WO2012157352A1 - Composition de photoréserve - Google Patents

Composition de photoréserve Download PDF

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Publication number
WO2012157352A1
WO2012157352A1 PCT/JP2012/059020 JP2012059020W WO2012157352A1 WO 2012157352 A1 WO2012157352 A1 WO 2012157352A1 JP 2012059020 W JP2012059020 W JP 2012059020W WO 2012157352 A1 WO2012157352 A1 WO 2012157352A1
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Prior art keywords
group
structural unit
carbon atoms
photoresist composition
polymer component
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English (en)
Japanese (ja)
Inventor
一樹 笠原
憲彦 池田
浩光 中島
吉田　昌史
雅史 堀
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JSR Corp
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JSR Corp
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Priority to JP2013515042A priority Critical patent/JP5967082B2/ja
Publication of WO2012157352A1 publication Critical patent/WO2012157352A1/fr
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—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 photoresist composition.
  • Lithography using short-wavelength radiation typified by KrF excimer laser light (wavelength 248 nm) and ArF excimer laser light (wavelength 193 nm) in order to obtain a higher degree of integration in the field of microfabrication for manufacturing integrated circuit elements, etc.
  • a photoresist material adapted to these radiations from the viewpoint of high sensitivity, high resolution, etc., a chemical amplification type containing a component having an acid dissociable group and an acid generator that generates an acid upon irradiation with radiation. These photoresist compositions are widely used (see Japanese Patent Application Laid-Open No. 59-45439).
  • photoresist compositions as a composition suitable for shorter wavelength ArF excimer laser light, for example, a composition containing a polymer containing an alicyclic group in the skeleton having no large absorption in the 193 nm region It has been known.
  • a composition containing a polymer containing an alicyclic group in the skeleton having no large absorption in the 193 nm region It has been known.
  • the polymer those having a spirolactone structure have been proposed (see Japanese Patent Application Laid-Open Nos. 2002-82441 and 2002-308937). It is said that such a polymer having a spirolactone structure can improve the development contrast of a photoresist composition containing the polymer.
  • a conventional photoresist composition has lithography characteristics using MEEF (Mask Error Enhancement Factor), DOF (Depth Of Focus), LWR (Line Width Roughness), etc. as indices indicating mask error tolerance.
  • MEEF Mesk Error Enhancement Factor
  • DOF Depth Of Focus
  • LWR Line Width Roughness
  • the photoresist composition for forming a finer resist pattern has improved lithography performance using not only basic characteristics such as sensitivity and resolution but also MEEF, DOF, LWR, etc. as an index. Etc. are desired.
  • the present invention has been made based on the circumstances as described above, and its purpose is not only basic characteristics such as sensitivity, but also a photoresist composition that sufficiently satisfies lithography performance with MEEF, DOF, LWR, etc. as an index. Is to provide things.
  • the invention made to solve the above problems is [A] Polymer component having the structural unit (I) represented by the following formula (1) and the acid dissociable group-containing structural unit (II) represented by the following formula (2) in the same or different polymers (Hereinafter also referred to as “[A] polymer component”) and [B] a photoresist composition containing an acid generator.
  • R 0 is a hydrogen atom, a fluorine atom, a hydroxyl group or a monovalent organic group having 1 to 20 carbon atoms.
  • R 1 and R 2 are independently a hydrogen atom or a fluorine atom.
  • a hydroxyl group or a monovalent organic group having 1 to 20 carbon atoms, or R 1 and R 2 are bonded to each other to form a ring structure having 3 to 10 carbon atoms together with the carbon atom to which they are bonded.
  • A is an integer of 1 to 6.
  • R 3 and R 4 are each independently A hydrogen atom, a fluorine atom, a hydroxyl group, or a monovalent organic group having 1 to 20 carbon atoms, or a group having 3 to 10 carbon atoms together with the carbon atoms to which R 3 and R 4 are bonded to each other.
  • R 0 ⁇ R 4 is a group containing a hetero atom.
  • R 5 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R 6 and R 7 are each independently an alkyl group having 1 to 4 carbon atoms or an alicyclic group having 4 to 20 carbon atoms, or R 6 and R 7 are bonded to each other.
  • a divalent alicyclic group is formed together with the carbon atom.
  • R 8 is an alkyl group having 1 to 4 carbon atoms or an alicyclic group having 4 to 20 carbon atoms.
  • the photoresist composition has a structural unit (I) containing a lactone structure represented by the above formula (1) and an acid dissociable group-containing structural unit (II) represented by the above formula (2) [ A] Since the polymer component is contained, the lithography performance using MEEF, LWR, DOF, etc. as an index is excellent.
  • the polymer component preferably contains at least one selected from the group consisting of structural units represented by the following formulas (2A) to (2C) as the structural unit (II).
  • R 5 has the same meaning as in the above formula (2).
  • Each R A is independently an alkyl group having 1 to 4 carbon atoms.
  • M1 and m2 are Each independently an integer from 1 to 6.
  • the photoresist composition maintains an improvement in lithography performance using the MEEF, LWR, DOF, etc. as an index. However, the occurrence of bridge defects can be suppressed.
  • the polymer component preferably further includes at least one selected from the group consisting of structural units represented by the following formulas (2D) to (2I) as the structural unit (II).
  • R 5 is as defined in the above formula (2) .
  • R A is as defined in the above formula (2A) ⁇ (2C) .
  • R B are each independently And an alkyl group having 1 to 4 carbon atoms.
  • the photoresist composition maintains an improvement in lithography performance using the MEEF, LWR, DOF, etc. as an index.
  • the occurrence of bridge defects can be suppressed and the resistance to pattern collapse of the resist pattern can be enhanced.
  • the polymer component is preferably a structural unit other than the structural unit (I) and the structural unit (II), and further has a structural unit (III) containing a polar group. Since the [A] polymer component further has the structural unit (III) containing a polar group, the compatibility between the [A] polymer component and other components such as the [B] acid generator is improved.
  • the said photoresist composition can make the lithography performance which used MEEF, LWR, DOF etc. as a parameter
  • the polymer component preferably further has at least one group (a) selected from the group consisting of a lactone group, a cyclic carbonate group and a sultone group.
  • group (a) selected from the group consisting of a lactone group, a cyclic carbonate group and a sultone group.
  • the group (a) is preferably contained in a structural unit (IV) other than the structural unit (I).
  • the photoresist composition can further improve the lithography performance using MEEF, LWR, DOF, etc. as an index.
  • the group (a) is also preferably contained in the structural unit (I). Even when the group (a) is contained in the structural unit (I), the photoresist composition can further improve the lithography performance using MEEF, LWR, DOF, etc. as an index.
  • the acid dissociable group contained in the structural unit (II) has 4 to 9 carbon atoms.
