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WO2007135836A1 - Composition de résist positif pour exposition par immersion et procédé de formation d'un motif de résist - Google Patents

Composition de résist positif pour exposition par immersion et procédé de formation d'un motif de résist Download PDF

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Publication number
WO2007135836A1
WO2007135836A1 PCT/JP2007/058759 JP2007058759W WO2007135836A1 WO 2007135836 A1 WO2007135836 A1 WO 2007135836A1 JP 2007058759 W JP2007058759 W JP 2007058759W WO 2007135836 A1 WO2007135836 A1 WO 2007135836A1
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WO
WIPO (PCT)
Prior art keywords
group
alkyl group
structural unit
resin
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/058759
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English (en)
Japanese (ja)
Inventor
Kotaro Endo
Makiko Irie
Takeshi Iwai
Yoshiyuki Utsumi
Yasuhiro Yoshii
Tsuyoshi Nakamura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokyo Ohka Kogyo Co Ltd
Original Assignee
Tokyo Ohka Kogyo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tokyo Ohka Kogyo Co Ltd filed Critical Tokyo Ohka Kogyo Co Ltd
Priority to US12/300,760 priority Critical patent/US7799507B2/en
Publication of WO2007135836A1 publication Critical patent/WO2007135836A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0395—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 a backbone with alicyclic moieties
    • 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 method for forming a resist pattern, which are used in immersion exposure (immersion lithography).
  • Lithography method is frequently used for the manufacture of fine structures in various electronic devices such as semiconductor devices and liquid crystal devices. With the miniaturization of device structures, the resist pattern has become finer in the lithography process. It is requested. Currently, it is possible to form a fine resist pattern with a line width of about 90 nm in the most advanced area using, for example, an ArF excimer laser by the lithographic method. Pattern formation is required.
  • a chemically amplified resist containing an acid generator that generates an acid upon irradiation with radiation and a base resin whose alkali solubility is changed by the action of the acid generated from the acid generator has attracted attention. Development is underway. With chemically amplified resists, high resolution is achieved, and catalysis and chain reaction of acids generated by irradiation of radiation can be used, resulting in a quantum yield of 1 or higher and high sensitivity. .
  • a resin having an acid dissociable, dissolution inhibiting group is mainly used.
  • the acid dissociable, dissolution inhibiting group include an acetal group such as an ethoxyethyl group, a tertiary alkyl group such as a tert-butyl group, a tert-butoxycarbonyl group, and a tert-butoxycarbonylmethyl group.
  • (Meth) acrylic acid means one or both of an acrylic ester having a hydrogen atom bonded to the ⁇ -position and a methacrylic ester having a methyl group bonded to the a-position.
  • (meth) acrylate means either an acrylate having a hydrogen atom bonded to the ⁇ -position or a metatalate having a methyl group bonded to the ⁇ -position.
  • the g-line with the main spectrum of the mercury lamp is 436 nm with a resist resolution of about 0.3
  • the i-line with the main spectrum of the mercury lamp of 365 nm is also used with about 0.5 to 0.30.
  • a 248 nm KrF excimer laser beam is used at about 0.30 to 0.15 m
  • a 193 nm ArF excimer laser beam is used at about 0.15 m or less.
  • F excimer laser 157 nm
  • Ar excimer laser 126 nm
  • EUV extra pole
  • immersion exposure immersion lithography
  • an inert gas such as air or nitrogen
  • the resist film on the wafer is larger than the refractive index of air!
  • immersion exposure even when a light source with the same exposure wavelength is used, the same high resolution as when using a light source with a shorter wavelength or using a high NA lens can be achieved, and moreover, It is said that there is no drop in the depth of the point.
  • immersion exposure can be performed using an existing exposure apparatus. For this reason, immersion exposure is expected to be able to form resist patterns with low cost, high resolution, and excellent depth of focus, requiring a large amount of capital investment.
  • In the manufacture of the required semiconductor elements much attention has been paid to the fact that it has great effects on the semiconductor industry in terms of cost and lithography properties such as resolution. At present, water is mainly considered as the immersion medium.
  • Patent Document 1 JP-A-10-161313
  • Non-Patent Document 1 Journal of Vacuum Science & Technology B (USA), 1999, No. 17, No. 6, pages 3306-3309.
  • Non-Patent Document 2 Journal of Vacuum Science & Technology B (USA), 2001, 19th, No. 6, 2353-2 356.
  • Non-Patent Document 3 Proceedings of SPIE (USA) 2002, 4691, 459-465.
  • the present invention has been made in view of the above circumstances, and can form a resist film having high hydrophobicity on the film surface and good lithographic properties, and is suitable for immersion exposure. It is an object to provide a composition and a method for forming a resist pattern.
  • the first aspect (aspect) of the present invention is an immersion exposure light comprising a resin component (A) whose alkali solubility is increased by the action of an acid and an acid generator component (B) which generates an acid upon exposure.
  • the resin component (A) has a main chain cyclic resin (A1) containing a fluorine atom and having no acid dissociable group, and a structural unit (a) derived from acrylic acid. And a positive resist composition for immersion exposure containing a resin (A2) that does not contain a fluorine atom.
  • the second aspect (aspect) of the present invention is a step of forming a resist film on a substrate using the positive resist composition for immersion exposure according to the first aspect (aspect).
  • a resist pattern forming method including a step of developing the resist film to form a resist pattern.
  • structural unit means a monomer unit constituting a polymer (resin).
  • alkyl group includes linear, branched and cyclic monovalent saturated hydrocarbon groups.
  • a “lower alkyl group” is an alkyl group having 1 to 5 carbon atoms.
  • Exposure includes not only irradiation of light but also irradiation of whole radiation such as electron beam. The concept is
  • a positive resist composition for immersion exposure and resist pattern formation suitable for immersion exposure can be formed because a resist film with high hydrophobicity on the film surface and good lithography characteristics can be formed.
  • 1 is a diagram for explaining 2).
  • 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 (B) (hereinafter referred to as component (B)) is included.
  • the component (A) is insoluble in alkali before exposure.
  • the acid increases the alkali solubility of the component (A).
  • the resin (A1) is a main chain cyclic resin containing a fluorine atom and having no acid dissociable group.
  • the “acid-dissociable group” means a group dissociated by the action of an acid generated from the component (B) by exposure.
  • the “acid-dissociable group” means a group dissociated by the action of an acid generated from the component (B) by exposure.
  • Rataton-containing cyclic groups in the structural unit (a2), polar group-containing aliphatic hydrocarbon groups in the structural unit (a3), polycyclic aliphatic hydrocarbon groups in the structural unit (a4), etc. are ⁇ acid-dissociable groups '' Is not included.
  • 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 the component (B).
  • the acid-dissociable, dissolution-inhibiting group of the base resin for chemically amplified resists It can be used as proposed.
  • Specific examples of the acid dissociable, dissolution inhibiting group include those similar to those exemplified as the acid dissociable, dissolution inhibiting group for the structural unit (al) described later in the structural unit (al). here,
  • the “dissolution inhibition” in the acid dissociable dissolution inhibiting group means that the 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, dissolution inhibiting group of the structural unit (al) is an acid dissociable group that is dissociated by the action of an acid generated from the component (B). A) The alkali solubility of the component increases.
  • the “acid-dissociable group” may be one having a dissolution inhibitory property or not having a dissolution inhibitory property.
  • main chain cyclic type rosin means that the structural unit constituting the aliphatic has a monocyclic or polycyclic ring structure, and the ring of the ring structure. It means that at least one of the above, preferably two or more carbon atoms have a structural unit constituting the main chain (hereinafter sometimes referred to as main chain cyclic structural unit).
  • etching resistance is improved. The improvement in etching resistance is presumed to be due to the fact that the carbon density is increased by having the main chain cyclic structural unit.
