b-2) include diphenols.
  • nonafluorobutanesulfonate (4-methoxyphenyl) diphenylate or its nonafnorenobutanesulfonate, tri (4 tertbutinore) phenenolesnore or its nonafrobutanesulfonate, diphenyl
  • mono (4-methoxy) naphthyl) ate or nonafluorobutanesulfonate thereof, and di (1naphthinore) phenylsulfonate include nonafrobutanesulfonate.
  • onium salts in which the anion portion of these onium salts is replaced by methanesulfonate, n-propanesulfonate, or n-butanesulfonate Kn-octanesulfonate can also be used.
  • an anion salt system in which the anion part is replaced with an anion part represented by the following general formula (b-3) or (b-4)
  • An acid generator can also be used (the cation moiety is the same as (b-1) or (b-2)).
  • X represents a 26-carbon alkylene group in which at least one hydrogen atom is substituted with a fluorine atom; ⁇ " ⁇ "independently represents at least one hydrogen atom is a fluorine atom.
  • a substituted carbon number; represents an alkyl group having from 10 to 10.
  • X is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 26 carbon atoms, preferably 35 carbon atoms, Most preferably, it has 3 carbon atoms.
  • ⁇ " ⁇ " each independently represents a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms. , Preferably 1 to 7 carbon atoms, more preferably 1 to 3 carbon atoms.
  • the carbon number of the alkylene group of X ′′ or the carbon number of the alkyl group of “ ⁇ ⁇ ⁇ ⁇ ” and “ ⁇ ” is preferably as small as possible within the range of the above-mentioned carbon number for reasons such as good solubility in a resist solvent.
  • the ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%. Most preferably, it is a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
  • the oxime sulfonate acid generator is a compound having at least one group represented by the following general formula (B-1), and generates an acid upon irradiation with radiation. It is what has.
  • Such oxime sulfonate acid generators are widely used for chemically amplified resist compositions, and can be arbitrarily selected and used.
  • R 31 and R 32 each independently represents an organic group.
  • the organic group of R 31 and R 32 is a group containing a carbon atom, and an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.) ) Etc.).
  • an atom other than a carbon atom for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.)
  • a linear, branched or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent.
  • the substituent is not particularly limited, and examples thereof include a fluorine atom, a linear, branched or cyclic alkyl group having 6 to 6 carbon atoms.
  • “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
  • carbon number 1 to 20 is preferable 1 to 10; carbon number 10 is more preferable 1 to 8 is more preferable;! To 6 is particularly preferable carbon number 1 to 4 is most preferred.
  • a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable.
  • the partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated alkyl group means that all the hydrogen atoms are halogen atoms. It means an alkyl group substituted by.
  • the halogen atom include a fluorine atom, a chlorine atom, an fluorine atom, and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group! /.
  • the aryl group is most preferably 4 to 20 carbon atoms, preferably 4 to 20 carbon atoms; and more preferably 6 to 10 carbon atoms, more preferably 10 carbon atoms.
  • a partially or completely halogenated aryl group is particularly preferable.
  • a partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and a fully halogenated aryl group means that all hydrogen atoms are halogenated.
  • R 31 is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms! /.
  • organic group for R 32 a linear, branched or cyclic alkyl group, aryl group or cyan group is preferable.
  • alkyl group and aryl group for R 32 include the same alkyl groups and aryl groups as those described above for R 31 .
  • R 32 is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.
  • oxime sulfonate acid generator examples include compounds represented by the following general formula (B-2) or (B-3).
  • R 33 represents a cyano group, an alkyl group having no substituent, or a halogenated group. It is an alkyl group.
  • R 34 is an aryl group.
  • R 35 represents an alkyl group having no substituent or a halogenated alkyl group.
  • R d ° represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group.
  • R 37 is a divalent or trivalent aromatic hydrocarbon group.
  • R 38 is an alkyl group having no substituent or a halogenated alkyl group. p "is 2 or 3.]
  • alkyl or halogenated alkyl group having no substituent group for R 33 it is 1 to carbon atoms; 10 preferably implement more favorable is C1-8 Most preferred is 1 to 6 carbon atoms.
  • R 33 is more preferably a fluorinated alkyl group, preferably a halogenated alkyl group.
  • the fluorinated alkyl group for R 33 preferably has 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, and even more preferably 90% or more. .
  • the aryl group of R 3 is a hydrogen from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group, or a phenanthryl group.
  • an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group, or a phenanthryl group.
  • Examples include a group in which one atom is removed, and a heteroaryl group in which a part of the carbon atoms constituting the ring of these groups is substituted with a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom.
  • a fluorenyl group is preferable.
  • the aryl group of R 34 may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group.
  • the alkyl group or halogenated alkyl group in the substituent is more preferably 1 to 4 carbon atoms, preferably 1 to 8 carbon atoms.
  • the halogenated alkyl group is preferably a fluorinated alkyl group.
  • the alkyl group or halogenated alkyl group having no substituent of R 35 has carbon number;
  • R db is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group, and more preferably a partially fluorinated alkyl group.
  • the fluorinated alkyl group in R 35 preferably has a hydrogen atom of the alkyl group of 50% or more fluorinated, more preferably 70% or more, and still more preferably 90% or more. This is preferable because the strength of the generated acid is increased. Most preferably, it is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted.
  • the alkyl group or halogenated alkyl group having no substituent of R 36 has no substituent of R 33 ! /, An alkyl group or a halogenated group. Examples are the same as the alkyl group.
  • Examples of the divalent or trivalent aromatic hydrocarbon group for R 37 include groups obtained by further removing 1 or 2 hydrogen atoms from the aryl group for R 34 .
  • Examples of the alkyl group or halogenated alkyl group having no substituent of R 38 include those similar to the alkyl group or halogenated alkyl group having no substituent of the above 5 .
  • P is preferably 2.
  • oxime sulfonate-based acid generators include ⁇ ( ⁇ toluenesulfonyloxyimino) benzyl cyanide, ⁇ ( ⁇ chlorobenzenesulfonyloxyimino) benzyl cyanide, ⁇ - (4 Benzenesulfonyloxymino) Benzyl cyanide, ⁇ (4 12 tallow 2 trifluoromethylbenzenesulfonyloxymino) benzyl cyanide, ⁇ (benzenesulfonyloxymino) -4 clonal benzil cyanide, ⁇ — (Benzenesulfonyloxyimino) -2, 4-dichlorodiphenylcyanide, ⁇ (benzenesulfonyloxyimino) -2,6-dichlorodiethylcyanide, ⁇ (benzenesulfonyloxyimino) -4-Met
  • JP-A-9 208554 (paragraph) [0012] to [0014] in [Chemical Formula 18] to [Chemical Formula 19]), disclosed in WO2004 / 074242A2 (Examples on pages 65 to 85; Examples 40 to 40)
  • the oxime sulfonate acid generator that has been used can also be suitably used.
  • bisalkyl or bisarylsulfonyldiazomethanes include bis (isopropylsulfonyl) diazomethane, bis (p-toluenenolehoninore) diazomethane, bis (1, 1 -Dimethinoleethinoresnorehoninore) diazomethane, bis (cyclohexenolesnorehoninore) diazomethane, bis (2,4 dimethinolefuinorenorehoninore) diazomethane, and the like.
  • diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552 and JP-A-11-035573 can also be suitably used.
  • poly (bissulfonyl) diazomethanes include 1,3-bis (phenylsulfonyldiazomethylsulfonyl) pronone, 1,4-bis (disclosed in JP-A-11 322707.
  • one type of these acid generators may be used alone, or two or more types may be used in combination.
