WO2019172054A1 - 感放射線性樹脂組成物及びその製造方法並びにレジストパターン形成方法 - Google Patents
感放射線性樹脂組成物及びその製造方法並びにレジストパターン形成方法 Download PDFInfo
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- WO2019172054A1 WO2019172054A1 PCT/JP2019/007675 JP2019007675W WO2019172054A1 WO 2019172054 A1 WO2019172054 A1 WO 2019172054A1 JP 2019007675 W JP2019007675 W JP 2019007675W WO 2019172054 A1 WO2019172054 A1 WO 2019172054A1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/435—Sulfonamides
Definitions
- the present invention relates to a radiation sensitive resin composition, a method for producing the same, and a method for forming a resist pattern.
- Such a radiation sensitive resin composition generates an acid in an exposed portion by irradiation with exposure light such as far ultraviolet rays, extreme ultraviolet rays (EUV), electron beams such as ArF excimer laser, and the exposed portion is exposed by the catalytic action of this acid. And a difference in dissolution rate of the unexposed portion with respect to the developer, and a resist pattern is formed on the substrate.
- exposure light such as far ultraviolet rays, extreme ultraviolet rays (EUV), electron beams such as ArF excimer laser
- Such a radiation-sensitive resin composition not only has excellent resolution, but also has few defects in the resist pattern, excellent defect suppression, and LWR (Line Width when a line and space pattern is formed). Roughness) is small, the LWR performance is required to be excellent, and it is required that a highly accurate pattern can be formed.
- various studies have been made on the molecular structure and polymerization method of the polymer contained in the radiation-sensitive resin composition (JP 2009-098687, JP 2009-102659, and JP 2016-186079).
- the miniaturization of the resist pattern has progressed to a level of 40 nm or less, the required level of the performance is further increased.
- the conventional radiation-sensitive resin composition The request cannot be satisfied.
- EUV or the like has been used as exposure light, and the radiation-sensitive resin composition is required to have improved sensitivity to EUV or the like.
- the present invention has been made based on the circumstances as described above, and its object is to provide a radiation-sensitive resin composition, a resist pattern forming method, and a radiation-sensitive material that are excellent in defect suppression and LWR performance and improved in sensitivity.
- An object of the present invention is to provide a method for producing a conductive resin composition.
- the invention made in order to solve the above-mentioned problems includes a first structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (I)”) and an acid dissociation property represented by the following formula (2).
- a polymer hereinafter referred to as “[A] polymer” having a second structural unit (hereinafter also referred to as “structural unit (II)”) containing a group (hereinafter also referred to as “acid-dissociable group (a)”).
- a first acid generator that generates a first acid upon irradiation with radiation hereinafter also referred to as “[B] acid generator”
- a second acid generator that generates a second acid upon irradiation with radiation.
- [C] acid generator an acid that dissociates the acid dissociable group (a) in the polymer, and the second acid generated from the [C] acid generator is It is an acid that does not substantially dissociate the acid-dissociable group (a) under conditions, and the ratio of the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of the [A] polymer to the number average molecular weight ( Mw / Mn) is a radiation sensitive resin composition (hereinafter also referred to as “radiation sensitive resin composition (I)”) less than 1.5.
- radiation sensitive resin composition hereinafter also referred to as “radiation sensitive resin composition (I)
- Ar is a group obtained by removing (n + 1) hydrogen atoms from an arene having 6 to 20 carbon atoms.
- R 1 is a hydroxy group, a sulfanyl group, or a monovalent group having 1 to 20 carbon atoms.
- N is an integer of 0 to 11.
- R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. It is.
- R 3 is a monovalent group having 1 to 20 carbon atoms and containing the acid dissociable group (a).
- Z is a single bond, an oxygen atom or a sulfur atom.
- R 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
- a first structural unit represented by the following formula (1) and an acid dissociable group (acid dissociation) represented by the following formula (2).
- a polymer having a second structural unit (structural unit (II)) containing a functional group (a)) (hereinafter also referred to as [A ′] polymer), the above [B] acid generator, and the above [C].
- a radiation-sensitive resin composition (hereinafter also referred to as “radiation-sensitive resin composition (II)”), which contains an acid generator, and wherein the polymer [A ′] is a living polymerization product.
- Ar is a group obtained by removing (n + 1) hydrogen atoms from an arene having 6 to 20 carbon atoms.
- R 1 is a hydroxy group, a sulfanyl group, or a monovalent group having 1 to 20 carbon atoms.