  • the main chain cyclic structural unit includes a structural unit derived from polycycloolefin (polycyclic olefin), a structure containing an anhydride of the dicarboxylic acid mentioned in the structural unit (a'3) described later. Examples include units.
  • the main chain has a structural unit from which a polycyclic linker is also derived.
  • a structural unit from which polycycloolefin is derived a structural unit having a basic skeleton represented by the following general formula (a ′) is preferable.
  • a is 0 or 1, and is preferably 0 in consideration of industrial availability.
  • the structural unit having the basic skeleton represented by the general formula (a ′) is the structural unit represented by the general formula (a ′) (ie, bicyclo [2.2.1] —2-heptene (norbornene)). Force-induced structural units, and tetracyclo [4. 4. 0. I 2 ' 5. 1. 7 1 °] —3-dodecene force-induced structural units).
  • the ring skeleton may have a substituent.
  • “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.
  • the resin (A1) has a structural unit other than the main chain cyclic structural unit, for example, a structural unit (a) (structural unit in which acrylic acid power is also induced) mentioned in the later described resin (A2).
  • a structural unit (a) structural unit in which acrylic acid power is also induced
  • the main chain cyclic type in rosin (A1) constituent units, based on the combined total of all structural units constituting the ⁇ (A1), 50 ⁇ : L00 as preferred that have been included mol%, 80 ⁇ :! L00 Monore 0/0 preferably from force / ⁇ .
  • the resin (A1) is excellent in the effect of the present invention (the effect that it can form a resist film with high hydrophobicity on the film surface and good lithography properties), it is represented by the following general formula (I). It preferably has a structural unit (a ′ 1).
  • 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 the group (la) represented by the general formula (la).
  • the hydrophobicity of the resist film surface is improved by having a structural unit that can be obtained.
  • lithography properties are improved.
  • the reason why such a strong 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 (A1) can be obtained. This is presumed to contribute to improvements in various characteristics of lithography, such as resolution and resist pattern shape.
  • a is the same as a in the above formula (a ′).
  • the alkyl group of I ⁇ to R 4 may be linear or branched.
  • the alkyl group having 1 to 10 carbon atoms is preferable.
  • the alkyl group having 1 to 8 carbon atoms is more preferable.
  • the alkyl group is more preferable.
  • Examples of a strong 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 I ⁇ 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 ⁇ 100% is more preferred 50 ⁇ 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 is preferably an alkylene group having 1 to 8 carbon atoms, which is preferably a linear or branched chain, and more preferably an alkylene group having 1 to 8 carbon atoms.
  • An alkylene group having 1 to 5 carbon atoms is more preferable.
  • the strong 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 from the viewpoint of synthesis and the like, 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 preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and still more preferably 6 to C: L0.
  • 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 ⁇ 100% is more preferred 50-100% is particularly preferred 100%, ie hydrogen atoms It is most preferable that all are substituted with 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 (A1) in the component (A) 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 and a pentafluoroethyl group.
  • I ⁇ to R 4 is a group (la) represented by the general formula (la), and the remaining 0 to 3 are a hydrogen atom, linear or branched A chain alkyl group and a linear or branched fluorinated alkyl group are one or more selected.
  • 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 Preferably it is a hydrogen atom.
  • a structural unit represented by the following general formula (lb) is particularly preferable.
  • p is an integer of 1 to 10, and an integer of 1 to 8 is preferred, and 1 is most preferred.
  • q is an integer from 1 to 5, and an integer from 1 to 4 is preferred, and 1 is most preferred.
  • the proportion of structural units ( a , 1) in rosin (A1) is preferably 30 mol% or more, more preferably 40 mol% or more, based on the total of all structural units constituting rosin (A1). Preferred 45 mol% or more Power S More preferred. By making it 30 mol% or more, the effect of the present invention is improved.
  • the upper limit of the proportion of the structural unit (a ′ 1) may be 100 mol% without particular limitation. For example, when other structural units such as structural unit (a '2) described later are included, considering the balance with those structural units, 95 mol% or less is preferable, and 90 mol% or less is more preferable. 70 mol% or less is more preferable.
  • a monomer for deriving the structural unit (a'1) can be synthesized, for example, by the method disclosed in US Pat. No. 6,420,503.
  • the resin (A1) preferably has a structural unit (a′2) represented by the following general formula (IV) in addition to the structural unit (a′1).
  • the resin (A1) has the structural unit (a ′ 2), the hydrophobicity of the resist film surface is further improved.
  • R 7 is a fluorinated alkyl group; a is 0 or 1; ]
  • a is the same as a in the above formula (a ′).
  • fluorinated alkyl group for R 7 examples include the same groups as those described above for the fluorinated alkyl group for R 5 in formula (la).
  • fluorinated alkyl group for R 7 a fluorinated alkyl group in which a part of the hydrogen atom of the alkyl group is substituted with a fluorine atom is preferred.
  • the force of one hydrogen atom of the alkyl group And a group substituted with a perfluoroalkyl group a group in which an alkylene group is bonded to a perfluoroalkyl group.
  • fluorinated alkyl group those having a fluorination rate of 30 to 90% are particularly preferred, and 50 to 80% are more preferred.
  • the fluorination rate is 30% or more, the effect of improving the hydrophobicity of the resist film surface is excellent.
  • fluorination rate is 90% or less, the lithography characteristics are improved.
  • one type may be used alone, or two or more types may be used in combination.
  • the proportion of the structural unit (a, 2), relative to the combined total of all structural units ⁇ (A1), 5 to 60 Monore 0/0 force S Preferably, 10 to 60 Monore 0 / more preferably 0 force S, 30 to 60 Monore 0/0 force S further favorable preferable.
  • the effect of having the structural unit (a ′ 2) is excellent (an effect of further improving the hydrophobicity of the resist film surface), and by setting it to the upper limit value or less, A balance can be achieved and the lithography properties are improved.
  • Monomers for deriving the structural unit (a, 2) include, for example, a fluorinated alkyl ester of (meth) acrylic acid, cyclopentadiene or diene as described in JP-A-2000-235263. This can be synthesized by reacting cyclopentagen with the Diels-Alder reaction, which is a known reaction.
  • the resin (A1) is a component that does not impair the effects of the present invention (the effect of forming a resist film having high hydrophobicity on the film surface and good lithography properties). Including structural unit (a '3) other than (a, 2).
  • the structural unit (a ′ 3) there is no acid dissociable group, and the above structural units (a ′ l) to (a ′ 2)
  • 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) is derived from an acrylic acid salt such as the structural unit (a2) to the structural unit (a4) listed in the later-described resin (A2).
  • Structural units, dicarboxylic acid anhydride-containing structural units, polycycloalkylene force without substituents, derived structural units, polycycloolefin forces with polycyclic alicyclic groups as substituents Examples are derived structural units.
  • the acid anhydride-containing structural unit of dicarboxylic acid refers to a structural unit having a -C (0) -0 -C (0) structure.
  • Examples of such include structural units containing monocyclic or polycyclic cyclic acid anhydrides, and more specifically, monocyclic maleic anhydride shown in the following (a'31).
  • a structural unit derived from a polycyclohexylene force having a polycyclic alicyclic group as a substituent the structural unit that does not have the above-described substituent and from which a polycycloolefin is also derived can be used.
  • the substituent include a structural unit having a polycyclic group such as a tricyclodecanyl group, an adamantyl group, or a tetracyclopropyl group.
  • the combination and ratio of the structural units such as the structural units (a, 1) to (a, 3) can be appropriately adjusted depending on the required characteristics.
  • the resin (A1) has at least the structural unit (a ′ 1) because it is excellent in the effects of the present invention (the effect of forming a resist film having high hydrophobicity on the film surface and good lithography properties). It is preferable.