  • an onium salt having a fluorinated alkylsulfonic acid anion as the component (B).
  • the content of the component (B) in the positive resist composition for immersion exposure according to the present invention is 0.5 to 30 parts by mass, preferably! To 10 parts by mass with respect to 100 parts by mass of the component (A). Is done. Above By forming the enclosure, pattern formation is sufficiently performed. In addition, a uniform solution is obtained and storage stability is improved, which is preferable.
  • the positive resist composition for immersion exposure of the present invention contains, as component (C), a non-main chain cyclic resin (C1) containing a fluorine atom and having no acid-dissociable group, and a fluorine atom. However, it contains no acid-dissociable groups! / And contains a main chain cyclic resin (C2).
  • the resist film obtained from the positive resist composition of the present invention has high hydrophobicity on its surface, and as described later, substance elution into an immersion medium such as water is suppressed. Is done.
  • the “acid-dissociable group” means a group dissociated by the action of an acid generated from the component (B) by exposure.
  • the latathone-containing cyclic group in the structural unit (a 2) the polar group-containing aliphatic hydrocarbon group in the structural unit (a3), the polycyclic aliphatic hydrocarbon group in the structural unit (a4), etc. Not included in “acid-dissociable groups”.
  • the acid-dissociable group is not particularly limited as long as it is a group that can be dissociated by the action of the acid generated from component (B) .
  • it has been proposed as an acid-dissociable, dissolution-inhibiting group for base resins for chemically amplified resists. Being! / Can be something.
  • Specific examples of the acid dissociable dissolution inhibiting group include the same force S as exemplified in the structural unit (al) as the acid dissociable dissolution inhibiting group of the structural unit (a1).
  • dissolution inhibition in the acid dissociable dissolution inhibiting group means that this group has an action (dissolution inhibiting property) for inhibiting the solubility of the component (A) in an alkali such as an alkali developer.
  • the “acid-dissociable group” may have a dissolution inhibitory property or may have a dissolution inhibitory property.
  • the resin (C1) is not particularly limited as long as it is a non-main chain cyclic resin containing a fluorine atom and having no acid dissociable group! /.
  • non-main-chain cyclic resin means a resin in which none of the carbon atoms constituting the main chain is a carbon atom constituting a ring structure.
  • the resin (C1) preferably has an alkali-soluble group.
  • the alkali solubility is increased, contributing to improvement of various lithography properties such as resolution and resist pattern shape.
  • having an alkali-soluble group containing a fluorine atom, such as a fluorinated hydroxyalkyl group, which will be described later, is excellent in improving the hydrophobicity of the resist film and suppressing the elution of the substance during immersion exposure. Usefulness for immersion exposure is further improved.
  • the alkali-soluble group is a group that enhances the alkali solubility of the resin, and is particularly limited to a group having a relatively small pKa (Ka is an acid dissociation constant) similar to a phenolic hydroxyl group. Although not preferred, groups having a pKa in the range of 6 to 12 are preferred.
  • examples of the alkali-soluble group include groups having OH at the terminal, such as a hydroxyl group (phenolic hydroxyl group, alcoholic hydroxyl group) and a carboxyl group.
  • groups having OH at the terminal include, for example, an alcoholic hydroxyl group; a hydrogen atom bonded to a carbon atom having a hydroxyl group bonded to the hydroxyalkyl group (a carbon atom at the ⁇ - position) is electron withdrawing.
  • Group substituted with a functional group (electron-withdrawing group-substituted hydroxyalkyl group); carboxyl group and the like.
  • the alkali-soluble group is preferably an electron-withdrawing group-substituted hydroxyalkyl group.
  • the alkyl group is preferably linear or branched.
  • the number of carbon atoms of the electron-withdrawing group-substituted hydroxyalkyl group is not particularly limited, but !!-20 is preferable 4 to 16 force S is more preferable, and 4 to 12 is most preferable.
  • the number of hydroxyl groups is not particularly limited, but one is preferred.
  • Examples of the electron-withdrawing group include a halogen atom or a halogenated alkyl group.
  • the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferable.
  • the halogenated alkyl group the halogen is the same as the halogen atom, and the alkyl group is preferably a lower alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, or a propyl group, more preferably a methyl group or
  • the number of electron withdrawing groups is 1 or 2, preferably 2.
  • the electron-withdrawing group-substituted hydroxyalkyl group has a CR 71 R 72 OH group, and R 71 and R 72 are each independently an alkyl group having 1 to 5 carbon atoms, a halogen atom Or at least one of which is an electron-withdrawing group selected from a halogen atom or a halogenated alkyl group.
  • the resin (C1) preferably has a fluorinated hydroxyalkyl group as the electron-withdrawing group-substituted hydroxyalkyl group.
  • LER Line Edge Roughness: uneven unevenness of line side walls.
  • Diffeta is a general defect detected when a developed resist pattern is observed from directly above, for example, with a surface defect observation device (trade name “KLA”) manufactured by KLA Tencor. Examples of such defects include scum, bubbles, dust, bridges between resist patterns, uneven color, and precipitates after development.
  • the “fluorinated hydroxyalkyl group” refers to a hydroxyalkyl group in which a part of hydrogen atoms of the alkyl group is substituted with a hydroxyl group! /, And the remaining hydrogen atoms in the hydroxyalkyl group A part or all of (hydrogen atom not substituted with hydroxyl group of alkyl group) is substituted with fluorine.
  • the hydrogen atom of the hydroxyl group is easily liberated by fluorination.
  • the alkyl group is preferably linear or branched.
  • the number of carbon atoms of the alkyl group is not particularly limited, but 1 to 20 is preferably 4 to 16; 16 is more preferably 4 to 12;
  • the number of hydroxyl groups is not particularly limited! /, But one is preferred! /.
  • a fluorinated hydroxyalkyl group a fluorinated alkyl group and / or a fluorine atom is bonded to a carbon atom to which a hydroxyl group is bonded (here, the ⁇ -position carbon atom of the hydroxyalkyl group). I like things! /.
  • a perfluoroalkyl group in which all of the hydrogen atoms of the fluorinated alkyl group alkyl group bonded to the ⁇ -position are substituted with fluorine is preferable.
  • the resin (C 1) has a group represented by the following general formula (III).
  • X is an integer of 0 to 5
  • y and ⁇ are each independently an integer of 1 to 5.
  • X is preferably an integer of 0 to 3, and 0 or 1 is particularly preferable.
  • y and z are preferably integers of 1 to 3, with 1 being most preferred.
  • the resin (C 1) preferably contains a structural unit (a ′′) that also induces acrylic acid power.
  • Acrylic acid includes, for example, a substitution group (atom or group other than a hydrogen atom) bonded to the ⁇ -position carbon atom of narrowly defined acrylic acid! /, A substituted acrylic acid, and these acrylic acids And acrylic acid esters in which the hydrogen atom of the carboxyl group is substituted with an organic group.
  • the “organic group” is a group containing a carbon atom, and the organic group in the acrylate ester is not particularly limited.
  • the organic group may be a structural unit (aO) or the structural units (al) to (a4) described later.
  • a group bonded to the ester side chain of the acrylate ester (a group having a fluorinated hydroxyalkyl group, an acid dissociable, dissolution inhibiting group, a ratatone-containing cyclic group) Group, polar group-containing aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group and the like.
  • the ⁇ -position ( ⁇ -position carbon atom) is a carbon atom to which a carbonyl group is bonded, unless otherwise specified.
  • substituent of the ⁇ - substituted acrylic acid include a lower alkyl group having 1 to 5 carbon atoms and a halogenated lower alkyl group.
  • a lower linear or branched alkyl group such as a group.