  • the photoresist composition particularly improves lithography performance using MEEF, LWR, DOF, etc. as an index. be able to.
  • the total content of the structural unit (I) and the structural unit (II) in the polymer component is 20 mol% to 70 mol%, and the content of the structural unit (I) is 5 mol% to 60 mol. It is preferable that it is below mol%.
  • the photoresist composition can be used in addition to basic performance such as sensitivity, MEEF, LWR, DOF. Lithographic performance can be particularly improved using the above as an index.
  • the content of the structural unit in the [A] polymer component is determined by measuring the 13 C-NMR spectrum of the [A] polymer component, and calculating from the area ratio of the peak corresponding to each structural unit in the obtained spectrum.
  • the photoresist composition of the present invention contains the [A] polymer component having the structural unit (I) containing a specific lactone structure and the acid dissociable group-containing structural unit (II). Therefore, in addition to basic characteristics such as sensitivity, the lithography performance using MEEF, LWR, DOF, etc. as an index is excellent. Therefore, a fine pattern can be formed with high accuracy by using the photoresist composition.
  • the photoresist composition contains a [A] polymer component and a [B] acid generator. Moreover, you may contain another component, unless the effect of this invention is impaired. Hereinafter, each component will be described in detail.
  • the polymer component is a structural unit (I) represented by the above formula (1) and an acid dissociable group-containing structural unit (II) represented by the above formula (2) in the same or different polymers. It is a polymer component having By containing the [A] polymer component, the photoresist composition satisfies basic characteristics such as sensitivity, and is excellent in lithography performance with MEEF, LWR, DOF, etc. as an index.
  • the [A] polymer component is a copolymer of a plurality of types of monomer compounds such as a monomer compound that provides the structural unit (I) and a monomer compound that provides the structural unit (II). Or two or more polymers obtained by blending a plurality of polymers such as a polymer of a monomer compound that gives the structural unit (I) and a polymer of the monomer compound that gives the structural unit (II).
  • the component may be included.
  • the polymer component preferably has a structural unit (III) containing a polar group in addition to the structural unit (I) and the structural unit (II).
  • the polymer component preferably further has at least one group (a) selected from the group consisting of a lactone group, a cyclic carbonate group and a sultone group.
  • This group (a) may be contained in the structural unit (I), may be contained in a structural unit (IV) other than the structural unit (I), or may be contained in both of the above. Also good.
  • the photoresist composition can improve lithography performance with MEEF, LWR, DOF, etc. as an index. Furthermore, you may have another structural unit, unless the effect of this invention is impaired.
  • the photoresist composition contains the below-mentioned [F] polymer
  • the polymer containing the structural unit (II) in a [A] polymer component does not contain a fluorine atom.
  • each structural unit will be described in detail.
  • the structural unit (I) is represented by the above formula (1). [A] Since the polymer component has a structural unit (I) containing a specific lactone structure directly connected to the polymer main chain, the photoresist composition is excellent in lithography performance with MEEF, DOF and LWR as indices. .
  • R 0 is a hydrogen atom, a fluorine atom, a hydroxyl group or a monovalent organic group having 1 to 20 carbon atoms.
  • R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, a hydroxyl group, or a monovalent organic group having 1 to 20 carbon atoms, or R 1 and R 2 are bonded to each other and bonded to each other.
  • a ring structure having 3 to 10 carbon atoms is formed together with the carbon atoms.
  • a is an integer of 1 to 6. However, when a is 2 or more, the plurality of R 1 and R 2 may be the same or different.
  • R 3 and R 4 are each independently a hydrogen atom, a fluorine atom, a hydroxyl group, or a monovalent organic group having 1 to 20 carbon atoms, or R 3 and R 4 are bonded to each other.
  • a ring structure having 3 to 10 carbon atoms is formed together with the carbon atoms.
  • one part or all part of the hydrogen atom which the said ring structure has may be substituted.
  • at least one of R 0 to R 4 is a group containing a hetero atom.
  • Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R 0 to R 4 include a chain hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, And an aromatic hydrocarbon group having 6 to 20 carbon atoms, a heterocyclic group having 3 to 10 nuclear atoms, an epoxy group, a cyano group, a carboxy group, and a group represented by —R′—QR ′′.
  • R ′ is a single bond or a hydrocarbon group having 1 to 20 carbon atoms.
  • R ′′ is an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • Q is —O—, —CO—, —NH—, —SO 2 —, —SO— or a combination thereof.
  • halogen atoms such as fluorine atoms, cyano groups, carboxy groups, hydroxyl groups, thiol groups, etc. May be.
  • Examples of the chain hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group.
  • a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group are preferable, and a methyl group and an ethyl group are more preferable.
  • Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclohexyl group, cyclooctyl group, and cyclodecyl group; norbornyl group And a polycyclic alicyclic hydrocarbon group such as an adamantyl group.
  • Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.
  • heterocyclic group having 3 to 10 nuclear atoms examples include a lactone group, a cyclic carbonate group, a sultone group, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. And a group to be included.
  • a lactone group, a cyclic carbonate group, and a sultone group are preferable, a lactone group is more preferable, and a butyrolactone group is more preferable.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ′ and R ′′ in —R′—QR ′′ include, for example, a chain hydrocarbon group having 1 to 20 carbon atoms, and 3 to 20 carbon atoms. And an alicyclic hydrocarbon group and an aromatic hydrocarbon group having 6 to 20 carbon atoms. For each, the same groups as those exemplified for the monovalent organic group having 1 to 20 carbon atoms represented by R 0 to R 4 can be given.
  • R 1 and R 2 are bonded together and the ring structure formed with the carbon atom to which they are bonded, and R 3 and R 4 are bonded together and formed with the carbon atom to which they are bonded.
  • the group having a ring structure having 3 to 10 carbon atoms include alicyclic groups such as cyclopropanediyl group, cyclohexanediyl group, norbornanediyl group and adamantanediyl group, oxygen atom, sulfur atom, nitrogen atom and the like.
  • Examples include heterocyclic groups containing a hetero atom.
  • the cycloaliphatic group is preferably a cyclopentanediyl group, cyclohexanediyl group or adamantanediyl group
  • the heterocyclic group is preferably a cyclic ether group, a lactone group or a sultone group.
  • the hetero atom contained in at least one of R 0 to R 4 is not particularly limited as long as it is an atom other than a carbon atom and a hydrogen atom, but is preferably an oxygen atom, a nitrogen atom, a sulfur atom, an iodine atom and a halogen atom, An oxygen atom and a fluorine atom are more preferable, and an oxygen atom is still more preferable.
  • a is preferably 1
  • R 1 is preferably a hydrogen atom.
  • Examples of the structural unit (I) include structural units represented by the following formulas (1-1) to (1-79).
  • structural units further containing a lactone structure other than the lactone structure directly bonded to the polymer main chain include the following formulas (1-7), (1-8), (1-68), (1-70).