  • strong resin include a structural unit (a '1) and a solid unit polymer (a' 3) that does not include a powerful structural unit ( a '2).
  • Yo ⁇ ) and the like include a structural unit (a '1) and the structural unit (a' 2) and binary polymers containing (except configuration unit (a '3).
  • the ratio (molar ratio) of each structural unit is the effect of the present invention. All of the components that make up the resin (A1) are excellent in (the effect of forming a resist film with high hydrophobicity on the film surface and good lithography properties) and the control of the synthesis of the polymer.
  • a tool 40-90 mole 0 / possible power Ri preferably fixture 40 to 70 mol% is 0 that is a structural unit (a '1) 40 to 95 mole 0/0 It is most preferable that the structural unit (a'2) is 5 to 60 mol%, more preferably 10 to 60 mol%, and 30 to 60 mol%. Most preferably.
  • the resin (A1) is obtained by, for example, polymerizing a monomer for deriving a predetermined structural unit by a known radical polymerization using a radical polymerization initiator such as azobis isobutyoxy-tolyl (AIBN). Can be obtained.
  • a radical polymerization initiator such as azobis isobutyoxy-tolyl (AIBN).
  • the mass average molecular weight (Mw; polystyrene-converted mass average molecular weight by Gel Permeation Chromatography (GPC). The same shall apply hereinafter) of the resin (A1) is not particularly limited, but is 20000 or less. More preferably 10,000 or less.
  • Mw is 20000 or less, the effects of the present invention (the effect that a resist film with high hydrophobicity on the film surface and good lithography characteristics can be formed) are improved, and in particular, the lithography characteristics such as resolution are improved. .
  • 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.
  • KL A surface defect observation apparatus
  • the lower limit value of Mw is not particularly limited, but is preferably 2000 or more, force S, and more preferably 4000 or more. When the Mw is 4000 or more, there are advantages such as improved etching resistance and resist pattern swelling that hardly occurs during development and resists pattern collapse.
  • the degree of dispersion (MwZMn (number average molecular weight)) is preferably about 1.0 to 5.0, more preferably 1.0 to 3.0.
  • the rosin (A1) may be used alone or in combination of two or more.
  • the content of cocoa butter (A1) in the component is more preferably in the range of 0.1 to 50% by mass, and more preferably 0.1 to 25% by mass. Mass% is particularly preferred 0.1 to: L0 mass% is most preferred.
  • the content power of the resin (A1) is 0.1% by mass or more, the hydrophobicity of the surface of the resist film formed using the resist composition is improved, and the resistance to the immersion medium is improved.
  • the content is 50% by mass or less, the balance with the resin (A2) becomes good and the lithography properties are improved.
  • the resin (A2) is a resin having a structural unit (a) derived from an acrylic acid salt and containing no fluorine atom.
  • the resin (A2) is not particularly limited as long as it has a structural unit (a) that also induces acrylic acid power and does not contain a fluorine atom, and so far, it has not been used for chemically amplified positive resists.
  • One or two or more types of fats proposed as base fats can be used.
  • the structural unit (a) derived from acrylic acid does not contain a fluorine atom.
  • the “structural unit in which acrylic acid power is also induced” means a structural unit formed by cleavage of an ethylenic double bond of acrylic acid.
  • the concept includes derivatives that are partially or wholly substituted with other groups or atoms.
  • acrylic acid for example, a substituent (an atom or group other than a hydrogen atom) is bonded to the carbon atom at the a position of acrylic acid in a narrow sense, and a substituted acrylic acid or carboxy of these acrylic acids is used. And acrylic acid esters in which the hydrogen atom of the 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, and examples thereof include the structural units listed in the structural units (al) to (a4) described later, Group bonded to the ester side chain of an acrylate ester (acid dissociable, dissolution inhibiting group, rataton-containing cyclic group, polar group-containing aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group, etc.) Is mentioned.
  • the a-position (a-position carbon atom) is a carbon atom to which a carbonyl group is bonded unless otherwise specified.
  • a halogen atom (however, a fluorine atom is excluded in the structural unit ( a )), a lower alkyl group, a halogenated lower alkyl group (however, a structural unit) In (a), a fluorinated lower alkyl group is excluded. ) And the like.
  • examples of the halogen atom as the substituent at the ⁇ -position include a chlorine atom, a bromine atom, and an iodine atom.
  • a lower linear or branched alkyl group such as a group.
  • halogenated lower alkyl group as the substituent at the a position include groups in which some or all of the hydrogen atoms of the lower alkyl group have been substituted with halogen atoms other than fluorine atoms.
  • halogen atom here include a chlorine atom, a bromine atom, and an iodine atom.
  • the ⁇ -position of acrylic acid is bonded to a hydrogen atom, a halogen atom other than a fluorine atom, a lower alkyl group, or a halogenated lower alkyl group (however, a fluorinated lower alkyl group).
  • a hydrogen atom or a lower alkyl group is preferred, and a hydrogen atom or a methyl group is most preferred! / ,.
  • examples of the structural unit (a) include structural units represented by the following general formula (a).
  • R is a hydrogen atom, a halogen atom other than a fluorine atom, a lower alkyl group, or a halogenated lower alkyl group (excluding a fluorinated lower alkyl group), and X is a hydrogen atom, or It is a monovalent organic group that does not contain fluorine atoms.
  • R halogen atom, lower alkyl group or halogenated lower alkyl group Excludes an elementary lower alkyl group. ) Are the same as the above halogen atoms (excluding fluorine atoms), lower alkyl groups or halogenated lower alkyl groups (excluding fluorinated lower alkyl groups) as substituents at the ⁇ -position. It is done.
  • Examples of the organic group for X include the same as the above-mentioned “organic group in acrylic ester” except that it does not contain a fluorine atom.
  • [0050] ⁇ ([alpha] 2) is a structural unit (a), against the total of all the structural units that constitute the ⁇ (A2), 50 to: be contained in a proportion of LOO mol 0/0 preferred instrument 70 to: LOO mol 0/0 it forces more preferable containing.
  • the resin (A2) since the effect of the present invention (the effect that a resist film with high hydrophobicity on the film surface and good lithography characteristics can be formed) is excellent, the resin (A2) has a structure derived from attalic acid. It is preferable that only unit (a) can be used.
  • the resin (A2) preferably has a structural unit (al) derived from an acrylate ester chain that does not have a fluorine atom and contains an acid dissociable, dissolution inhibiting group.
  • structural unit derived from an acrylate ester 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 (A2) insoluble in alkali before dissociation, and the entire resin (A2) is alkali-soluble after dissociation.
  • those proposed as acid dissociable, dissolution inhibiting groups for base resin for chemically amplified resists can be used.
  • As the acid dissociable, dissolution inhibiting group generally, a group that forms a cyclic or chain tertiary alkyl ester with a carboxyl group in (meth) acrylic acid or the like; an acetal such as an alkoxyalkyl group or the like.
  • Type acid dissociable, dissolution inhibiting groups are widely known.
  • the term "(meth) acrylic acid ester" acrylic acid ester having a hydrogen atom bonded to the ⁇ -position, means either or both of methacrylate ester having a methyl group bonded to the ⁇ -position.
  • the "tertiary alkyl ester” is an ester formed by substitution with a hydrogen atom of a carboxy group, a chain or cyclic alkyl group, and its carboalkyl group.
  • 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 the specification is a relative concept with respect to aromatics, and is defined to mean a group, a compound, or the like that does not have aromaticity.
  • “Aliphatic branched” means that it has a branched structure without aromaticity.
  • the structure of the “aliphatic branched acid dissociable, dissolution inhibiting group” is not limited to a carbon and hydrogen power group (hydrocarbon group), but is preferably a hydrocarbon group. Further, the “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated.