  • halogenated lower alkyl group as a substituent at the a-position, part or all of the hydrogen atoms of the lower alkyl group are substituted with a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or the like, or a rogen atom.
  • Bonded to the ⁇ -position of acrylic acid is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, preferably a hydrogen atom, a lower alkyl group or a fluorinated lower alkyl group.
  • a hydrogen atom or a methyl group is most preferable.
  • Examples of the structural unit ( a ) include structural units represented by the following general formula (a").
  • R 2 ° is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and X is a hydrogen atom or a monovalent organic group
  • a lower alkyl group or a halogenated lower alkyl group R 2 ° is the same as the lower alkyl group or a halogenated lower alkyl group as a substituent of the ⁇ -position thereof.
  • Examples of the organic group for X include the same as the “organic group in acrylic ester” described for the structural unit (a ′′).
  • the resin (C1) preferably contains the structural unit (a ") in a proportion of 50 to 100 mol% with respect to the total of all the structural units constituting the resin (C1). ⁇ ; Contains 100 mol% It is particularly preferable. In particular, since the effect of the present invention is particularly excellent, it is preferable that the resin (C1) is composed only of the structural unit (a ′′) derived from attalic acid! /.
  • the resin (C1) preferably has a structural unit (aO) derived from an acrylate ester having a fluorinated hydroxyalkyl group in the side chain portion! /.
  • the “side chain portion” means a portion not constituting the main chain.
  • Examples of the structural unit (aO) include structural units in which X in the general formula (a ′′) is a group having a fluorinated hydroxyalkyl group.
  • the structural unit (aO) includes a structural unit represented by the following general formula (aO-2).
  • R 2 ° is a hydrogen atom, a lower alkyl group, a lower halogenated alkyl group; a R 22, R 2 3 each independently hydrogen atom or a monovalent aliphatic cyclic group, R 22 And at least one of R 23 is an aliphatic cyclic group; f is an integer of 0 to 5; b and c are each independently an integer of! ]
  • the structural unit represented by the general formula (aO-2) (hereinafter referred to as the structural unit (aO-2) and! /, U) has one hydrogen atom in the methyl group (CH)-
  • R 2U in the general formula (aO-2) is the same as R in the above formula (a "), preferably a hydrogen atom or a lower alkyl group, and most preferably a hydrogen atom or a methyl group.
  • b and c are each independently an integer of 1 to 5, preferably an integer of 1 to 3, and 1 is most preferable.
  • f is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, with 1 being most preferred.
  • R 22 and R 23 are each independently a hydrogen atom or a monovalent aliphatic cyclic group, and at least one of R 22 and R 23 is an aliphatic cyclic group.
  • one of R 22 and R 23 is a hydrogen atom and the other is an aliphatic cyclic group.
  • the aliphatic cyclic group for R 22 and R 23 may be monocyclic or polycyclic.
  • “Monocyclic aliphatic cyclic group” means a monocyclic group having no aromaticity
  • “polycyclic aliphatic cyclic group” means a polycyclic group having no aromaticity. Means.
  • An aliphatic cyclic group is a hydrocarbon group consisting of carbon and hydrogen (an alicyclic group), and some of the carbon atoms constituting the ring of the alicyclic group are oxygen atoms, nitrogen atoms, sulfur atoms, etc. Heterocyclic groups substituted with a heteroatom are included. As the aliphatic cyclic group, an alicyclic group is preferable.
  • the aliphatic cyclic group may be either saturated or unsaturated, but is preferably saturated because it is highly transparent to ArF excimer laser, etc., and has excellent resolution and depth of focus (DOF). .
  • the aliphatic cyclic group for R 22 and R 23 preferably has 5 to 15 carbon atoms, more preferably 6 to 12 carbon atoms.
  • groups in which one or more hydrogen atoms have been removed from cyclohexane, cyclopentane, norbornane, tricyclodecane, or tetracyclododecane are particularly preferred.
  • Groups in which one or more hydrogen atoms have been removed from cyclohexane are preferred. .
  • the structural unit (aO-2) in particular, the structural unit represented by the following general formula (aO-2-1) is effective, easy to synthesize, and highly etched. It is preferable from the point that tolerance is obtained. [0137] [Chemical 43]
  • the structural unit (aO) includes a fluorinated hydroxyalkyl group and a monocyclic or polycyclic aliphatic group in the side chain as in the structural unit (aO-2).
  • a structural unit having a cyclic group is preferred, and a structural unit represented by the general formula (aO-2-1) is preferred.
  • one type may be used alone, or two or more types may be used in combination.
  • Resin (C1) the proportion of the structural unit (aO-), relative to the combined total of all the structural units that constitute the resin (C1),. 30 to; 100 Monore 0/0 Ca Preferably, 50; 100 Monore 0/0 more preferably Ca, 70; 100 molar% and most preferably more preferably tool 100 mole 0/0.
  • 100 Monore 0/0 Ca Preferably, 50; 100 Monore 0/0 more preferably Ca, 70; 100 molar% and most preferably more preferably tool 100 mole 0/0.
  • the resin (C1) may contain other structural units other than the structural unit (aO) as long as the effects of the present invention are not impaired.
  • the other structural unit is not classified as the structural unit (aO) described above, has no acid-dissociable group, the carbon atom constituting the main chain is not a carbon atom constituting the ring structure!
  • the structural unit (aO) it is not particularly limited.
  • ArF excimer laser KrF excimer laser
  • a number of hitherto known materials can be used for resist resins such as one for one (preferably for ArF excimer laser).
  • all the carbon atoms constituting the main chain constitute a ring structure. And those that are not carbon atoms.
  • the combination and ratio of the structural unit (aO) and other structural units can be appropriately adjusted depending on the required characteristics and the like.
  • the resin (C1) is preferably composed only of the structural unit (aO).
  • Resin (C1) is a monomer derived from each structural unit, for example, radicals such as azobisisoptylonitrile triol (AIBN) or dimethyl-2,2, -azobis (2-methylpropionate). It can be obtained by polymerizing by known radical polymerization using a polymerization initiator.
  • radicals such as azobisisoptylonitrile triol (AIBN) or dimethyl-2,2, -azobis (2-methylpropionate.
  • the mass average molecular weight of the resin (C1) (Mw; mass average molecular weight in terms of polystyrene by gel permeation chromatography) is not particularly limited, but 2000-40000 is preferred ⁇ , 2000-30000 Preferred ⁇ , 3000-25,000 more preferred! By setting it within this range, a good dissolution rate in an alkali developer can be obtained, which is preferable from the viewpoint of high resolution. Within this range, the lower the molecular weight, the better when good characteristics can be obtained.
  • the degree of dispersion (Mw / Mn) is about 1.0 to 5.0, preferably 1.0 to 3.0.
  • the resin (C1) may be used alone or in combination of two or more.
  • the content of the resin (C1) in the component (C) is preferably 0.1% by mass or more, more preferably in the range of 0.1 to 90% by mass, further 5 to 90% by mass
  • the preferred range is 10 to 85% by mass, and the most preferred range is 15 to 80% by mass.
  • the content of the resin (C1) is 0.1 mass% or more, the resistance of the resist film to the immersion medium is improved. Further, when the content is 90% by mass or less, the lithography characteristics are improved.
  • Resin (C2) is a main chain cyclic resin that contains fluorine atoms and has no acid dissociable groups It is.
  • the “acid-dissociable group” is the same as described above.
  • —Q—NH—SO—R 5 and the like in the structural unit (a ′ 1) described later are included in the “acid-dissociable group”. Absent.