  • ), (1-72), (1-73) and (1-76) are structural units containing a cyclic carbonate structure, the structural units represented by the following formulas (1-74), (1-77)
  • Examples of the structural unit in which the structural unit represented by (1-79) includes a sultone structure include structural units represented by the following formulas (1-75) and (1-78).
  • At least one group of R 3 and R 4 are structural units, structural units in which at least one group of R 3 and R 4 is a cyclic organic group, R 3 and R 4 are bonded to an oxygen atom And a structural unit that forms a ring structure with the carbon atom to which they are bonded.
  • the above formulas (1-1) to (1-9), (1-12) to (1-21), (1-25) to (1-47), (1-55) to (1-67) ), (1-69) to (1-79) are more preferred, and (1-1), (1-17), (1-19), (1-70) to (1- 79) is more preferred.
  • the content of the structural unit (I) is preferably 1 mol% or more and 80 mol% or less, and preferably 5 mol% or more and 60 mol% with respect to all the structural units constituting the [A] polymer component.
  • the mol% or less is more preferable.
  • the [A] polymer component may have 1 type, or 2 or more types of structural units (I).
  • Examples of the monomer that gives the structural unit (I) include compounds represented by the following formulas.
  • the monomer giving the structural unit (I) can be produced, for example, by the following method.
  • the polymer component has the structural unit (II) together with the structural unit (I). Since the structural unit (II) represented by the above formula (2) has an acid dissociable group that is easily dissociated by the action of an acid generated from the [B] acid generator upon exposure, the photoresist composition [A] Having the structural unit (II) in the polymer component sufficiently satisfies the basic characteristics such as sensitivity, and can form a resist pattern that is superior in lithography performance with MEEF, DOF, LWR, etc. as an index. It becomes possible.
  • the structural unit (II) is represented by the above formula (2).
  • R 5 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R 6 and R 7 are each independently an alkyl group having 1 to 4 carbon atoms or an alicyclic group having 4 to 20 carbon atoms, or R 6 and R 7 are bonded to each other.
  • a divalent alicyclic group is formed together with the carbon atom.
  • R 8 is an alkyl group having 1 to 4 carbon atoms or an alicyclic group having 4 to 20 carbon atoms.
  • Examples of the alkyl group having 1 to 4 carbon atoms represented by R 6 to R 8 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a tert-butyl group. , 2-methylpropyl group, 1-methylpropyl group and the like.
  • Examples of the alicyclic group having 4 to 20 carbon atoms represented by the above R 6 to R 8 and the alicyclic group formed together with the carbon atom to which R 6 and R 7 are bonded to each other are as follows: Examples thereof include polycyclic alicyclic groups having a bridged skeleton such as an adamantane skeleton and norbornane skeleton; and monocyclic alicyclic groups having a cycloalkane skeleton such as cyclopentane and cyclohexane. These groups may be substituted with one or more of linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, for example.
  • structural unit (II) structural units represented by the following formulas (2A) to (2I) are preferable.
  • R 5 has the same meaning as in the above formula (2).
  • Each R A is independently an alkyl group having 1 to 4 carbon atoms.
  • m1 and m2 are each independently an integer of 1 to 6.
  • Each R B is independently an alkyl group having 1 to 4 carbon atoms.
  • Examples of the alkyl group having 1 to 4 carbon atoms represented by R A and R B include the same groups as those exemplified as the alkyl group having 1 to 4 carbon atoms represented by R 6 to R 8 .
  • the polymer component is at least one selected from the group consisting of structural units represented by the above formulas (2A) to (2C) as the structural unit (II) (hereinafter referred to as “structural unit (II-1)”). In addition to the structural unit (II-1), and at least one selected from the group consisting of structural units represented by the above formulas (2D) to (2I) (hereinafter referred to as “structure”) More preferably, the unit (also referred to as unit (II-2) ”). [A] When the polymer component contains the structural unit (II-1) as the structural unit (II), it is possible to suppress the occurrence of bridge defects while maintaining the improvement of the lithography performance. In addition to this, when the [A] polymer component further contains the structural unit (II-2) as the structural unit (II), the resistance to pattern collapse of the resist pattern can be improved.
  • the structural units represented by the following formulas (2-11) to (2-13) are:
  • the structural unit represented by the formula (2E) is As the structural unit represented by the formula (2F)
  • structural units represented by the following formulas (2-16) and (2-17) are:
  • As the structural unit represented by the formula (2G) is As the structural unit represented by the formula (2H)
  • the structural unit represented by the following formula (2-18) is As the structural unit represented by the formula (2I)
  • a structural unit represented by the following formula (2-25) is preferable.
  • R ⁇ 5 > is synonymous with the said Formula (2).
  • the content of the structural unit (II) is preferably 10% by mole or more and 80% by mole or less, and more preferably 15% by mole or more with respect to all structural units constituting the [A] polymer component. 80 mol% or less is more preferable, and 20 mol% or more and 70 mol% or less is more preferable. By making the content rate of structural unit (II) into the said range, the lithography performance of the resist pattern obtained improves more.
  • the [A] polymer component may have 1 type, or 2 or more types of structural units (II).
  • Examples of the monomer that gives structural unit (II) include (meth) acrylic acid-bicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid-bicyclo [2.2.2] octa -2-yl ester, (meth) acrylic acid-tricyclo [5.2.1.0 2,6 ] dec-7-yl ester, (meth) acrylic acid-tricyclo [3.3.1.1 3,7 ] Deca-1-yl ester, (meth) acrylic acid-tricyclo [3.3.1.1 3,7 ] dec-2-yl ester, and the like.
  • the polymer component preferably has a structural unit (III).
  • the structural unit (III) is a structural unit other than the structural unit (I) and the structural unit (II) and includes a polar group. Since the [A] polymer component further has the structural unit (III), the compatibility between the [A] polymer component and other components such as the [B] acid generator is improved, so that the lithography performance of the resist pattern Can be made more excellent.
  • Examples of the polar group include a hydroxyl group, a ketonic carbonyl group, a carboxy group, an amide group, a urethane group, a urea group, a carbonate group, a sulfide group, a sulfonyl group, a halogenated alkyl group, a cyano group, and a thiol group.
  • a hydroxyl group, a sulfonyl group, and a halogenated alkyl group are preferable, and a hydroxyl group is more preferable.
  • Examples of the structural unit (III) include a structural unit represented by the following formula.
  • R 9 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • the content of the structural unit (III) in the polymer component is preferably 0 mol% or more and 50 mol% or less, and preferably 5 mol% or more and 40 mol%, based on all the structural units constituting the [A] polymer component.
  • the mol% or less is more preferable.
  • the polymer component may have one or more structural units (III).
  • the structural unit (IV) is a structural unit other than the structural unit (I) and includes the group (a).