  • a tertiary alkyl group having 4 to 8 carbon atoms is preferred. Specifically, a tert-butyl group, a tert-amyl group, a tert-heptyl group, etc. Can be mentioned.
  • Aliphatic cyclic group indicates that it has no aromaticity, and is a monocyclic group or a polycyclic group.
  • the “aliphatic cyclic group” in the structural unit (al) may or may not have a substituent.
  • the basic ring structure is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but may be a hydrocarbon group.
  • hydrocarbon group may be either saturated or unsaturated, but is usually preferably saturated.
  • the “aliphatic cyclic group” is preferably a polycyclic group. Specific examples of the aliphatic cyclic group may be substituted with, for example, a lower alkyl group, a halogen atom other than a fluorine atom, or 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.
  • 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.
  • Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and 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, specifically, 2-methyl 2-adamantyl. Group, 2-ethyl-2-adamantyl group and the like. Or, in a structural unit represented by the following general formula (al "), an aliphatic cyclic group such as an adamantyl group such as a group bonded to an oxygen atom of a carbo-oxy group (-C (O) -0-). And a group having a group and a branched alkylene group having a tertiary carbon atom bonded thereto.
  • R is the same as R in the general formula (a), and R 15 and R lb are alkyl groups (both linear and branched, preferably 1 to 5 carbon atoms) Indicates. ]
  • 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. And for exposure When more acid is generated, 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 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 IT 1 and R 2 include the same lower alkyl groups as those described above for R, and a methyl group is most preferred, which is preferably a methyl group or an ethyl group.
  • the acid dissociable, dissolution inhibiting group (pi) is preferably a group represented by the following general formula (pi-1).
  • Examples of the lower alkyl group for Y include the same as the lower alkyl group for R above.
  • aliphatic cyclic group for Y many conventionally proposed ArF resists and the like can be appropriately selected from monocyclic or polycyclic aliphatic cyclic groups. Examples thereof are the same as the “aliphatic cyclic group”.
  • examples of the acetal type acid dissociable, dissolution inhibiting group include groups 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 be bonded to form a ring.
  • R 17, R 18, the carbon number of the alkyl group is preferably 1 to 15, linear, branched either Yogu Echiru group, and most preferably preferred instrument methyl group is a methyl group .
  • one of R 17 and R 18 is preferably a hydrogen atom and the other is a katyl group.
  • R 19 is a linear, branched or cyclic alkyl group, preferably having 1 to 15 carbon atoms, and 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 an ethyl group or a methyl group, and most preferably an ethyl group.
  • R 19 is cyclic, it is preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and further preferably 5 to carbon atoms: LO is most preferable.
  • a monocycloalkane, bicycloalkane which may or may not be substituted with a halogen atom other than a fluorine atom or 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 tricycloalkane or tetracycloalkane.
  • Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. I can get lost. Among them, 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 chain. It is an alkylene group (preferably an alkylene group having 1 to 5 carbon atoms), and the end of R 19 and the end of R 17 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.
  • a 4- to 7-membered ring is preferable, and a 4- to 6-membered ring is more preferable.
  • Specific examples of the cyclic group include a tetrahydrobiranyl group and a tetrahydrofuran group.
  • a structural unit represented by the following general formula (al-0-1) and a structural unit force represented by the following general formula (al-0-2) are selected. It is preferable to use one or more.
  • R represents a hydrogen atom, a halogen atom other than a fluorine atom, a lower alkyl group, or a halogenated lower alkyl group (excluding a fluorinated lower alkyl group);
  • X 1 represents acid-dissolving dissolution inhibition. Indicates a group.
  • R represents a hydrogen atom, a halogen atom other than a fluorine atom, a lower alkyl group, or a halogenated lower alkyl group (excluding a fluorinated lower alkyl group);
  • X 2 represents an acid solution;
  • Re represents a releasable dissolution inhibiting group;
  • Y 2 represents an alkylene group or an aliphatic cyclic group;
  • the halogen atom, lower alkyl group or halogenated lower alkyl group of R is a halogen atom, lower alkyl group or This is the same as the halogeno lower alkyl group.
  • 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 R in the above (al-0-1).
  • 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, and the aliphatic cyclic group is the above except that a group in which two or more hydrogen atoms are removed is used.
  • the same explanation as in the “aliphatic cyclic group” can be used.
  • the structural unit (al) includes structural units represented by the following general formulas (al-1) to (al-4).
  • X ′ represents a tertiary alkyl ester type acid dissociable, dissolution inhibiting group
  • Y represents carbon A lower alkyl group of 1 to 5 or an aliphatic cyclic group
  • n represents an integer of 0 to 3
  • m represents 0 or 1
  • R represents a hydrogen atom, a halogen atom other than a fluorine atom, or a lower alkyl Or a halogenated lower alkyl group (excluding a fluorinated lower alkyl group)
  • R 1 ′ and R 2 ′ each independently represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms o
  • At least one of the R 1 'and R 2 ' is preferably a hydrogen atom, 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 for X 1 above.
  • Examples of the aliphatic cyclic group for Y include the same groups as those exemplified above in the explanation of the “aliphatic cyclic group”.
  • one type may be used alone, or two or more types may be used in combination.
  • the structural unit represented by the general formula (al-1) is specifically preferred (al-1-11) to (al-1-6) or (al1-135) to (al- 1-41) It is more preferable to use at least one kind.
  • R represents a hydrogen atom, a halogen atom other than a fluorine atom, a lower alkyl group, or a halogenated lower alkyl group (excluding a fluorinated lower alkyl group), and R 11 represents a lower alkyl group.
  • R represents a hydrogen atom, a halogen atom other than a fluorine atom, a lower alkyl group, or a halogenated lower alkyl group (excluding a fluorinated lower alkyl group)
  • R 12 represents a lower alkyl group.
  • H represents an integer of 1 to 3
  • 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. [0089] In general formula (al-1-02)! /, And R! /, The same as R in general formula (a) above.
  • 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.
  • h is preferably 1 or 2, and most preferably 2.
  • the proportion of the structural unit (al) is based on all the structural units that constitute the ⁇ (A2), 10 to 80 Monore 0/0 force S Preferably, 20-70 Monore 0 / more preferably 0 force S, 25 to 50 Monore 0/0 force S further favorable preferable.
  • the lower limit value or more a pattern can be easily obtained when the resist yarn and the composition are made, and by setting it to the upper limit value or less, it is possible to balance with other structural units.
  • the resin (A2) preferably has, in addition to the structural unit (al), a structural unit (a2) that does not have a fluorine atom and is derived from an acrylate ester containing a latathone-containing cyclic group. .
  • the ratatone-containing cyclic group refers to a cyclic group containing one ring (lataton ring) containing a -o-c (o) structure.
  • the rataton ring is counted as the first ring, and if it is only a 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) has a high affinity for the resist film to the substrate or the affinity for a developer containing water when the resin (A2) is used for forming the resist film. It is effective in raising the level.
  • any unit can be used without any particular limitation.
  • examples of the latatatone-containing monocyclic group include a group in which one hydrogen atom is removed from the petit latatotone.
  • examples of the latathone-containing polycyclic group include groups in which a bicycloalkane, tricycloalkane, or tetracycloalkane having a latathone ring has one hydrogen atom removed.
  • examples of the structural unit (a2) include structural units represented by the following general formulas (a2 ⁇ 1) to (a2 ⁇ 5).
  • R is a hydrogen atom, a halogen atom other than a fluorine atom, a lower alkyl group, or a halogenated lower alkyl group (excluding a fluorinated lower alkyl group), and R ′ is a hydrogen atom, a lower alkyl group. Or an alkoxy group having 1 to 5 carbon atoms, and m is an integer of 0 or 1. ]
  • R in the general formulas (a2-l) to (a2-5) is the same as R in the structural unit (al).