  • main-chain cyclic resin means that the structural unit constituting the resin has a monocyclic or polycyclic ring structure, and It means that at least one, preferably two or more carbon atoms on the ring have a structural unit constituting the main chain (hereinafter referred to as a main chain cyclic type structural unit and a singing force S). .
  • etching resistance is improved. The improvement in etching resistance is presumed to be due to the fact that the carbon density is increasing due to having the main chain cyclic structural unit.
  • the main chain cyclic structural unit includes a structural unit derived from polycycloolefin (polycyclic olefin) and a structure containing an anhydride of the dicarboxylic acid mentioned in the structural unit (a'3) described later. Examples include units.
  • the etching resistance when used as a resist is particularly excellent, it is preferable to have a structural unit derived from a polycyclorefiner in the main chain.
  • a structural unit derived from polycycloolefin a structural unit having a basic skeleton represented by the following general formula (a ′) is preferable.
  • a is 0 or 1, and 0 is preferable in consideration of easy industrial availability.
  • the “structural unit having a basic skeleton represented by the general formula (a ′)” is the structural unit represented by the general formula (a ′).
  • Forming units i.e. bicyclo [2 ⁇ 2.1] - 2- heptene (norbornene) configuration unit force is also induced, and tetracyclo [4 ⁇ 4. 0. I 2 ⁇ 5 ⁇ 1. 7 1 °] - 3- Dodecene force-derived structural unit), and also has a substituent on its ring skeleton, such as structural units (a ′ :! to (a ′ 3) described later. Also good.
  • the structural unit having the basic skeleton represented by the general formula (a ′) includes the ring skeleton (bicyclo [2. 2. 1] —2-heptane or tetracycline [4. 4.0. I 2 ' 5 1.1.7 1 °] —includes structural units in which some or all of the hydrogen atoms bonded to the carbon atoms constituting 3-dodecane are substituted with atoms or substituents other than hydrogen atoms.
  • the resin (C2) is a structural unit other than the main chain cyclic structural unit, for example, the structural unit (a) (structural unit derived from acrylic acid) listed in the resin (A1)!
  • the main chain cyclic structural unit is 50% of all the structural units constituting the resin (C2). It is preferable that 100 mol% is contained. It is more preferable that 80-100 mol% is contained.
  • the resin (C2) is preferably composed only of a main chain cyclic structural unit.
  • consisting only of the main chain cyclic structural unit means that the main chain of the resin (C2) is composed only of the main chain cyclic structural unit and does not include other structural units. .
  • the resin (C2) is excellent in the effects of the present invention, the resin (C2) preferably has a structural unit (a, 1) represented by the following general formula (I)!
  • I ⁇ to R 4 are each independently a hydrogen atom, a linear or branched alkyl group, a linear or branched fluorinated alkyl group, or the following general formula (la ) And at least one of I ⁇ to R 4 is the group (la); a is 0 or 1. ]
  • Q is a linear or branched alkylene group having 1 to 5 carbon atoms; R 5 is a fluorinated alkyl group.
  • the structural unit (a'1) represented by the general formula (I) is substituted at a specific position on the ring in the structural unit having the basic skeleton represented by the general formula (a ').
  • the group has at least a group (la) represented by the general formula (la).
  • the hydrophobicity of the resist film surface is improved by having force and a structural unit.
  • lithography properties are improved.
  • the reason why such an effect can be obtained is not clear, but by having the group (la), the effect of improving the hydrophobicity of the resist film by fluorine atoms can be obtained, and the alkali solubility of the resin (C2) can be improved.
  • the group (la) the effect of improving the hydrophobicity of the resist film by fluorine atoms can be obtained, and the alkali solubility of the resin (C2) can be improved.
  • a is the same as a in the above formula (a ′).
  • the alkyl group of Ri to R 4 may be linear or branched, having 1 to 5 carbon atoms; the alkyl group having 10 is preferable, and the alkyl group having 1 to 8 carbon atoms is more preferable.
  • the alkyl group is more preferable. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, an isopentyl group, and a neopentyl group.
  • the fluorinated alkyl group represented by Ri to R 4 is a group in which part or all of the hydrogen atoms of a linear or branched alkyl group are substituted with fluorine atoms.
  • the alkyl group that put the fluorinated alkyl group, the same alkyl groups as those for the I ⁇ to R 4 can be cited.
  • the fluorination rate of the fluorinated alkyl group (ratio of the number of fluorine atoms to the total number of hydrogen atoms and fluorine atoms in the fluorinated alkyl group (%)) is preferably 10 to 100%. 30 to 100% force is preferred, 50 to 100% is more preferred. When the fluorination rate is 10% or more, the effect of improving the hydrophobicity of the resist film surface is excellent.
  • the alkylene group of Q may be linear or branched; the alkylene group having 1 to 8 carbon atoms is more preferable, and the alkylene group having 1 to 8 carbon atoms is more preferable. More preferred is an alkylene group having 1 to 5 carbon atoms.
  • Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a pentene group, an isopentene group, and a neopentene group.
  • a linear alkylene group is preferred in view of ease of synthesis, and a methylene group is particularly preferred.
  • the fluorinated alkyl group for R 5 is a group in which part or all of the hydrogen atoms of a linear, branched or cyclic alkyl group are substituted with fluorine atoms.
  • the straight chain or branched chain alkyl group the same as the fluorinated alkyl group of the I ⁇ to R 4 can be cited.
  • the cyclic alkyl group is most preferably 4 to 10 carbon atoms, preferably 5 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms.
  • the fluorination rate of the fluorinated alkyl group (ratio of the number of fluorine atoms to the total number of hydrogen atoms and fluorine atoms in the fluorinated alkyl group (%)) is preferably 10 to 100%. 30 to 100% force is preferred, 50 to 100% is particularly preferred 100%, that is, all hydrogen atoms are replaced by fluorine atoms.
  • the fluorination rate is 10% or more, the effect of improving the hydrophobicity of the resist film surface is excellent. Therefore, even if the ratio of the resin (C2) in the component (C) is small, a sufficient hydrophobicity improving effect can be obtained.
  • fluorinated alkyl group for R 5 a linear or branched fluorinated alkyl group is preferable, and a fluorinated alkyl group having 1 to 5 carbon atoms is more preferable. Particularly, all the hydrogen atoms of the alkyl group are fluorine. Preference is given to perfluoroalkyl groups substituted with atoms! /. Specific examples of the perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, and the like.
  • I ⁇ to R 4 is a group (la) represented by the general formula (la), and the remaining 0 to 3 are a hydrogen atom, straight chain or branched A chain alkyl group, and One or more selected from linear or branched fluorinated alkyl groups.
  • one of I ⁇ to R 4 is a group (la).
  • one of I ⁇ to R 4 is a group (la), and the other three are A hydrogen atom is preferred.
  • p is an integer from 1 to 10; an integer from! to 8 is preferred, and 1 is most preferred.
  • q is an integer from 1 to 5; an integer from! to 4 is preferred, and 1 is most preferred.
  • the structural unit (a '1) may be used in combination of two or more Yogu be used alone.
  • the resin (C2) preferably contains the structural unit (a′1) in a proportion of 50 to 100 mol% with respect to the total of all the structural units constituting the resin (C2) 80 to; It is more preferable to contain 100 mol%.
  • the resin (C2) is preferably composed of only the structural unit (a′1)! /.
  • the monomer for deriving the structural unit (a'1) can be synthesized by, for example, the technique disclosed in US Pat. No. 6,420,503!
  • the resin (C2) is a component other than the structural unit (a ′ 1) as long as the effects of the present invention are not impaired. Including the unit (a 3)!