- N is an integer of 0 to 11.
- R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. It is.
- R 3 is a monovalent group having 1 to 20 carbon atoms including the acid dissociable group.
- Z is a single bond, an oxygen atom or a sulfur atom.
- R 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
- the radiation-sensitive resin composition (I) and the radiation-sensitive resin composition (II) may be collectively referred to as “the radiation-sensitive resin composition”.
- Still another invention made to solve the above-described problems includes a step of directly or indirectly coating the substrate with the radiation-sensitive resin composition (I) or the radiation-sensitive resin composition (II), and the coating described above.
- a resist pattern forming method comprising a step of exposing a resist film formed by a processing step and a step of developing the exposed resist film.
- Still another invention made to solve the above problems is represented by the monomer represented by the following formula (i) (hereinafter also referred to as “monomer (i)”) and the following formula (ii).
- Living polymerization of a monomer composition containing a monomer having an acid dissociable group (acid dissociable group (a)) (hereinafter also referred to as “monomer (ii)”), and the living polymerization step A polymer ([A] polymer) having a ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight to number average molecular weight measured by gel permeation chromatography formed by (1.5) polymer, by irradiation with radiation
- Obtaining a mixture comprising a first acid generator that generates a first acid ([B] acid generator) and a second acid generator that generates a second acid upon irradiation with radiation ([C] acid generator);
- the first acid generated from the first acid generator is An acid that dis
- Ar is a group obtained by removing (n + 1) hydrogen atoms from an arene having 6 to 20 carbon atoms.
- R 1 is a hydroxy group, a sulfanyl group or a monovalent group having 1 to 20 carbon atoms.
- N is an integer of 0 to 11.
- R 1 When n is 2 or more, the plurality of R 1 are the same or different, and R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. It is.
- R 3 is a monovalent group having 1 to 20 carbon atoms and containing the acid dissociable group (a).
- Z is a single bond, an oxygen atom or a sulfur atom.
- R 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
- the radiation-sensitive resin composition and the resist pattern forming method of the present invention a resist pattern with improved sensitivity, fewer defects, and smaller LWR can be formed.
- the manufacturing method of the radiation sensitive resin composition of this invention the said radiation sensitive resin composition can be manufactured simply and reliably. Accordingly, these can be suitably used for semiconductor device processing processes and the like that are expected to be further miniaturized in the future.
- the radiation sensitive resin composition (I) contains a [A] polymer, a [B] acid generator, and a [C] acid generator.
- the said radiation sensitive resin composition (I) may contain the [D] solvent as a suitable component, and may contain the other arbitrary components in the range which does not impair the effect of this invention.
- the radiation sensitive resin composition (I) contains a [A] polymer, a [B] acid generator and a [C] acid generator, and the Mw / Mn of the [A] polymer is smaller than 1.5. By doing, it is excellent in defect suppression property, LWR performance, and sensitivity.
- the reason why the radiation-sensitive resin composition (I) exhibits the above-described effect by having the above-described configuration is not necessarily clear, but can be inferred as follows, for example. That is, the radiation sensitive resin composition (I) includes a [A] polymer that is a copolymer of a (meth) acrylic acid ester containing a styrene monomer and an acid dissociable group, and a [A] polymer.
- the polymer has the structural unit (I) and the structural unit (II), and the number average molecular weight (Mn) of the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC). Is a polymer having a ratio (Mw / Mn) of less than 1.5.
- the radiation sensitive resin composition (I) may contain one or more [A] polymers.
- Mw / Mn of the polymer is a value smaller than 1.5, and a value smaller than 1.35 is more preferable.
- the Mw / Mn is usually 1 or more, preferably 1.1 or more, and more preferably 1.2 or more.
- the lower limit of the Mw of the polymer is preferably 1,000, more preferably 3,000, still more preferably 4,000, particularly preferably 5,000, still more preferably 6,000, and 6,500 Is most preferred.
- the upper limit of Mw is preferably 50,000, more preferably 30,000, still more preferably 20,000, particularly preferably 10,000, still more preferably 8,000, and most preferably 7,000.
- the lower limit of Mn of the polymer is preferably 800, more preferably 2,500, still more preferably 3,000, particularly preferably 4,000, still more preferably 4,600, and most preferably 5,200. preferable.
- the upper limit of Mw is preferably 40,000, more preferably 23,000, still more preferably 15,000, particularly preferably 8,000, still more preferably 6,000, and most preferably 5,200.