  • the lower alkyl group for R ′ is the same as the lower alkyl group for R in the structural unit (al).
  • 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.
  • Ratio of ⁇ (A2) structural unit in (a2), relative to the combined total of all structural units constituting the ⁇ (A2), 5 to 70 Monore 0/0 force S Preferably, 10 to 60 Monore 0 / more preferably 0 force S, 20 to 50 Monore 0/0 force S more preferred.
  • the effect of containing the structural unit (a2) by setting it to the lower limit value or more is sufficient.
  • the balance with other structural units can be obtained by setting the value to less than the upper limit.
  • Liquor (A2) is added to the structural unit (al) or to the structural units (al) and (a2). Further, it is preferable that the structural unit (a3) derived from an acrylate ester having no fluorine atom and containing a polar group-containing aliphatic hydrocarbon group is contained.
  • the resin (A2) has the 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 the 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 having 1 to 10 carbon atoms (preferably an alkylene group) and a polycyclic aliphatic hydrocarbon group (polycyclic group).
  • a resin selected from a large number of proposed resins for ArF excimer laser resist compositions can be used.
  • the polycyclic group preferably has 7 to 30 carbon atoms.
  • a structural unit derived from an acrylate ester group 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.
  • two or more hydrogen atoms are removed from adamantane, two or more hydrogen atoms are removed from norbornane, and two or more hydrogen atoms are removed from tetracyclododecane.
  • the industrial group is preferred.
  • 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: LO carbon atoms, the hydroxy group of acrylic acid is used. A structural unit derived from a tilester is preferred. When the hydrocarbon group is a polycyclic group, a structural unit represented by the following formula (a3-1), a structural unit represented by (a3-2), etc. Are listed as preferred.
  • R is a hydrogen atom, a halogen atom other than a fluorine atom, a lower alkyl group, or a no- or lower-alkylated lower alkyl group (excluding a fluorinated lower alkyl group), and j is an integer of 1 to 3. And k is an integer from 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.
  • j is 1, a hydroxyl group is preferably bonded to the 3rd position of the adamantyl group.
  • j is preferably 1, especially when the hydroxyl group is bonded to the 3-position of the adamantyl group.
  • k is preferably 1.
  • the cyan group is preferably bonded to the 5th or 6th position of the norbornyl group.
  • one type may be used alone, or two or more types may be used in combination.
  • the resin (A2) does not impair the effects of the present invention (if the film surface is highly hydrophobic and can form a resist film with good lithography properties! Including other structural units (a4) other than (al) to (a3).
  • the structural unit (a4) does not contain a fluorine atom and is not classified into the above structural units (al) to (a3)! /
  • Other ArF excimer lasers are not particularly limited. Many known hitherto known strengths can be used for resist resins such as for KrF excimer lasers (preferably for ArF excimer lasers).
  • As the structural unit (a4) for example, a structural unit derived from an ester acrylate ester containing an acid non-dissociable aliphatic polycyclic group is preferable. Examples of the polycyclic group include those exemplified in the case of the structural unit (al), for ArF excimer laser, for KrF excimer laser (preferably for ArF excimer laser).
  • a large number of conventionally known strengths can be used as the oil component of the resist composition.
  • At least one kind selected from tricyclodecanyl group, adamantyl group, tetracyclododecyl group, isobornyl group and norbornyl group is preferable in terms of industrial availability.
  • These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.
  • R is a hydrogen atom, a halogen atom other than a fluorine atom, a lower alkyl group, or a halogenated lower alkyl group (excluding a fluorinated lower alkyl group).
  • 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 (A2)
  • the structural unit (a4) is contained in an amount of 1 to 30 mol%, preferably 1% to the total of all the structural units constituting the resin (A2). It is preferable to contain 10 to 20 mol%.
  • the resin (A2) is a copolymer having at least the structural units (al), (a2) and (a3). Examples thereof include copolymers having the structural units (a 1), (a2) and (a3), and copolymers comprising the structural units (al), (a2), (a3) and (a 4). .
  • the resin (A2) those containing three kinds of structural units represented by the following general formula (A2-11) are particularly preferable.
  • R 41 , R 4d and R 44 are each independently a hydrogen atom, a halogen atom other than a fluorine atom, a lower alkyl group, or a lower alkyl group in which a hydrogen atom is substituted with a halogen atom other than a fluorine atom (halogen group)
  • R 42 is a lower alkyl group.
  • the lower alkyl group for 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 above, and is most preferably a methyl group or a methyl group, preferably an ethyl group.
  • the resin (A2) is obtained by polymerizing monomers for deriving each structural unit by a known radical polymerization using a radical polymerization initiator such as azobisisobutyl-tolyl (AIBN). Therefore, it can be obtained.
  • a radical polymerization initiator such as azobisisobutyl-tolyl (AIBN). Therefore, it can be obtained.
  • the mass average molecular weight (Mw) of the resin (A2) (polystyrene conversion standard by gel permeation chromatography) is not particularly limited, but preferably 2000 to 50000.
  • the degree of dispersion (Mw / Mn) i is preferably 1.0 to 5.0 force S, more preferably 1.0 to 3.0 force S, and most preferably 1.2 to 2.5.
  • rosin (A2) may be used alone or in combination of two or more.
  • the content of cocoa butter (A2) in component (A) is preferably in the range of 50-99.9% by mass, more preferably 75-99.9% by mass, 80-99.9 More preferred is mass%.
  • the content of the resin (A2) is 99.9% by mass or less, the balance with the resin (A1) is improved, and the hydrophobicity of the resist film surface formed using the resist composition is improved. And the immersion medium resistance is improved. If it is 50% by mass or more, the lithography properties are improved.
  • the component (B) is not particularly limited, and those that have been proposed as acid generators for chemical amplification resists can be used.
  • acid generators include onium salt acid generators such as ododonium salts and sulfo salt, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes.
  • onium salt acid generators such as ododonium salts and sulfo salt, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes.
  • a wide variety of acid generators such as diazomethane acid generators such as poly (bissulfol) diazomethanes, nitrobenzilsulfonate acid generators, iminosulfonate acid generators, and disulfone acid generators are known.
  • Examples of the acid salt-based acid generator include an acid generator represented by the following general formula (b-O).
  • 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 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
  • the cyclic alkyl group preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and still more preferably 6 to carbon atoms: LO.
  • the linear or branched fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. preferable.
  • the cyclic fluorinated alkyl group preferably has 4 to 12 carbon atoms, preferably 5 to carbon atoms, more preferably 6 to LO, and most preferably LO.
  • 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: LOO%, more preferably 50 to 100%, Particularly preferred is one in which all hydrogen atoms are substituted with fluorine atoms, since the strength of the acid increases.
  • R 51 is most preferably a linear alkyl group or a linear fluorinated alkyl group.
  • R 52 is a hydrogen atom, a hydroxyl group, a halogen atom, are straight or branched chain alkyl group, a linear or branched Harogeni spoon alkyl 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 1 to 5, particularly 1 to 4, and more preferably 1 to 3.
  • the linear or branched alkyl halide group is a group in which some or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms.
  • the alkyl group here are the same as those of the “alkyl group” in R 52 .
  • the halogen atom to be substituted are the same as those described for the “halogen atom” in R 52 above.
  • the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.
  • R 52 is preferably a hydrogen atom.
  • R 53 is an aryl group which may have a substituent, and the structure of the basic ring (matrix ring) excluding the substituent includes a naphthyl group, a phenyl group, an anthracene group and the like.
  • a phenol group is desirable.
  • substituents examples 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).
  • aryl group for R 53 those having no substituent are more preferable.
  • 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-0) include the following.
  • R 1 " ⁇ 3 ", R 5 "to 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. Represents 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 R lw to R 3 is not particularly limited, for example, an aryl group having 6 to 20 carbon atoms, in which part or all of the hydrogen atoms are alkyl groups, alkoxy groups. It may not be substituted with a group, a halogen atom, etc.