  • the structural unit (a ′ 3) does not have an acid-dissociable group and is not classified as the above structural unit (a ′ 1), and is a copolymer with a monomer that derives the structural unit ( a ′ 1). There is no particular limitation as long as it is a structural unit derived from a possible monomer.
  • a structural unit (a ′ 3) a structural unit derived from a known compound having an ethylenic double bond can be arbitrarily used depending on the purpose.
  • the structural unit (a'3) for example, a structural unit derived from acrylic acid such as the structural unit ( a2 ) to the structural unit (a4) listed in the resin (A1).
  • Dicarboxylic acid anhydride-containing structural units, no substituents! / Structural units derived from polycyclohexylene, polycycloolefins having polycyclic alicyclic groups as substituents Examples include structural units.
  • An acid anhydride-containing structural unit of a dicarboxylic acid refers to a structural unit having a C (O)-O- C (O) structure.
  • Examples of such include structural units containing a monocyclic or polycyclic cyclic anhydride, and more specifically, a monocyclic anhydrous represented by the following formula (a′31).
  • a structural unit derived from maleic acid, a structural unit derived from a polycyclic anhydrous maleic acid represented by the following formula (a'32), and a structure derived from itaconic acid represented by the following formula (a'33) Examples include units.
  • Structural units derived from polycycloolefin include bicyclo [2.2.1] —2-heptene (norbornene), tetracyclo [4. 4. 0. I 2 ' 5. 1. 7 1 °] — 3 -decene and the like.
  • a structural unit ring derived from polycycloolefin examples include a structural unit having a polycyclic group such as a tricyclodecanyl group, an adamantyl group, or a tetracyclododecanyl group.
  • the combination and ratio of the structural units such as the structural units (a ′ 1) and (a ′ 3) can be appropriately adjusted depending on the required characteristics.
  • the resin (C2) is preferably composed only of the structural unit (a ′ 1).
  • Resin (C2) is obtained, for example, by polymerizing a monomer that derives a predetermined structural unit by a known radical polymerization using a radical polymerization initiator such as azobisisoptyronitrile (AIBN). Obtainable.
  • a radical polymerization initiator such as azobisisoptyronitrile (AIBN).
  • the mass average molecular weight of the resin (C2) (Mw; polystyrene-reduced mass average molecular weight by gel permeation chromatography (GPC); the same shall apply hereinafter) is not particularly limited, but is not more than 20 000 force S, preferably 10000 or less More preferred.
  • Mw force is 0000 or less
  • the effect of the present invention is improved, and in particular, lithography properties such as resolution are improved.
  • it has excellent solubility in organic solvents, and can suppress the generation of foreign substances and development defects.
  • the foreign matter is a solid matter such as a particulate matter generated in the solution when the composition is used as a solution.
  • Development defects are all defects detected when a developed resist pattern is observed from directly above, for example, with a surface defect observation apparatus (trade name “KL A”) manufactured by KLA Tencor. Examples of such defects include scum, bubbles, dust, bridges (bridge structures between resist patterns), uneven color, and precipitates after development.
  • the lower limit of Mw is particularly limited Although it is not a thing, 2000 or more force S is preferable and 4000 or more are more preferable. When the Mw force is 000 or more, the etching resistance is improved, and the resist pattern does not swell at the time of development.
  • the degree of dispersion (Mw / Mn (number average molecular weight)) is preferably about 1.0 to 5.0, and more preferably 1.0 to 3.0.
  • the resin (C2) may be used alone or in combination of two or more.
  • the content of the resin (C2) in the component (C) is preferably 0.1% by mass or more, more preferably in the range of 0.1 to 95% by mass, and more preferably 10 to 95% by mass.
  • a preferred range is 15 to 90% by mass, and a particularly preferred range is 20 to 85% by mass.
  • the content of the resin (C2) is 0.1% by mass or more, the resistance of the resist film to the immersion medium is improved. Further, if it is 50% by mass or less, the lithography characteristics are improved.
  • the content of the component (C) with respect to the component (A) is preferably 0.1% by mass or more, more preferably in the range of 0.5 to 50% by mass, 0.5 to 25% by mass. % Is more preferred 1.0 to 20% by weight is particularly preferred 1.5 to 10% by weight is most preferred.
  • the content force of component (C) with respect to component (A) is 0.1% by mass or more, the resistance of the resist film to the immersion medium is improved.
  • it is 50% by mass or less the balance with the component (A) is good and the lithography one characteristic is improved.
  • the resins (C1) and (C2) used as the component (C) in the present invention do not have an acid-dissociable group, they are generally used, for example, as a base resin for a positive resist composition. Compared to existing resins (resins having acid dissociable, dissolution inhibiting groups), they have advantages such as easy synthesis and availability at low cost.
  • the positive resist composition for immersion exposure according to the present invention improves the resist pattern shape, retention time 3 ⁇ 4 / E, post exposure stability of the latent image rormed by the pattern-wise exposure of the resist layer, etc. Therefore, a nitrogen-containing organic compound (D) (hereinafter referred to as “component (D)”) can be added as an optional component.
  • component (D) a nitrogen-containing organic compound
  • aliphatic amines particularly secondary aliphatic amines, especially tertiary aliphatic amines, can be used arbitrarily from known ones.
  • the aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms.
  • Aliphatic amines include at least one hydrogen atom of ammonia NH, carbon number;
  • alkylamines or alkyl alcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, etc .; Trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-peptylamine, tri-n-octylamine, tri-n nonenoleamine, tri-n-decanylamine, tri-n n Trialkylamines such as dodecylamine; diethanolamine, triethanolanolamine, diisopropanolamine, triisopropanolamine, dioctanolamine, triethanolamine n O click pentanolamine
  • alkyl alcoholamines are preferred, with alkyl alcoholamines and trialkylamines being preferred.
  • alkyl alcoholamines triethanolamine and triisopropanolamine are most preferred.
  • Examples of the cyclic amine include a heterocyclic compound containing a nitrogen atom as a hetero atom.
  • the heterocyclic compound may be monocyclic (aliphatic monocyclic ammine) or polycyclic (aliphatic polycyclic ammine).
  • aliphatic monocyclic amine examples include piperidine and piperazine.
  • Aliphatic polycyclic amines having 6 to 10 carbon atoms are preferred. Specifically, 1,5-diazabicyclo [4. 3. 0] — 5 nonene, 1, 8 diazabicyclo [5.4 0] — 7 undecene, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane.
  • Component (D) is usually used in the range of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).
  • the positive resist composition for immersion exposure according to the present invention has a sensitivity deterioration prevention, resist pattern shape, left-handed Kyoheiji Temple, post exposure stability of the latent image formed by At least one selected from the group consisting of organic carboxylic acids and phosphorus oxoacids and their derivatives as components for improving the pattern-wise exposure of the resist layer.
  • Compound (E) (hereinafter referred to as component (E)) can be contained.
  • the organic carboxylic acid for example, acetic acid, malonic acid, citrate, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
  • Examples of phosphorus oxoacids and derivatives thereof include phosphoric acid, phosphonic acid, and phosphinic acid. Among these, phosphonic acid is particularly preferable.
  • Examples of the derivative of oxo acid of phosphorus include esters in which the hydrogen atom of the oxo acid is substituted with a hydrocarbon group.
  • Examples of the hydrocarbon group include an alkyl group having 1 to 5 carbon atoms and a carbon number of 6 ⁇ ; 15 aryl groups and the like.
  • phosphoric acid derivatives examples include phosphate esters such as di-n-butyl phosphate and diphenyl phosphate.
  • phosphonic acid derivatives include phosphonic acid esters such as phosphonic acid dimethylolestenole, phosphonic acid diol n-butyl ester, fenenorephosphonic acid, phosphonic acid diphenenoresestenole, and phosphonic acid dibenzyl ester.