  • the said photoresist composition can improve the lithography performance which used MEEF, DOF, and LWR as a parameter
  • the structural unit (IV) is preferably a structural unit represented by the following formula (3).
  • the said photoresist composition can improve the lithography performance which made MEEF, DOF, and LWR a parameter
  • R 10 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R 11 is a hydrocarbon group having 1 to 10 carbon atoms.
  • X is —O—, —COO—, —OCO— or —NH—.
  • n is an integer of 0 to 10. When n is 2 or more, the plurality of R 11 and X may be the same or different.
  • R 12 is a single bond or a hydrocarbon group having 1 to 5 carbon atoms.
  • R 13 is the group (a). However, some or all of the hydrogen atoms contained in R 11 to R 13 may be substituted.
  • Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R 11 include a chain hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and 6 to 6 carbon atoms. 10 aromatic hydrocarbon groups and the like.
  • Examples of the chain hydrocarbon group having 1 to 10 carbon atoms include a methylene group, an ethylene group, and a propylene group. Of these, a methylene group and an ethylene group are preferred.
  • Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms include a cyclopropylene group, a cyclohexylene group, and an adamantylene group. Of these, an adamantylene group is preferred.
  • Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenylene group and a naphthylene group.
  • X is preferably —O— or —COO—.
  • N is preferably an integer of 0 to 5, more preferably 0 and 1.
  • Examples of the hydrocarbon group having 1 to 5 carbon atoms represented by R 12 include a chain hydrocarbon group having 1 to 5 carbon atoms and an alicyclic hydrocarbon group having 3 to 5 carbon atoms.
  • Examples of the chain hydrocarbon group having 1 to 5 carbon atoms include a methylene group, an ethylene group, and a propylene group. Of these, a methylene group is preferred.
  • Examples of the alicyclic hydrocarbon group having 3 to 5 carbon atoms include a cyclopropylene group and a cyclobutylene group.
  • R 12 is preferably a single bond or a methylene group.
  • Examples of the group (a) represented by R 13 include: Examples of cyclic carbonate groups include ethylene carbonate groups, 1,3-propylene carbonate groups, cyclopentene carbonate groups, cyclohexene carbonate groups, norbornene carbonate groups, As sultone groups, propiosluton groups, butyrosulton groups, valerosultone groups, adamantane sultone groups, etc. Examples of the lactone group include a propiolactone group, a butyrolactone group, a valerolactone group, an adamantane lactone group, and the like.
  • the cyclic carbonate group is preferably an ethylene carbonate group
  • the sultone group is preferably a norbornane sultone group
  • the lactone group is preferably a norbornane lactone group or a butyrolactone group.
  • Examples of the substituent in which part or all of the hydrogen atoms of R 11 to R 13 may be substituted include, for example, a halogen atom, a hydroxyl group, a carboxy group, a keto group, a sulfonamide group, an amino group, an amide group, A cyano group, an acetyl group, etc. are mentioned.
  • structural unit (IV) structural units represented by the following formulas (3-1) to (3-18) can be mentioned as preferred structural units.
  • R 10 has the same meaning as in the above formula (3).
  • the structural units represented by the above formulas (3-1) to (3-14) are more preferable, and the above formulas (3-1), ( The structural units represented by 3-3) and (3-5) are more preferable.
  • the content of the structural unit (IV) is preferably 5 mol% or more and 80 mol% or less, preferably 5 mol% or more and 60 mol% or less with respect to all the structural units constituting the [A] polymer component.
  • the mol% or less is more preferable.
  • Examples of the monomer compound that gives the structural unit (IV) include compounds represented by the following formulas as preferred compounds.
  • the polymer component may further contain a structural unit (V) derived from a non-acid dissociable compound as another structural unit.
  • the non-acid dissociable compound refers to a compound that does not contain a group (acid dissociable group) that is dissociated by the action of an acid.
  • Non-acid dissociable compounds for generating the structural unit (V) include, for example, styrene, ⁇ -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, isobornyl acrylate, tricyclodeca Nyl (meth) acrylate, tetracyclododecenyl (meth) acrylate, etc. are mentioned. Of these, styrene, ⁇ -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, and tricyclodecanyl acrylate are preferable.
  • the content of the structural unit (V) in the polymer component is preferably 60 mol% or less, more preferably 50 mol% or less, based on all structural units constituting the [A] polymer component. It is. When this content rate exceeds 60 mol%, there exists a possibility that a lithography characteristic may deteriorate.
  • 1 type of structural units (V) may be contained in the [A] polymer component, and may be contained 2 or more types.
  • the content of the structural unit (I) in the polymer component [A] is 1 mol% or more and 70 mol% or less, and
  • the total content of the structural unit (I) and the structural unit (II) is preferably 10 mol% or more and 80 mol% or less, and the content of the structural unit (I) is 5 mol% or more and 60 mol% or less. More preferably, the total content of the structural unit (I) and the structural unit (II) is 20 mol% or more and 70 mol% or less.
  • the content of the structural unit (I) is from 10 mol% to 50 mol%, and the total content of the structural unit (I) and the structural unit (II) is from 30 mol% to 60 mol%. Further preferred.
  • the weight average molecular weight of the polymer (i) having the structural unit (I) It is preferably larger than the weight average molecular weight of the polymer (ii) having the unit (IV).
  • the photoresist composition when the polymer component [A] is a blend of the polymer (i) having the structural unit (I) and the polymer (ii) having the structural unit (IV), When the weight average molecular weight of the polymer (i) is larger than the weight average molecular weight of the polymer (ii), the lithography performance using MEEF, LWR or the like as an index is excellent.
  • the polymer component can be produced, for example, by polymerizing monomers corresponding to predetermined structural units in a suitable solvent using a radical polymerization initiator.
  • a method of dropping a solution containing a monomer and a radical initiator into a reaction solvent or a solution containing the monomer to cause a polymerization reaction, a solution containing the monomer, and a solution containing the radical initiator Separately, a method of dropping a reaction solvent or a monomer-containing solution into a polymerization reaction, a plurality of types of solutions containing each monomer, and a solution containing a radical initiator, It is preferable to synthesize by a method such as a method of dropping it into a reaction solvent or a solution containing a monomer to cause a polymerization reaction.
  • the reaction temperature in these methods may be appropriately determined depending on the initiator type. Usually, it is 30 ° C to 180 ° C, preferably 40 ° C to 160 ° C, and more preferably 50 ° C to 140 ° C.
  • the dropping time varies depending on the reaction temperature, the type of initiator, the monomer to be reacted, etc., but is usually 30 minutes to 8 hours, preferably 45 minutes to 6 hours, more preferably 1 hour to 5 hours. .
  • the total reaction time including the dropping time varies depending on the conditions as in the dropping time, but is usually from 30 minutes to 8 hours, preferably from 45 minutes to 7 hours, and more preferably from 1 hour to 6 hours.