  • the aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at low cost. For example, a phenol group and a naphthyl group can be mentioned.
  • alkyl group on which the hydrogen atom of the aryl group may be substituted examples include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group, which are preferably alkyl groups having 1 to 5 carbon atoms. That is the most preferred.
  • alkoxy group that may be substituted with a hydrogen atom of the aryl group, a methoxy group and an ethoxy group are preferred, with an alkoxy group having 1 to 5 carbon atoms being preferred.
  • the halogen atom that may be substituted for the hydrogen atom of the aryl group is preferably a fluorine atom.
  • the “ ⁇ ” alkyl group is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. From the viewpoint of excellent resolution, the number of carbon atoms is preferably 1 to 5. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, A decanyl group and the like can be mentioned, and a methyl group can be mentioned as a preferable one because it is excellent in resolution and can be synthesized at low cost.
  • R lw to R 3 ′′ are 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. Most preferably, it is 1 to 4 carbon atoms.
  • the cyclic alkyl group is a cyclic group as shown by the above R 1 ′′, preferably a carbon number of 4 to 15 carbon atoms, more preferably a carbon number of 4 to 10 carbon atoms. Most preferably, the number is from 6 to 10.
  • the fluorinated alkyl group is most preferably 1 to 4 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Further, the fluorination rate of the fluorine alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to: LO 0%, more preferably 50 to 100%. Those substituted with atoms are preferred because the strength of the acid is increased.
  • 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.
  • ⁇ R 6 at least one represents an aryl group. All of R 5 ′′ to R 6 , are preferably aryl groups.
  • Examples of the aryl group of R 5 "to R 6 include those similar to the aryl group of R1" to r 3 ".
  • Examples of the alkyl group for R 5 "to R 6 " include the same alkyl groups as for,, to ".
  • R 5 ′′ to R 6 ′′ are phenol groups.
  • Those similar to - "(1 b) R 4 in the formula is as" the like R 4 of formula (b-2) in.
  • sodium salt-based acid generator represented by the formulas (b-1) and (b-2) include trifluoromethanesulfonate or nonafluorobutanesulfonate of diphlo-rhodonium, Bis (4-tert-butylphenol) trifluoromethane sulfonate or nonafluorobutane sulfonate, trifluoromethane sulfonate of trifluorosulfone, heptafluoropropane sulfonate or nonafluorolob Tansusulfonate, tri (4 methylphenol) sulfurium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfotrifluoromethane Lomethanesulfonate and its heptafluoropropanesulfonate Or its
  • ohmic salts in which the ionic part of these ohmic salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can also be used.
  • the anion part is replaced with a caron part represented by the following general formula (b-3) or (b-4).
  • a -um salt-based acid generator can also be used (the cation moiety is the same as (b-1) or (b-2)).
  • X represents a C 2-6 alkylene group in which at least one hydrogen atom is replaced by a fluorine atom; ⁇ ", ⁇ "each independently represents at least one hydrogen atom is fluorine. Represents an alkyl group having 1 to 10 carbon atoms substituted with an atom.
  • 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 2 to 6 carbon atoms, preferably 3 to 3 carbon atoms. 5 and most preferably 3 carbon atoms.
  • ⁇ "and ⁇ " are each independently 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 It is C1-C7, More preferably, it is C1-C3.
  • 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 because it has good solubility in the resist solvent within the above carbon number range. ⁇ .
  • the proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to: L00%, and most preferably, 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.).
  • 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 and a linear, branched or cyclic alkyl group having 1 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.
  • 1 to 20 carbon atoms are preferable. 1 to 10 carbon atoms are more preferable. 1 to 8 carbon atoms are more preferable. 1 to 6 carbon atoms are particularly preferable.
  • halogenated alkyl group 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 completely halogenated alkyl group means that all of the hydrogen atoms are halogen atoms. Put in Means a substituted alkyl group.
  • 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 preferably 4 to 20 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, more preferably LO.
  • 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 completely 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.
  • the organic group for R 32 is preferably a linear, branched or cyclic alkyl group, aryl group or cyan group.
  • Examples of the 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.
  • More preferable examples of the oxime sulfonate acid generator include compounds represented by the following general formula (B-2) or (B-3).
  • R 34 is an aryl group.
  • R 35 represents an alkyl group having no substituent or a halogenated alkyl group.
  • R 36 represents a cyano group, an alkyl group having no substituent, or a halogenalkyl 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.]
  • R 33 is more preferably a fluorinated alkyl group, preferably a halogenated alkyl group.
  • the fluorinated alkyl group in R 33 is preferably fluorinated with 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, and even more preferably 90% or more. I like it! /
  • the aryl group of R 34 includes an aromatic hydrocarbon such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group, and a phenanthryl group.
  • 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 preferably has 1 to 4 carbon atoms, more preferably 1 to 4 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 preferably has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. Most preferred.
  • R 35 is preferably a fluorinated alkyl group, preferably a halogenated alkyl group, more preferably a partially or fully fluorinated alkyl group.
  • the fluorinated alkyl group in R 35 preferably has 50% or more of the hydrogen atoms of the alkyl group fluorinated, more preferably 70% or more, and even more preferably 90% or more. This is preferable because the strength of the 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 the halogenated alkyl group having no substituent of R 36 is an alkyl group or a group having no substituent of R 33 described above. Examples thereof are the same as the halogenalkyl group.
  • Examples of the divalent or trivalent aromatic hydrocarbon group for R 37 include groups in which the aryl group strength of R 34 is one or two hydrogen atoms removed.
  • P is preferably 2.
  • oxime sulfonate-based acid generators include ⁇ - (p-toluenesulfo-oxyximino) monobenzyl cyanide, ⁇ - ( ⁇ chlorobenzene-sulfo-oxyoximino) -benzyl cyanide, ⁇ - ( 4-Nitrobenzenesulfo-luoxyimino) -Benzyl cyanide, Hiichi (4-troo 2 trifluoromethylbenzenesulfo-ruximino) Benzyl cyanide, ⁇ - (Benzenesulfo-ruximino) —4-Clorobenzoylcia-do , ⁇ (Benzenesulfo-ruximino) — 2, 4 dichlorobenzil cyanide, ⁇ — (Benzenesulfo-ruximino) — 2, 6 dichlorobenzil cyanide, ⁇ (Benzenes
  • oxime sulfonate acid generator include the following four compounds.
  • bisalkyl or bisarylsulfol diazomethanes include bis (isopropylsulfol) diazomethane, bis (p toluenesulfol) diazomethane, bis (1 , 1-dimethylethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, bis (2,4 dimethylphenylsulfol) 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 (bissulfol) diazomethanes include 1,3 bis (phenylsulfol diazomethylsulfol) pronone, 1, 4 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 ohmic salt having a fluorinated alkyl sulfonic acid ion as the ion! / it is preferable to use, as the component (B), an ohmic salt having a fluorinated alkyl sulfonic acid ion as the ion! /.
  • the content of the component (B) in the positive resist composition for immersion exposure of the present invention is as follows: For 100 parts by mass, 0.5 to 30 parts by mass, preferably 1 to L0 parts by mass. By setting the above range, pattern formation is sufficiently performed. In addition, it is preferable because a uniform solution is obtained and storage stability is good.
  • the positive resist composition for immersion exposure of the present invention is intended to improve the resist pattern shape, post exposure stability of the latent image formed by the pattern-wise exposure of the resist layer, etc. Furthermore, 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 and tertiary aliphatic amines, can be used arbitrarily from known ones. Is preferred.
  • the aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic groups preferably have from 12 to 12 carbon atoms.