  • phosphinic acid derivatives examples include phosphinic acid esters such as phenylphosphinic acid.
  • one type may be used alone, or two or more types may be used in combination.
  • Component (E) is used at a ratio of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).
  • the positive resist composition for immersion exposure according to the present invention further contains a miscible additive, for example, an additional resin for improving the performance of the resist film, and a coating for improving the coating property.
  • a miscible additive for example, an additional resin for improving the performance of the resist film
  • a coating for improving the coating property.
  • Surfactants, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, and the like can be appropriately added and contained.
  • the positive resist composition for immersion exposure of the present invention can be produced by dissolving a material in an organic solvent (hereinafter, sometimes referred to as (S) component and V).
  • each component used can be dissolved to form a uniform solution.
  • any one or more of known solvents for chemically amplified resists can be appropriately selected and used.
  • latones such as ⁇ -butyrolatatatone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl- ⁇ -pentyl ketone, methyl isopentyl ketone, 2-heptanone; ethylene glycolol, diethylene glycolol, propylene Polyhydric alcohols such as glyconole and dipropylene alcohol and derivatives thereof; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetate; Or monoanolequinolete such as monomethyl ether, monoethinoreethenore, monopropinoreethenore, monobutinoreethenore, etc. Or Monofu derivatives of polyhydric ⁇ alcohols such as compounds having an ether bond such as enyl ether; cyclic ethers such as Jiokisan; methyl lacty
  • organic solvents may be used alone or as a mixed solvent of two or more.
  • PGMEA propylene glycol monomethyl ether acetate
  • PGME propylene glycol monomethyl ether
  • EL EL
  • a mixed solvent in which PGMEA and a polar solvent are mixed is preferable.
  • the mixing ratio may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Within range! /.
  • the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2.
  • the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: Three.
  • a mixed solvent of at least one selected from the medium strengths of PGMEA and EL and a ⁇ -bubble outlet is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70: 30-95: 5.
  • component (S) a mixture of the above-mentioned mixed solvent of PGMEA and PGME and ⁇ -butyrolatatone is also preferable.
  • the amount of component (S) used is not particularly limited, but it is a concentration that can be applied to a substrate and the like, and is appropriately set according to the coating film thickness.
  • the solid content concentration of the resist composition is 2 -20% by mass, preferably 5 to 15% by mass.
  • the material can be dissolved in the component (S) by, for example, mixing and stirring each of the above components in the usual manner. If necessary, a dissolver, a homogenizer, a three-roll mill, etc. You may disperse and mix using a disperser. Also, after mixing, you can further filter using a mesh or membrane filter!
  • the positive resist composition for immersion exposure according to the present invention can form a highly hydrophobic resist film on the film surface.
  • the lithography properties are also good, which is suitable when a resist pattern is formed using immersion exposure.
  • the resin (C1) and (C2) have a force S, a fluorine atom, a structure having no acid-dissociable group, and the resin (A1) Since it has an acrylic structure that does not contain fluorine atoms, when a resist film is formed using the positive resist composition for immersion exposure, the relatively hydrophobic resins (C1) and (C2) It is presumed that is distributed near the outer surface of the resist film, while the relatively hydrophilic resin (A1) is distributed inside the resist film.
  • the resins (C1) and (C2) are distributed near the outer surface of the resist film, for example, the hydrophobicity of the obtained resist film surface is improved as compared with the case where the resin (A1) is used alone. It is presumed that the resin (A1) is distributed inside the resist film to ensure good lithography characteristics.
  • the resist film has excellent resistance to the immersion medium, such as suppression of elution (substance elution) of the components in the resist film into the immersion solvent when the immersion exposure process is performed. Therefore, it is suitable for immersion exposure. That is, the resist film formed using the positive resist composition for immersion exposure according to the present invention has a contact angle [for example, static] with respect to water as compared with the case where the component (C) is not added.
  • Static contact angle angle between the surface of the water drop on the resist film in the horizontal state and the resist film surface
  • dynamic contact angle water drop when the resist film is tilted
  • sliding angle the tilt angle of the resist film when water droplets start to fall when the resist film is tilted
  • the advance angle is such that when the plane 2 on which the droplet 1 is placed is gradually tilted, the droplet 1 moves (drops) on the plane 2.
  • the angle ⁇ between the droplet surface at the upper end lb of the droplet 1 and the plane 2 is the receding angle
  • the tilt angle ⁇ of plane 2 is the falling angle.
  • the resist film contacts an immersion solvent such as water during immersion exposure. Therefore, it is presumed that substance elution is affected by the characteristics of the resist film surface (for example, hydrophilicity / hydrophobicity).
  • the hydrophobicity of the film surface is improved, so that the substance elution suppressing effect is also improved.
  • the immersion medium is easily repelled from the membrane surface, the contact area and contact time between the membrane surface and the immersion medium can be reduced, and the influence of the immersion medium can be reduced. It is estimated that. For example, after immersion exposure, the immersion medium can be quickly removed from the resist film surface when removing the immersion medium.
  • the static contact angle, dynamic contact angle, and rolling angle can be measured, for example, as follows.
  • a resist composition solution is spin-coated on a silicon substrate, and then heated for 60 seconds under a predetermined condition, for example, a temperature condition of 100 to 110 ° C., to form a resist film.
  • DROP MASTER-700 manufactured by Kyowa Interface Science
  • AUTO SLIDING ANGLE SA-30DM
  • AUTO DIS PENSER AD-31 (manufactured by Kyowa Interface Science)
  • Etc. can be measured using a commercially available measuring device.
  • the positive resist composition for immersion exposure according to the present invention preferably has a measured force of a receding angle of 60 degrees (°) or more in a resist film obtained using the positive resist composition.
  • 0 ° force is preferred 60-; 130 ° is particularly preferred 65-; 100 ° is most preferred.
  • the receding angle force is 0 ° or more, the resist film surface is excellent in hydrophobicity and the substance elution suppression effect is improved, and when the receding angle is 150 ° or less, the lithography properties and the like are good.
  • the positive resist composition for immersion exposure according to the present invention preferably has a measured advance angle of 80 ° or more in a resist film obtained using the resist composition. ⁇ ; 110. Is more preferred 80 ⁇ ; 100 ° is particularly preferred.
  • the positive resist composition for immersion exposure according to the present invention preferably has a measured value of a static contact angle of 70 ° or more in a resist film obtained using the resist composition ⁇ 70 to 100 ° is more preferred, and 75 to 95 ° is particularly preferred.
  • the measured value of the falling angle in a resist film obtained using the resist composition is preferably 25 ° or less, more preferably 10 to 25 °. In particular, 12 to 25 ° is particularly preferable, and 15 to 23 ° is most preferable.
  • the falling angle is 25 ° or less, the substance elution suppression effect during immersion exposure is improved.
  • the falling angle is 10 ° or more, the lithography characteristics and the like are good.
  • the static contact angle, dynamic contact angle, and sliding angle are determined by the composition of the positive resist composition for immersion exposure, for example, the mixing ratio of the (A) component and the (C) component, It can be adjusted by adjusting the proportion of each structural unit such as the structural unit (a 3) in the component A). For example, by setting the content of component (C) to component (A) to be 0.1% by mass or more, the static contact angle and dynamic contact are much greater than when component (C) is not added. Increases the angle and decreases the falling angle
  • a high-resolution resist pattern can be formed, for example, a resist pattern having a dimension of 120 nm or less can be formed.
  • a resist pattern having a good shape in which the generation of foreign matters and development defects is suppressed it is possible to form a resist pattern having a good shape in which the generation of foreign matters and development defects is suppressed.