  • radical initiator used in the polymerization examples include azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropyl). Propionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropionitrile), and the like. Two or more of these initiators may be mixed and used.
  • the polymerization solvent is not limited as long as it is a solvent other than a solvent that inhibits polymerization (nitrobenzene having a polymerization inhibiting effect, mercapto compound having a chain transfer effect, etc.) and can dissolve the monomer.
  • the polymerization solvent include alcohol solvents, ketone solvents, amide solvents, ester / lactone solvents, nitrile solvents, and mixed solvents thereof. These solvents can be used alone or in combination of two or more.
  • the resin obtained by the polymerization reaction is preferably recovered by a reprecipitation method. That is, after completion of the polymerization reaction, the target resin is recovered as a powder by introducing the polymerization solution into a reprecipitation solvent.
  • a reprecipitation solvent alcohols or alkanes can be used alone or in admixture of two or more.
  • the resin can be recovered by removing low-molecular components such as monomers and oligomers by a liquid separation operation, a column operation, an ultrafiltration operation, or the like.
  • the polymer component is a polymer component having the structural unit (I), the structural unit (II), etc. in the same polymer
  • the monomer or structural unit giving the structural unit (I) A monomer or the like that gives (II) can be produced by copolymerization by the method described above.
  • the polymer component is a polymer component having a structural unit such as the structural unit (I) or the structural unit (II) in a different polymer
  • the monomer that gives each structural unit is the above-described monomer. By polymerizing by the method and mixing them, the [A] polymer component can be prepared.
  • the polystyrene-reduced weight average molecular weight (Mw) of the polymer component by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1,000 or more and 500,000 or less, and preferably 2,000 or more and 400,000 or less. More preferred.
  • Mw of the [A] polymer is less than 1,000, the heat resistance when used as a resist tends to decrease.
  • Mw of the [A] polymer exceeds 500,000, the developability when used as a resist tends to be lowered.
  • the ratio (Mw / Mn) of Mw to polystyrene-converted number average molecular weight (Mn) by GPC of the polymer component is usually from 1 to 5, preferably from 1 to 3, preferably from 1 to 2. More preferred. By setting Mw / Mn in such a range, the photoresist film has excellent resolution performance.
  • the polymer component is a polymer component having the structural unit (I) and the structural unit (II) in different polymers
  • the Mw and Mw / Mn in the respective polymers are as described above. It is good if it is in the same range.
  • Mw and Mn are GPC columns (Toso, G2000HXL, 1 G3000HXL, 1 G4000HXL), flow rate of 1.0 ml / min, elution solvent tetrahydrofuran, column temperature of 40 ° C. The value measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard.
  • the acid generator is a compound that generates an acid by light passing through a mask in an exposure process, which is one process of forming a resist pattern.
  • the [B] acid generator in the photoresist composition, even in an embodiment of a compound as described later (hereinafter, this embodiment is also referred to as “[B] acid generator”), as a part of the polymer It may be a built-in embodiment or both of these embodiments.
  • Examples of the acid generator include onium salt compounds, N-sulfonyloxyimide compounds, halogen-containing compounds, and diazoketone compounds. Of these [B] acid generators, onium salt compounds are preferred.
  • sulfonium salt examples include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept.
  • triphenylsulfonium trifluoromethanesulfonate triphenylsulfonium nonafluoro-n-butanesulfonate
  • triphenylsulfonium 2-adamantan-1-yl-1,1-difluoroethane sulfonate are preferred.
  • Nonafluoro-n-butanesulfonate 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio Phenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium trifluoro Lomethanesulfonate, 1- (6-n-butoxynaphthalene) 2-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (6-n-butoxy)
  • iodonium salt examples include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl.
  • N-sulfonyloxyimide compounds include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyl).
  • ⁇ Optional component> As optional components that may be contained in the photoresist composition, [C] acid diffusion controller, [D] additive, [E] solvent, [F] polymer containing fluorine atom, alicyclic skeleton containing Examples thereof include compounds, surfactants and sensitizers. Hereinafter, each component will be described in detail.
  • the photoresist composition may further contain a [C] acid diffusion controller.
  • This [C] acid diffusion control agent controls the diffusion phenomenon in the resist film of the acid generated from the [B] acid generator by exposure, and suppresses an undesirable chemical reaction in the non-exposed region.
  • the storage stability of the resulting photoresist composition is improved, the resolution as a resist is further improved, and from exposure to heat treatment after exposure.
  • a change in the line width of the resist pattern due to fluctuations in the holding time (PED) can be suppressed, and a composition having excellent process stability can be obtained.
  • a nitrogen-containing compound having an Nt-alkoxycarbonyl group is preferably used.
  • nitrogen-containing compounds such as tertiary amine compounds, quaternary ammonium hydroxide compounds, and nitrogen-containing heterocyclic compounds are used as the [C] acid diffusion controller.
  • tertiary amine compounds include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octyl.
  • Tri (cyclo) alkylamines such as amine, cyclohexyldimethylamine, dicyclohexylmethylamine, and tricyclohexylamine; Fragrances such as aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline Group amines; Alkanolamines such as triethanolamine, N, N-di (hydroxyethyl) aniline; N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, 1,3-bis [1- (4-aminophenyl) -1- Methylethyl] benzenetetramethylenediamine, bis (2-dimethylaminoethyl) ether, bis (2-dieth
  • Examples of the quaternary ammonium hydroxide compound include tetra-n-propylammonium hydroxide and tetra-n-butylammonium hydroxide.
  • nitrogen-containing heterocyclic compound examples include 2-phenylbenzimidazole, pyridine, 2-methylpyridine, pyrazine, pyrazole and the like. Of these, 2-phenylbenzimidazole is preferred.
  • an onium salt compound that decomposes by exposure and loses basicity as acid diffusion controllability can be used.
  • an onium salt compound include a sulfonium salt compound represented by the following formula (4-1) and an iodonium salt compound represented by the following formula (4-2).
  • Diphenyl-4-hydroxyphenylsulfonium salicylate bis (4-tert-butylphenyl) iodonium hydroxide, bis (4-tert-butylphenyl) iodonium acetate, bis (4-tert-butylphenyl) iodonium hydroxide, Bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium salicylate, 4-t Butylphenyl-4-hydroxyphenyliodonium hydroxide, 4-t-butylphenyl-4-hydroxyphenyliodonium acetate, 4-t-butylphenyl-4-hydroxyphenyliodonium salicylate, bis (4-t-butylphenyl) Examples thereof include iodonium 10-camphor sulfonate, diphenyl iodonium 10-camphor sulfonate, triphenyl sulfonium 10-
  • the photoresist composition can be blended with an additive [D] when a resist pattern is formed using an immersion exposure method.