  • At least one hydrogen atom of ammonia has a carbon number of 1
  • Examples thereof include amines (alkylamines or alkylalcoholamines) substituted with 12 or less alkyl groups or hydroxyalkyl groups.
  • Specific examples thereof include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-noramine and n-decylamine; jetylamine, di-n-propylamine and di-n- Dialkylamines such as ptylamine, di-n-octylamine, dicyclohexylamine; trimethylolamine, triethinoreamine, tri-n-propylamine, tri-n-butynoleamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-amine Trialkylamines such as ptyramine, tri-n-otatylamin, tri-n-noramine, tri-n-de-ramine, tri-
  • 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. Can be mentioned.
  • 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, such as 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 of the present invention has a post exposure stability of the latent image formed by the pattern.
  • component of s organic carboxylic acid, and at least one compound selected from the group power consisting of phosphorus oxoacid and its derivatives (E) (Hereinafter referred to as “component (E)”).
  • component (E) 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 preferred.
  • Examples of derivatives of phosphorus oxoacids include esters in which the hydrogen atom of the oxoacid 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 phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.
  • Examples of the phosphonic acid derivatives include phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid diol n-butenoresestenole, phenolinophosphonic acid, phosphonic acid diphenolinoestenole, and phosphonic acid dibenzyl ester.
  • phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid diol n-butenoresestenole, phenolinophosphonic acid, phosphonic acid diphenolinoestenole, and phosphonic acid dibenzyl ester.
  • phosphinic acid esters such as phenol phosphinic acid Is mentioned.
  • one type may be used alone, or two or more types may be used in combination.
  • Component (E) is used in a proportion 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 may further contain a miscible additive as desired, for example, an additional resin for improving the performance of the resist film and a coating property.
  • a miscible additive for example, an additional resin for improving the performance of the resist film and a coating property.
  • surfactants, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, and the like can be added as appropriate.
  • the positive resist composition for immersion exposure of the present invention can be produced by dissolving the material in an organic solvent (hereinafter sometimes referred to as the component (S)).
  • each component to be used it is sufficient if each component to be used can be dissolved into a uniform solution. Any one of conventionally known solvents for chemically amplified resists can be used. Two or more kinds can be appropriately selected and used.
  • latones such as ⁇ -butyrolatatane
  • ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl- ⁇ -amyl ketone, methyl isoamyl ketone, 2-heptanone
  • Polyhydric alcohols such as glycol and derivatives thereof; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; the above polyhydric alcohols or the above Monomethyl ether, monoethylenoatenore, monopropinoreatenore, monobutenoleatenore, etc.
  • polyhydric alcohols such as compounds having ether bonds such as phenol ether; cyclic ethers such as dioxane; methyl lactate, ethyl lactate ( ⁇ L), methyl acetate, ethyl acetate, butyl acetate, pyruvic acid Esters such as methyl, ethyl pyruvate, methyl methoxypropionate, ethoxypropionate, etc .; And aromatic organic solvents such as tenole, phenenole, butinolevenoleethenole, ethenorebenzene, jetinolebenzene, amylbenzene, isopropylbenzene, toluene, xylene, cymene and mesitylene. These organic solvents can be used alone or as a mixed solvent of two or more. Of these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGMEA), prop
  • 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, but is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Preferably 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 among PGMEA and EL and ⁇ -petit-mouth rataton is also preferable.
  • the mixing ratio of the former and the latter is preferably 70: 30-95: 5.
  • the amount of component (S) used is not particularly limited, but it is a concentration that can be applied to a substrate, etc., and can be appropriately set according to the coating film thickness. It is used so as to be in the range of 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-mentioned components in the usual manner. If necessary, a dissolver, a homogenizer, a three-roll mill, etc. You may disperse and mix using a disperser. Further, after mixing, the mixture may be filtered using a cocoon mesh or a 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 as described above. Also, the lithography characteristics are good, and a resist pattern can be formed without practical problems when used as a resist in immersion exposure.
  • rosin (A1) has a main chain cyclic structure containing a fluorine atom and no acid-dissociable group. Does not contain fluorine atoms! Therefore, when the resist film is formed using the positive resist composition for immersion exposure, the hydrophobicity is relatively high and the resin (A1) is the resist film.
  • a relatively hydrophilic resin ( ⁇ 2) distributed near the outer surface is distributed inside the resist film. It is presumed that it may be used for spreading.
  • the distribution of the resin (A1) near the outer surface of the resist film improves the hydrophobicity of the resulting resist film surface (retraction angle), for example, compared to the case where the resin (A2) is used alone. It is presumed that good lithography characteristics can be secured by distributing the resin (A2) inside the resist film together with the increase in the falling angle and the falling angle.
  • the powerful resist film has excellent resistance to the immersion medium, for example, by suppressing the elution (substance elution) of the components in the resist film into the immersion solvent during the immersion exposure process. It is suitable for immersion exposure.
  • the resist film formed using the positive resist composition for immersion exposure according to the present invention has a contact angle with water [for example, static] as compared with the case where only the resin (A2) is used as the component (A).
  • Contact angle angle between the surface of the water droplet on the resist film in the horizontal state and the resist film surface
  • dynamic contact angle contact angle when the water droplet starts to fall when the resist film is tilted
  • Contact angle at the end point in front of the drop direction and contact angle (retreat angle) at the end point in the fall direction;)
  • drop angle when the resist film is tilted
  • the resist film comes into contact with 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 membrane surface is improved, so that the substance elution suppression effect is also improved.
  • the immersion medium can be easily repelled in addition to the membrane surface force, and the contact area and contact time between the membrane surface and the immersion medium can be reduced. It is estimated that it can be reduced.
  • the resist film surface force immersion medium can be quickly removed when the immersion medium is removed after immersion exposure.
  • the receding angle and the falling angle are measured as follows.
  • a resist composition solution is spin-coated on a 6-inch diameter silicon substrate, and then heated at 90 ° C. for 90 seconds to form a resist film.
  • the measured value of the receding angle in a resist film obtained using the positive resist composition is 55 ° or more. It is most preferable that the angle is 55 to 130 °, and it is most preferable that the angle is 60 to 100 °.
  • the receding angle is 55 ° 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 characteristics are good.
  • the positive resist composition for immersion exposure according to the present invention preferably has a measured value of the falling angle in a resist film obtained using the resist composition of 36 ° or less, preferably 30 ° or less. Is more preferably 25 ° or less, and most preferably 20 ° or less.
  • the sliding angle is 36 ° or less, the substance elution suppression effect during immersion exposure is improved.
  • the measured value of the sliding angle is preferably 10 ° or more, more preferably 12 ° or more, and further preferably 15 ° or more.
  • the falling angle is 10 ° or more, the lithography characteristics and the like are good.
  • the size of the receding angle and the sliding angle depends on the composition of the positive resist composition for immersion exposure, for example, the mixing ratio of the resin (A1) and the resin (A2) in the component (A), It can be adjusted by adjusting the proportion of each structural unit such as structural unit (a3). For example, by setting the ratio of the resin (A1) in the component (A) to 1% by mass or more, the receding angle is greatly increased and the falling angle is smaller than when the resin (A2) is used alone. .
  • a high-resolution resist pattern can be formed, for example, a resist pattern having a dimension of 120 nm or less can be formed.
  • the positive resist composition for immersion exposure according to the present invention 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 resin (A1) used as the component (A) does not have an acid-dissociable group.
  • the resin used as the base resin of the di-resist composition resin having an acid dissociable, dissolution inhibiting group
  • it has advantages such as easy synthesis and availability at low cost.
  • the resist pattern forming method of the present invention includes a step of forming a resist film on a substrate using the positive resist composition for immersion exposure of the present invention, a step of immersing the resist film, and developing the resist film. And a step of forming a resist pattern.