  • the resist pattern forming method includes a step of forming a resist film on a support using the positive resist composition for immersion exposure according to the present invention, a step of immersion exposure of the resist film, and the resist film. And developing a resist pattern.
  • the support is not particularly limited, and a conventionally known support can be used.
  • a substrate for an electronic component or a substrate on which a predetermined wiring pattern is formed More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given.
  • a material for the wiring pattern for example, copper, aluminum, nickel, gold or the like can be used.
  • the support may be a substrate in which an inorganic and / or organic film is provided on the substrate as described above.
  • An inorganic antireflection film (inorganic BAR C) is an example of the inorganic film.
  • examples of the organic film include an organic antireflection film (organic BARC).
  • the resist pattern forming method of the present invention can be performed, for example, as follows. That is, first, the resist composition of the present invention is applied onto a substrate such as a silicon wafer using a spinner or the like, and a pre-beta (post-apply bake (PAB)) is applied at a temperature of 80 to 150 ° C. 40-; 120 seconds, preferably 60-90 seconds, to form a resist film.
  • PAB post-apply bake
  • a predetermined exposure light source Is selectively exposed (immersion exposure) in an immersion medium. That is, exposure is performed through a mask pattern in an immersion medium, or drawing is performed by direct irradiation with an electron beam without using a mask pattern.
  • heat treatment post-exposure baking (PEB)
  • PEB post-exposure baking
  • this alkali developer for example, 0 -;!
  • a developing treatment using a 1-10 mass 0/0 tetramethylammonium Niu arm hydroxide (TMAH) aqueous solution preferably performed by rinsing with pure water.
  • the water rinsing can be performed, for example, by dropping or spraying water on the substrate surface while rotating the substrate to wash away the developer on the substrate and the resist composition for immersion exposure dissolved by the developer.
  • a resist pattern can be formed by drying.
  • An organic or inorganic antireflection film is provided between the substrate and the coating layer of the resist composition.
  • the wavelength used for the exposure is not particularly limited. KrF excimer laser, ArF excimer laser, F excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam),
  • the resist composition of the present invention is particularly effective for ArF excimer laser.
  • the positive resist composition of the present invention can be suitably used for immersion exposure.
  • the step of immersing and exposing the resist film can be performed, for example, as follows. First, the space between the resist film obtained as described above and the lens at the lowest position of the exposure apparatus is filled with a solvent (immersion medium) having a refractive index larger than that of air, and in that state, Exposure (immersion exposure) is performed with or without a desired mask pattern.
  • a solvent immersion medium having a refractive index larger than that of air
  • a solvent having a refractive index larger than the refractive index of air and smaller than the refractive index of a resist film formed using the positive resist composition of the present invention is preferable.
  • the refractive index of such a solvent is not particularly limited as long as it is within the above range.
  • the solvent having a refractive index larger than the refractive index of air and smaller than the refractive index of the resist film include water, a fluorine-based inert liquid, a silicon-based solvent, and the like.
  • fluorinated inert liquids include c HC1 F, CF OCH, CF OC H, C
  • Examples include liquids mainly composed of fluorine-based compounds such as HF, and boiling point of 70 to 180 ° C.
  • the fluorinated inert liquid has a boiling point in the above range, the medium used for immersion can be removed after exposure by a simple method, which is preferable.
  • a perfluorinated alkyl compound in which all the hydrogen atoms of the alkyl group are replaced with fluorine atoms is particularly preferred! /.
  • Specific examples of the perfluorinated alkyl compound include perfluoroalkyl ether compounds and perfluoroalkylamine compounds.
  • examples of the perfluoroalkyl ether compound include perfluoro (2-butyl monotetrahydrofuran) (boiling point: 102 ° C.).
  • examples of the perfluoroalkylamine compound include: Raising perfluorotributylamine (boiling point 174 ° C) with force S.
  • the positive resist composition of the present invention is excellent in sensitivity and resist pattern shape that are not easily affected by water
  • water is preferably used as a solvent having a refractive index larger than that of air. Used. Water is also preferable from the viewpoints of cost, safety, environmental issues, and versatility.
  • post-exposure heating post exposure beta (P EB)
  • development using an alkali developer composed of an alkaline aqueous solution preferably, water rinsing is performed using pure water.
  • water rinse for example, water is dropped or sprayed on the surface of the substrate while rotating the substrate to wash away the developer on the substrate and the positive resist composition for immersion exposure dissolved by the developer.
  • drying is performed to obtain a resist pattern in which the resist film (the coating film of the positive resist composition for immersion exposure) is patterned into a shape corresponding to the mask pattern.
  • Example 1 comparative example;! ⁇ 2
  • Each component shown in Table 1 was mixed and dissolved to prepare a positive resist composition.
  • (A) —1 A polymer represented by the following chemical formula (A) — 1.
  • the number attached to the lower right of () indicates the ratio (mol%) of each structural unit.
  • (B) -1 (4 methylphenol) diphenylsulfoumonium fluoro-butanesulfonate.
  • (C) 1, (C) 3 Polymers represented by the following chemical formulas (C) 1, (C) 3, respectively.
  • the number attached to the lower right of 0 indicates the proportion of the structural unit (mol%).
  • the (A) -1 was obtained by copolymerization by a known dropping polymerization method using a monomer for deriving each structural unit.
  • the (C) 1 was obtained by polymerization using a monomer that induces a structural unit by a known dropping polymerization method.
  • the hydrophobicity of the resist film was evaluated by measuring the static contact angle, the falling angle, and the receding angle (hereinafter referred to as the contact angle) of the resist film surface before and after exposure in the following procedure. .
  • Example 1 and Comparative Examples 1 and 2 were applied onto an 8-inch silicon wafer using a spinner, and pre-baked (PAB) at 110 ° C. for 60 seconds on a hot plate. Then, a resist film having a thickness of 150 nm was formed by drying. Water was added dropwise to the surface of this resist film (resist film before exposure), and contact angles and the like were measured using DROP MASTER-700 manufactured by Kyowa Interface Science Co., Ltd.
  • Table 2 shows the measurement results such as the contact angle of the resist film before and after exposure.
  • the resist film obtained using the resist composition of Example 1 was exposed as compared with the resist films obtained using the resist compositions of Comparative Examples 1 and 2. Before and after exposure, the static contact angle and receding angle are large, and the falling angular force S is small. By adding (C) 1 and (C) 3, a highly hydrophobic film can be obtained. It could be confirmed.
  • a resist film was formed in the same manner as in the above hydrophobicity evaluation except that an 8-inch silicon wafer having a hexamethyldisilazane (HMDS) treatment on the surface was used.
  • HMDS hexamethyldisilazane
  • the exposed resist film was analyzed in the same manner as described above, and after exposure, the cationic (PAG +) and anion (PAG) components of component (B) and the elution amount of component (D) (X 10 — 12 mo 1 / cm 2 ) was measured and the total amount (X 10 12 mol / cm 2 ) was determined. These results are not shown in Table ⁇ 3.
  • Example 1 About the resist composition of Example 1 and Comparative Examples 1-2, the resist pattern was formed in the following procedures, respectively.
  • the organic anti-reflective coating composition “ARC-29A” (trade name, manufactured by Pruss Science Co., Ltd.) was applied onto an 8-inch silicon wafer using a spinner and baked on a hot plate at 205 ° C. for 60 seconds. By drying, an organic antireflection film having a thickness of 77 nm was formed. On this antireflection film, the resist compositions of Example 1 and Comparative Examples 1 and 2 were applied using a spinner, pre-beta (PAB) at 120 ° C. for 60 seconds on a hot plate, and dried. As a result, a resist film having a thickness of 150 nm was formed.