  • the [D] additive that may be contained in the photoresist composition include ⁇ -butyrolactone, propylene carbonate, and the like. Of these, ⁇ -butyrolactone is preferred.
  • an alcohol solvent for example, Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, tert- Pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n- Nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptan
  • ether solvent examples include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether and the like.
  • ketone solvent examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n.
  • ester solvents include diethyl carbonate, methyl acetate, ethyl acetate, ⁇ -valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, and n-acetate.
  • hydrocarbon solvent examples include aliphatic carbonization such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane
  • Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene Group hydrocarbon solvents and the like.
  • organic solvents may be used alone or in combination of two or more.
  • Monomers that give a structure in which a fluorinated alkyl group is bonded to the main chain and side chain include, for example, ⁇ -trifluoromethylacrylic acid, ⁇ -trifluoromethylacrylic acid, ⁇ , ⁇ -trifluoromethylacrylic acid Such as a fluorinated alkyl group or a derivative thereof, or a compound in which one or more vinyl moiety hydrogens are substituted with a fluorinated alkyl group such as a trifluoromethyl group.
  • an alicyclic olefin compound shows the compound in which a part of ring is a double bond.
  • the polymer preferably has a structural unit (f1) represented by the following formula (6) and / or a structural unit (f2) represented by the formula (7), and the structural unit (f1) and You may have "another structural unit” other than a structural unit (f2).
  • a structural unit (f1) represented by the following formula (6) and / or a structural unit (f2) represented by the formula (7)
  • the structural unit (f1) and You may have "another structural unit” other than a structural unit (f2).
  • each structural unit will be described in detail.
  • R 17 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R 18 is a linear or branched alkyl group having 1 to 6 carbon atoms having a fluorine atom, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms having a fluorine atom. However, in the alkyl group and alicyclic hydrocarbon group, part or all of the hydrogen atoms may be substituted.
  • Examples of the monomer that gives the structural unit (f1) include trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro n-propyl ( (Meth) acrylate, perfluoro i-propyl (meth) acrylate, perfluoro n-butyl (meth) acrylate, perfluoro i-butyl (meth) acrylate, perfluoro t-butyl (meth) acrylate, perfluorocyclohexyl (meth) Acrylate, 2- (1,1,1,3,3,3-hexafluoro) propyl (meth) acrylate, 1- (2,2,3,3,4,4,5,5-octafluoro) pentyl ( (Meth) acrylate, 1- (2,2,3,3,4,4,5,5-octafluoro) he Sil (me
  • R 17 has the same meaning as in the above formula (6).
  • the structural unit (f2) is a structural unit represented by the following formula (7).
  • Examples of the structural unit (f2) include structural units represented by the following formulas (7-1) and (7-2).
  • R 19 has the same meaning as in the above formula (7).
  • the polymer further includes, as “other structural units”, a structural unit having a lactone structure, a cyclic carbonate structure or a sultone structure for enhancing solubility in a developer, and an alicyclic structure for enhancing etching resistance.
  • One or more structural units may be included.
  • Examples of the structural unit containing an alicyclic structure include a structural unit represented by the following formula (8).
  • R 22 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • Y 2 is an alicyclic hydrocarbon group having 4 to 20 carbon atoms.
  • Examples of the monomer that gives a structural unit containing an alicyclic compound include (meth) acrylic acid-bicyclo [2.2.1] hept-2-yl ester and (meth) acrylic acid-bicyclo [2.2. 2] Oct-2-yl ester, (meth) acrylic acid-tricyclo [5.2.1.0 2,6 ] dec-7-yl ester, (meth) acrylic acid-tricyclo [3.3.1.1] 3,7 ] dec-1-yl ester, (meth) acrylic acid-tricyclo [3.3.1.1 3,7 ] dec-2-yl ester, and the like.
  • the structural unit (f1), the structural unit (f2), and the other structural unit may have only one kind of each structural unit or may contain two or more kinds.
  • the polymer preferably contains no unit having an aromatic group.
  • an ArF light source when used, it may cause a decrease in sensitivity. Further, when developing with a negative developer, the shape may deteriorate.
  • the content of the polymer is preferably 1 part by mass to 15 parts by mass, and more preferably 2 parts by mass to 10 parts by mass with respect to 100 parts by mass of the polymer component [A].
  • the reaction temperature in the above polymerization is usually preferably 40 ° C to 150 ° C and 50 ° C to 120 ° C.
  • the reaction time is usually preferably 1 hour to 48 hours and 1 hour to 24 hours.
  • the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is preferably 1,000 to 50,000, more preferably 1,000 to 30,000, and 1,000. ⁇ 10,000 is particularly preferred.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • An alicyclic skeleton compound is a component that exhibits an action of further improving dry etching resistance, pattern shape, adhesion to a substrate, and the like.
  • Examples of the alicyclic skeleton compound include adamantane derivatives such as 1-adamantanecarboxylic acid, 2-adamantanone, and 1-adamantanecarboxylic acid t-butyl; deoxycholic acid t-butyl, deoxycholic acid t-butoxycarbonylmethyl, Deoxycholic acid esters such as 2-ethoxyethyl deoxycholate; Lithocholic acid esters such as tert-butyl lithocholic acid, t-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid; 3- [2-hydroxy-2 , 2-Bis (trifluoromethyl) ethyl] tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodecane
  • Surfactants are components that have the effect of improving coatability, striation, developability, and the like.
  • examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol diacrylate.
  • nonionic surfactants such as stearate
  • the following trade names are KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no.
  • step (1) A step of forming a coating film of the photoresist composition on a substrate (hereinafter also referred to as “step (1)”), (2) A step of irradiating at least a part of the coating film (hereinafter also referred to as “step (2)”), and (3) a step of developing the coating film irradiated with the radiation (hereinafter referred to as “step”). (Also referred to as (3)) And the like.
  • step (1) A step of forming a coating film of the photoresist composition on a substrate
  • step (2) A step of irradiating at least a part of the coating film
  • step (3) a step of developing the coating film irradiated with the radiation
  • a resist pattern excellent in MEEF, LWR and DOF can be formed using the photoresist composition. Therefore, even with radiation such as KrF excimer laser light, ArF excimer laser light, EUV, etc., a fine pattern can be formed from the photoresist composition with high accuracy and stability, and further miniaturization will progress in the future. It can be suitably used for expected semiconductor device manufacturing.
  • PEB post-exposure baking
  • a resist pattern is formed by developing the exposed resist film with a developer. After development, it is common to wash with water and dry.
  • the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyl Dimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0]
  • An alkaline aqueous solution in which at least one alkaline compound such as -5-nonene is dissolved is preferable.
  • an immersion liquid insoluble immersion protective film is formed on the resist film.