  • a positive resist composition for immersion exposure is applied onto a substrate such as a silicon wafer using a spinner and the like, and then subjected to pre-beta (post-apply beta (PAB) treatment) to form a resist film.
  • pre-beta post-apply beta
  • an organic or inorganic antireflection film may be provided between the substrate and the coating layer of the resist composition to form a two-layer laminate.
  • an organic antireflection film can be further provided on the resist film to form a two-layer laminate, and a three-layer laminate in which a lower antireflection film is further provided.
  • the antireflection film provided on the resist film is preferably soluble in an alkali developer.
  • the steps so far can be performed using a known method. It is preferable to set the operating conditions as appropriate according to the composition and characteristics of the positive resist composition used for immersion exposure. Yes.
  • immersion exposure Liquid Immersion Lithography
  • immersion exposure is selectively performed on the resist film obtained above through a desired mask pattern.
  • the space between the resist film and the lowermost lens of the exposure apparatus is previously filled with a solvent (immersion medium) having a refractive index larger than that of air, and exposure (immersion exposure) is performed in that state. .
  • the wavelength used for the exposure is not particularly limited, and can be performed using radiation such as an ArF excimer laser, a KrF excimer laser, or an F laser. Resist assembly that helps the present invention
  • the composition is effective for KrF or ArF excimer lasers, especially ArF excimer lasers.
  • the immersion film is filled with the immersion medium between the resist film and the lowermost lens of the exposure apparatus, and exposure (immersion exposure) is performed in that state.
  • a solvent having a refractive index which is larger than the refractive index of air and smaller than the refractive index of a resist film formed using a positive resist composition for immersion exposure preferable.
  • the refractive index of such a solvent is not particularly limited as long as it is within the above range.
  • Examples of the solvent having a refractive index larger than that of air and smaller than that of the resist film include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent.
  • fluorinated inert liquid examples include C HC F, C F OCH, C F OC H, C
  • Examples include liquids mainly composed of fluorine-based compounds such as HF, and boiling point of 70 to 180 ° C.
  • the thing of 80-160 degreeC is more preferable. If the fluorinated inert liquid has a boiling point in the above range, it is preferable that the medium used for immersion can be removed by a simple method after the exposure is completed.
  • 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.
  • perfluoroalkyl ether compound Fluoro (2-butyl monotetrahydrofuran) (boiling point 102 ° C.) can be mentioned, and examples of the perfluoroalkylamine compound include perfluorotributylamine (boiling point 174 ° C.).
  • the positive resist composition for immersion exposure of the present invention is particularly resistant to adverse effects due to water, and is excellent in sensitivity and resist pattern profile shape, and therefore has a refractive index greater than that of air.
  • water water is preferably used. Water also favors cost, safety, environmental issues and versatility.
  • post-exposure heating post exposure beta (P EB)
  • development using an alkaline developer having 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.
  • 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 is obtained.
  • (B) -1 Triphenylsulfo-mumnonafluoro-n-butanesulfonate.
  • the obtained positive resist composition is applied on a silicon wafer having a diameter of 8 inches using a spinner, pre-betaned on a hot plate at 115 ° C for 60 seconds, and dried to form a film.
  • a resist film having a thickness of 275 nm was formed. After dropping one drop (50 1) of pure water onto the resist film, the receding angle and the falling angle were measured with the following apparatus and conditions (the receding angle and the falling angle before exposure).
  • Example 1 19. 5 20. 5 60. 1 58. 6
  • Example 2 17. 5 19. 0 68. 1 67. 5
  • Example 3 17. 0 18. 5 68. 7 68. 0
  • Comparative Example 2 21. 0 ; 25. 0 58. 0 55. 3
  • the falling angle and the receding angle are for evaluating the hydrophilicity / hydrophobicity of the resist film.
  • the receding angle increases compared to Comparative Examples 1 and 2. Since the falling angle was reduced, it was confirmed that the resist films of Examples 1 to 3 were improved in comparison with the hydrophobic force comparison examples 1 and 2.
  • An organic antireflection coating composition “ARC-29” (trade name, manufactured by Bruichi Science Co., Ltd.) was applied onto an 8-inch silicon wafer using a spinner, and 205 ° C, 60 ° C. on a hot plate. By baking for 2 seconds and drying, an organic antireflection film having a film thickness of 77 nm was formed. Then, the positive resist compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were applied on the antireflection film using a spinner, respectively, on a hot plate at 115 ° C. for 60 seconds. Then, a pre-beta (PAB) treatment was performed and dried to form a resist film with a thickness of 275 nm.
  • PAB pre-beta
  • TMAH tetramethylammonium hydroxide
  • a line-and-space resist pattern (hereinafter referred to as LZS pattern and! /) was formed with a line width of 120 nm and a pitch of 240 nm.
  • the resist film formed using the positive resist composition for immersion exposure of the present invention using both the resin (A1) and the resin (A2) has high hydrophobicity.
  • the lithography characteristics were as good as or better than the conventional chemically amplified positive resist composition. Therefore, at present, an aqueous medium such as water is mainly studied as an immersion medium. Therefore, it is clear that the positive resist composition for immersion exposure according to the present invention, which can form a resist film having high hydrophobicity and good lithography characteristics, is suitable for immersion exposure.
  • formula (A) -9 the number attached to the lower right of () indicates the ratio (mol%) of each structural unit.
  • the receding angle and the falling angle were measured in the same manner as described above. The same equipment is used.
  • the static contact angle was measured using the same procedure. The results are shown in Table 4.
  • Table 4 the type of the resin (A1) used ((A) -6 to (A) -8) and the resin (A2) ((A) -9)
  • the content ratio hereinafter referred to as (A1) content (vs. (A2)), unit: mass%) is also shown.
  • the static contact angle, the falling angle, and the receding angle are for evaluating the hydrophilicity and hydrophobicity of the resist film. In Examples 4 to 15, the static contact angle and receding angle are higher than those in Comparative Example 3. It increased and the sliding angle decreased.
  • a resist pattern was formed in the same manner as in the above lithographic characteristics except that a mask pattern having a hole inner diameter of 140 nm and a pitch of 280 nm as a target was used.
  • the hole diameter is 140 nm and the pitch is 280 nm. A turn was formed.
  • the optimum exposure dose (Eop) (unit: mjZcm 2 (energy amount per unit area)
  • Eop the sensitivity at which a hole pattern with a hole inner diameter of 140 nm and a pitch of 280 nm is formed
  • the cross-sectional shape of the obtained hole pattern was observed by SEM.
  • the lithography characteristics of Examples 13 and 14 were particularly excellent.
  • a positive resist composition for immersion exposure and a resist pattern forming method suitable for immersion exposure which can form a resist film with high hydrophobicity on the film surface and good lithography characteristics. it can. Therefore, the present invention is extremely important in industry.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition de résist positif pour exposition par immersion, comprenant un ingrédient de résine (A) dont la solubilité en alcalis est accrue par l'action d'un acide et un ingrédient générateur d'acide (B) qui génère un acide lors d'une exposition à la lumière, l'ingrédient de résine (A) comprenant une résine (A1) de type à chaîne principale cyclique contenant des atomes de fluor et ne comportant pas de groupements dissociables en milieu acide et une résine (A2) comprenant une unité constitutive (a) dérivée de l'acide acrylique et ne contenant pas d'atome de fluor.
PCT/JP2007/058759 2006-05-18 2007-04-23 Composition de résist positif pour exposition par immersion et procédé de formation d'un motif de résist Ceased WO2007135836A1 (fr)

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JP4961374B2 (ja) * 2007-03-28 2012-06-27 富士フイルム株式会社 ポジ型レジスト組成物およびパターン形成方法
EP2189845B1 (fr) * 2008-11-19 2017-08-02 Rohm and Haas Electronic Materials LLC Compositions 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
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