  • PAB pre-beta
  • TMAH tetramethylammonium hydroxide
  • a line-and-space resist pattern (hereinafter referred to as an L / S pattern) having a line width of 120 nm and a pitch of 240 nm was formed by rinsing with water and performing spin-drying.
  • the optimum exposure dose (Eop) (unit: mj / cm 2 (energy amount per unit area)), that is, the sensitivity at which an L / S pattern with a line width of 120 nm and a pitch of 240 nm is formed was determined.
  • the sensitivity was equivalent in any of the resist compositions.
  • Length measurement SEM scanning electron microscope, acceleration voltage 800V, product name: S-9220, manufactured by Hitachi, Ltd.
  • the standard deviation ( ⁇ ) three times the value (3) was calculated as a measure of LWR.
  • the smaller the value of 3 ⁇ the smaller the line width roughness, and the more uniform L / S pattern was obtained.
  • the value of 3 ⁇ was the same for the examples using any resist composition.
  • an L / S pattern is formed using a mask pattern that targets an L / S pattern with a line width of 120 nm and a pitch of 260 nm and a mask pattern that targets an L / S pattern with a line width of 130 nm and a pitch of 260 nm.
  • the MEF value was obtained from the following equation.
  • CD and CD have a line width of 120 nm and a line width of 130 nm, respectively.
  • MEF is a fixed pitch.
  • the resist composition of Example 1 had good performance at the same level as the resist compositions of Comparative Examples 1 and 2 with respect to various lithography properties.
  • (A) -2 A polymer represented by the following chemical formula (A) -2.
  • the number attached to the lower right of () indicates the proportion (mol%) of each structural unit.
  • (C) 1-2 a polymer represented by the following chemical formula (C) 1-2.
  • chemical formula (C) -12 the number attached to the lower right of () indicates the proportion (mol%) of the structural unit.
  • the hydrophobicity of the resist film can be measured by measuring the static contact angle, the falling angle, the backward receding angle, and the advancing angle (hereinafter referred to as contact angle) of the resist film surface before and after exposure in the following procedure. evaluated.
  • the organic anti-reflective coating composition “ARC-29A” (trade name, manufactured by Pruss Science Co., Ltd.) was applied onto an 8-inch silicon wafer using a spinner and baked on a hot plate at 205 ° C. for 60 seconds. By drying, an organic antireflection film having a thickness of 77 nm was formed. On this antireflection film, the resist compositions of Examples 2 to 7 and Comparative Example 3 were applied using a spinner, pre-beta (PAB) at 100 ° C. for 60 seconds on a hot plate, and dried. As a result, a resist film having a thickness of 150 nm was formed.
  • PAB pre-beta
  • Tables 5 and 6 show the measurement results such as the contact angle of the resist film before and after exposure.
  • the resist films obtained using the resist compositions of Examples 2 to 7 were compared with the resist film obtained using the resist composition of Comparative Example 1 before exposure. Later, the static contact angle, receding angle, and advancing angle increased, and the sliding angle decreased, and it was confirmed that a highly hydrophobic film could be obtained by adding (C) 2 and (C) 3 Can It was.
  • the resist composition of the present invention is highly hydrophobic! /, Can form a resist film, suppresses substance elution during immersion exposure, and has good strength and lithography characteristics. Therefore, it can be suitably used as a resist composition for immersion exposure. Therefore, the present invention is extremely useful industrially.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

L'invention concerne une composition de résist positif pour une exposition à une immersion dans un liquide qui peut former un film de résist ayant une hydrophobicité de surface élevée et une excellente performance de lithographie ; et un procédé de formation d'un motif de résist. La composition de résist positif pour une exposition à une immersion dans un liquide est une composition comprenant (A) un composant de résine dont la solubilité dans les alcalis est augmentée par l'action d'un acide ; (B) un composant générateur d'acide capable de créer un acide lorsqu'il est exposé à la lumière ; et (C) un composant de résine contenant un atome de fluor mais n'ayant pas de groupe capable de dissocier un acide, le composant de résine (A) contenant (A1) une résine ayant (a) une unité constitutive issue de l'acide acrylique mais ne contenant pas d'atome de fluor, et le composant de résine (C) contenant (C1) une résine à chaîne principale non circulaire et (C2) une résine à chaîne principale circulaire.
PCT/JP2007/070749 2006-12-08 2007-10-24 Composition de résist positif pour une exposition à une immersion dans un liquide et procédé de formation de motif de résist WO2008068971A1 (fr)

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JP5186255B2 (ja) * 2007-03-20 2013-04-17 富士フイルム株式会社 レジスト表面疎水化用樹脂、その製造方法及び該樹脂を含有するポジ型レジスト組成物
JP5277128B2 (ja) * 2008-09-26 2013-08-28 富士フイルム株式会社 液浸露光用ポジ型レジスト組成物及びパターン形成方法
EP2189844A3 (fr) * 2008-11-19 2010-07-28 Rohm and Haas Electronic Materials LLC Compositions comportant un matériau de sulfonamide et procédés de photolithographie
JP5586294B2 (ja) 2009-03-31 2014-09-10 富士フイルム株式会社 感活性光線性または感放射線性樹脂組成物、及び該組成物を用いたパターン形成方法
JP5572643B2 (ja) * 2012-01-23 2014-08-13 富士フイルム株式会社 レジスト組成物及び該レジスト組成物を用いたパターン形成方法
JP6604049B2 (ja) * 2015-06-25 2019-11-13 住友ベークライト株式会社 半導体装置の製造方法
JP2017111447A (ja) * 2015-12-16 2017-06-22 住友ベークライト株式会社 感光性樹脂組成物および電子装置の製造方法

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JP2005316352A (ja) * 2004-03-31 2005-11-10 Central Glass Co Ltd トップコート組成物
JP2006048029A (ja) * 2004-07-07 2006-02-16 Fuji Photo Film Co Ltd 液浸露光用ポジ型レジスト組成物及びそれを用いたパターン形成方法
JP2006133712A (ja) * 2004-10-08 2006-05-25 Fuji Photo Film Co Ltd ポジ型レジスト組成物及びそれを用いたパターン形成方法
JP2006291177A (ja) * 2005-02-23 2006-10-26 Promerus Llc ノルボルネン系ポリマー、その組成物、及び該組成物を使用するリソグラフィ法
JP2007065024A (ja) * 2005-08-29 2007-03-15 Fujifilm Corp ポジ型レジスト組成物及びそれを用いたパターン形成方法
WO2007094192A1 (fr) * 2006-02-17 2007-08-23 Tokyo Ohka Kogyo Co., Ltd. Composition de resist pour lithographie par immersion et procede de formation d'un motif de resist

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JP2005232095A (ja) * 2004-02-20 2005-09-02 Central Glass Co Ltd 含フッ素環状化合物、含フッ素高分子化合物、それを用いたレジスト材料及びパターン形成方法
JP2005316352A (ja) * 2004-03-31 2005-11-10 Central Glass Co Ltd トップコート組成物
JP2006048029A (ja) * 2004-07-07 2006-02-16 Fuji Photo Film Co Ltd 液浸露光用ポジ型レジスト組成物及びそれを用いたパターン形成方法
JP2006133712A (ja) * 2004-10-08 2006-05-25 Fuji Photo Film Co Ltd ポジ型レジスト組成物及びそれを用いたパターン形成方法
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WO2007094192A1 (fr) * 2006-02-17 2007-08-23 Tokyo Ohka Kogyo Co., Ltd. Composition de resist pour lithographie par immersion et procede de formation d'un motif de resist

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