  • the immersion protective film include a solvent-peeling protective film that peels off with a solvent before the step (3) (see, for example, JP-A-2006-227632), and a developer that peels off simultaneously with the development in the step (3). Any of peelable protective films (see, for example, WO 2005-069096, WO 2006-035790, etc.) may be used.
  • Mw and Mn of the polymer were measured using GPC columns (manufactured by Tosoh Corporation, two G2000HXL, one G3000HXL, one G4000HXL) under the following conditions.
  • Sample injection volume 100 ⁇ L
  • Detector Differential refractometer Standard material: Monodisperse polystyrene
  • the structural unit derived from the monomer in the polymer was analyzed using a nuclear magnetic resonance apparatus (JNM-ECX400, manufactured by JEOL Ltd.) and using deuterated chloroform as a measurement solvent.
  • the content of the structural unit in the polymer can be determined as an average value in the polymer from the area ratio of peaks corresponding to each structural unit in the obtained spectrum by measuring the 13 C-NMR spectrum of the polymer.
  • this crude product was put into a 300 mL three-necked reactor, 100 mL of methylene chloride was added, and the mixture was stirred and dissolved with a magnetic stirrer. Thereto, 15.5 g (227 mmol) of imidazole and 4.2 g (34 mmol) of dimethylaminopyridine were added, and then the reactor was cooled to 0 ° C. Next, 25.7 g (170 mmol) of tert-butyldimethylsilyl chloride was added and reacted at 0 ° C. for 2 hours and then at room temperature for 6 hours. Next, an aqueous ammonium chloride solution was added for liquid separation.
  • the polymerization solution was cooled with water and cooled to 30 ° C. or lower.
  • the cooled polymerization solution was put into 800 g of methanol, and the precipitated white powder was separated by filtration.
  • the filtered white powder was washed twice with 160 g of methanol, filtered, and dried at 50 ° C. for 17 hours to obtain a white powdery polymer component (A-1) (30 g, yield 75%).
  • Mw of the obtained polymer component (A-1) was 4,500, and Mw / Mn was 1.4.
  • the content ratio of the structural unit derived from the compound (M-1) to the structural unit derived from the compound (Ss-1) was 50:50 (mol%).
  • the polymerization solution was cooled with water and cooled to 30 ° C. or lower.
  • the cooled polymerization solution was put into 800 g of methanol, and the precipitated white powder was separated by filtration.
  • the filtered white powder was washed twice with 160 g of methanol, filtered, and dried at 50 ° C. for 17 hours to obtain a white powdery polymer (35 g, yield 88%).
  • a polymer was obtained in the same manner as above except that 22.8 g (50 mol%) of compound (L-1) was used instead of 20 g (50 mol%) of compound (Ss-1).
  • the above two types of polymers were mixed at a molar ratio of 1: 1 to obtain a polymer component (A-29).
  • the physical properties of the two types of polymers are shown in Table 1.
  • Synthesis Example 32 A polymer component (A-30) was obtained in the same manner as in Synthesis Example 31, except that a predetermined amount of the monomers listed in Table 1 were blended. Moreover, Mw of each obtained polymer, Mw / Mn, and the content rate of the structural unit derived from each monomer in each polymer are shown together in Table 1.
  • the polymerization solution was cooled with water and cooled to 30 ° C. or lower.
  • the filtered white powder was washed twice with 120 g of methanol, filtered, and dried at 50 ° C. for 17 hours to obtain a white powdery polymer component (F-1) (24 g, yield 80%).
  • Mw of the obtained polymer (F-1) was 4,100, and Mw / Mn was 1.4.
  • the content ratio of the structural unit derived from the compound (M-7): the structural unit derived from the compound (X-5) was 48.5: 51.5 (mol%). .
  • Example 1 100 parts by mass of polymer component (A-1), 10 parts by mass of acid generator (B-1), 5 parts by mass of acid diffusion controller (C-3), 3 parts by mass of polymer (F-1), additive (D-1) 30 parts by mass, solvent (E-1) 2,600 parts and (E-2) 1,100 parts by mass were mixed, and the resulting mixed solution was filtered with a filter having a pore size of 0.2 ⁇ m. Thus, a photoresist composition was prepared.
  • an exposure amount at which a portion exposed through a mask pattern for forming a pattern of 50 nm Line 100 nm Pitch forms a Line having a line width of 50 nm was defined as an optimum exposure amount (Eop).
  • This optimum exposure dose was taken as the sensitivity (mJ / cm 2 ), and when this sensitivity was 40 (mJ / cm 2 ) or less, it was evaluated as good.
  • LS patterns were formed through mask patterns for forming patterns of 48 nm Line 100 nm Pitch, 49 nm Line 100 nm Pitch, 50 nm Line 100 nm Pitch, 51 nm Line 100 nm Pitch, and 52 nm Line 100 nm Pitch, respectively.
  • the slope of the straight line when the line size (nm) of the mask was plotted on the horizontal axis and the line width (nm) formed on the resist film using each mask pattern was plotted on the vertical axis was calculated as MEEF. As the MEEF (straight line) is closer to 1, the mask reproducibility is better.
  • LWR Line width 50 nm Line 100 nm Pitch formed by the Eop was observed from the upper part of the pattern using the scanning electron microscope, and the line width was measured at arbitrary 10 points.
  • the 3-sigma value (variation) of the measured line width was defined as LWR (nm). If the value of this LWR was 5.4 nm or less, it was evaluated that the formed pattern shape was good.
  • Pattern fall resistance When the amount of exposure is increased through a mask pattern for pattern formation of 50 nm Line 100 nm Pitch, the minimum line pattern dimension at which pattern collapse does not occur is measured using the scanning electron microscope, and this measured value is measured against pattern collapse resistance ( nm). At this time, if the measured value is 35 nm or less, the pattern collapse resistance is good, and if it exceeds 35 nm, it can be evaluated as defective.
  • the photoresist composition of the present invention was excellent in all lithography performances using sensitivity, MEEF, DOF, LWR and the like as indices.
  • the photoresist composition has at least one selected from the group consisting of structural units represented by the above formulas (2A) to (2C) as the structural unit (II)
  • the bridge defect suppression property is
  • the structural unit (II) further includes at least one selected from the group consisting of the structural units represented by the above formulas (2D) to (2I)
  • the bridge defect suppression property and the pattern collapse resistance are Both were good results.
  • the photoresist composition of the present invention is suitably used in the formation of resist patterns in the lithography process of various electronic devices such as semiconductor devices and liquid crystal devices.

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Abstract

La présente invention concerne une composition de photoréserve contenant [A] un composant polymère présentant un motif structural (I) représenté par la formule (1) et un motif structural (II) contenant un groupe labile à l'acide et représenté par la formule (2) dans un seul polymère ou dans des polymères différents, et [B] un générateur d'acide. Dans la formule (1), R0 représente un atome d'hydrogène, un atome de fluor, un groupe hydroxy ou un groupe organique monovalent comptant de 1 à 20 atomes de carbone ; R1 et R2 représentent indépendamment un atome d'hydrogène, un atome de fluor, un groupe hydroxy ou un groupe organique monovalent comptant de 1 à 20 atomes de carbone, ou R1 et R2 sont liés l'un à l'autre de façon à former, avec un atome de carbone auquel R1 et R2 sont liés, une structure cyclique comptant de 3 à 10 atomes de carbone ; R3 et R4 représentent indépendamment un atome d'hydrogène, un atome de fluor, un groupe hydroxy ou un groupe organique monovalent comptant de 1 à 20 atomes de carbone, ou R3 et R4 sont liés l'un à l'autre de façon à former, avec un atome de carbone auquel R3 et R4 sont liés, une structure cyclique comptant de 3 à 10 atomes de carbone ; au moins un cycle parmi R0 à R4 étant un groupe contenant un hétéroatome.
PCT/JP2012/059020 2011-05-19 2012-04-02 Composition de photoréserve Ceased WO2012157352A1 (fr)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013190637A (ja) * 2012-03-14 2013-09-26 Tokyo Ohka Kogyo Co Ltd 溶剤現像ネガ型レジスト組成物、レジストパターン形成方法
JP2013205837A (ja) * 2012-03-29 2013-10-07 Jsr Corp フォトレジスト組成物及びレジストパターン形成方法
JP2013213951A (ja) * 2012-04-02 2013-10-17 Jsr Corp フォトレジスト組成物及びレジストパターン形成方法
EP2623558A4 (fr) * 2010-09-30 2014-02-26 Jsr Corp Composition de résine sensible au rayonnement, polymère et composé
JP2014077999A (ja) * 2012-09-21 2014-05-01 Sumitomo Chemical Co Ltd 樹脂、レジスト組成物及びレジストパターンの製造方法
WO2014185279A1 (fr) * 2013-05-13 2014-11-20 株式会社ダイセル Composé d'ester de l'acide carbamique et composition de solvant pour la production de résines photosensibles le contenant
JP2015043079A (ja) * 2013-07-24 2015-03-05 Jsr株式会社 感放射線性樹脂組成物、レジストパターン形成方法、重合体、化合物及び化合物の製造方法
JP2018097125A (ja) * 2016-12-12 2018-06-21 Jsr株式会社 感放射線性樹脂組成物及びレジストパターン形成方法
KR20210010926A (ko) 2018-06-28 2021-01-28 후지필름 가부시키가이샤 감활성광선성 또는 감방사선성 수지 조성물, 패턴 형성 방법, 전자 디바이스의 제조 방법, 수지
JPWO2020054275A1 (ja) * 2018-09-13 2021-09-24 富士フイルム株式会社 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11212265A (ja) * 1998-01-26 1999-08-06 Sumitomo Chem Co Ltd 化学増幅型のポジ型レジスト組成物
JP2002308937A (ja) * 2001-02-22 2002-10-23 Samsung Electronics Co Ltd 酸により分解可能な保護基を有するラクトン基を含む感光性モノマー、感光性ポリマー及び化学増幅型レジスト組成物
JP2003107709A (ja) * 2001-09-28 2003-04-09 Fuji Photo Film Co Ltd ポジ型レジスト組成物
JP2007093909A (ja) * 2005-09-28 2007-04-12 Fujifilm Corp ポジ型レジスト組成物及びそれを用いたパターン形成方法
WO2012043685A1 (fr) * 2010-09-30 2012-04-05 Jsr株式会社 Composition de résine sensible au rayonnement, polymère et composé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11212265A (ja) * 1998-01-26 1999-08-06 Sumitomo Chem Co Ltd 化学増幅型のポジ型レジスト組成物
JP2002308937A (ja) * 2001-02-22 2002-10-23 Samsung Electronics Co Ltd 酸により分解可能な保護基を有するラクトン基を含む感光性モノマー、感光性ポリマー及び化学増幅型レジスト組成物
JP2003107709A (ja) * 2001-09-28 2003-04-09 Fuji Photo Film Co Ltd ポジ型レジスト組成物
JP2007093909A (ja) * 2005-09-28 2007-04-12 Fujifilm Corp ポジ型レジスト組成物及びそれを用いたパターン形成方法
WO2012043685A1 (fr) * 2010-09-30 2012-04-05 Jsr株式会社 Composition de résine sensible au rayonnement, polymère et composé

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2623558A4 (fr) * 2010-09-30 2014-02-26 Jsr Corp Composition de résine sensible au rayonnement, polymère et composé
US9459532B2 (en) 2010-09-30 2016-10-04 Jsr Corporation Radiation-sensitive resin composition, polymer and compound
JP2013190637A (ja) * 2012-03-14 2013-09-26 Tokyo Ohka Kogyo Co Ltd 溶剤現像ネガ型レジスト組成物、レジストパターン形成方法
JP2013205837A (ja) * 2012-03-29 2013-10-07 Jsr Corp フォトレジスト組成物及びレジストパターン形成方法
US20130280657A1 (en) * 2012-04-02 2013-10-24 Jsr Corporation Photoresist composition and resist pattern-forming method
US9329474B2 (en) * 2012-04-02 2016-05-03 Jsr Corporation Photoresist composition and resist pattern-forming method
JP2013213951A (ja) * 2012-04-02 2013-10-17 Jsr Corp フォトレジスト組成物及びレジストパターン形成方法
JP2014077999A (ja) * 2012-09-21 2014-05-01 Sumitomo Chemical Co Ltd 樹脂、レジスト組成物及びレジストパターンの製造方法
WO2014185279A1 (fr) * 2013-05-13 2014-11-20 株式会社ダイセル Composé d'ester de l'acide carbamique et composition de solvant pour la production de résines photosensibles le contenant
JP2015043079A (ja) * 2013-07-24 2015-03-05 Jsr株式会社 感放射線性樹脂組成物、レジストパターン形成方法、重合体、化合物及び化合物の製造方法
JP2018097125A (ja) * 2016-12-12 2018-06-21 Jsr株式会社 感放射線性樹脂組成物及びレジストパターン形成方法
JP7062874B2 (ja) 2016-12-12 2022-05-09 Jsr株式会社 感放射線性樹脂組成物及びレジストパターン形成方法
KR20210010926A (ko) 2018-06-28 2021-01-28 후지필름 가부시키가이샤 감활성광선성 또는 감방사선성 수지 조성물, 패턴 형성 방법, 전자 디바이스의 제조 방법, 수지
JPWO2020054275A1 (ja) * 2018-09-13 2021-09-24 富士フイルム株式会社 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法
JP7058339B2 (ja) 2018-09-13 2022-04-21 富士フイルム株式会社 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法

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