- the radiation-sensitive resin composition (I) makes the difference in solubility between the exposed part and the unexposed part more prominent, and the variation in solubility is further increased. As a result, defect suppression, LWR performance and sensitivity can be further improved.
- Mw and Mn of the polymer in this specification are values measured using gel permeation chromatography (GPC) under the following conditions.
- GPC column 2 "G2000HXL", 1 "G3000HXL” and 1 "G4000HXL” from Tosoh Corporation Column temperature: 40 ° C
- Elution solvent Tetrahydrofuran (Wako Pure Chemical Industries, Ltd.)
- Flow rate 1.0 mL / min
- Sample concentration 1.0% by mass
- Sample injection volume 100 ⁇ L
- Detector Differential refractometer Standard material: Monodisperse polystyrene
- the polymer is a structural unit containing a lactone structure, a cyclic carbonate structure, a sultone structure, or a combination thereof in addition to the structural units (I) and (II) (hereinafter also referred to as “structural unit (III)”) and It may have a structural unit containing an alcoholic hydroxyl group (hereinafter also referred to as “structural unit (IV)”), and may have other structural units other than the structural units (I) to (IV). .
- the polymer may have one or more of each structural unit. Hereinafter, each structural unit will be described.
- the structural unit (I) is a structural unit represented by the following formula (1).
- Ar is a group obtained by removing (n + 1) hydrogen atoms from an arene having 6 to 20 carbon atoms.
- R 1 is a hydroxy group, a sulfanyl group or a monovalent organic group having 1 to 20 carbon atoms.
- n is an integer of 0 to 11. When n is 2 or more, the plurality of R 1 are the same or different.
- R 2 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
- Examples of the C6-C20 arene that gives Ar in the above formula (1) include benzene, naphthalene, anthracene, phenanthrene, tetracene, and pyrene. Of these, benzene is preferred.
- Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R 1 include, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a carbon-carbon boundary of this hydrocarbon group, or a terminal on the bond side.
- Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 carbon atoms. And 20 monovalent aromatic hydrocarbon groups.
- the “hydrocarbon group” includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
- the “hydrocarbon group” may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
- the “chain hydrocarbon group” refers to a hydrocarbon group that does not include a cyclic structure but includes only a chain structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group.
- alicyclic hydrocarbon group means a hydrocarbon group containing only an alicyclic structure as a ring structure and not containing an aromatic ring structure, and includes a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic Includes both hydrocarbon groups.
- “Aromatic hydrocarbon group” refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic structure.
- Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, and t-butyl group; An alkenyl group such as an ethenyl group, a propenyl group, a butenyl group; Examples thereof include alkynyl groups such as ethynyl group, propynyl group and butynyl group.
- Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic alicyclic saturated hydrocarbon groups such as a cyclopentyl group and a cyclohexyl group; Monocyclic alicyclic unsaturated hydrocarbon groups such as cyclopentenyl group and cyclohexenyl group; Polycyclic alicyclic saturated hydrocarbon groups such as norbornyl group, adamantyl group and tricyclodecyl group; Examples thereof include polycyclic alicyclic unsaturated hydrocarbon groups such as a norbornenyl group and a tricyclodecenyl group.
- Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include aryl groups such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and an anthryl group; Examples thereof include aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group and anthrylmethyl group.
- hetero atom constituting the monovalent or divalent heteroatom-containing group examples include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, and a halogen atom.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Examples of the divalent heteroatom-containing group include —O—, —CO—, —S—, —CS—, —NR′—, —SO—, —SO 2 —, and combinations of two or more thereof. And the like.
- R ′ is a hydrogen atom or a monovalent carbon hydrogen group.
- Examples of the monovalent heteroatom-containing group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxy group, carboxy group, cyano group, amino group and sulfanyl group.
- R 1 is preferably a hydroxy group or a sulfanyl group, and more preferably a hydroxy group.
- At least one of R 1 in the above formula (1) is a hydroxy group.
- the polymer has such a phenolic hydroxyl group, the sensitivity when using KrF excimer laser light, EUV, electron beam, etc. can be further improved, thereby improving defect suppression and LWR performance. It can be improved further.
- Examples of the structural unit (I) include a structural unit represented by the following formula.
- R ⁇ 2 > is synonymous with the said Formula (1).
- a structural unit containing a phenolic hydroxyl group is preferable, and a structural unit derived from 4-hydroxystyrene, a structural unit derived from 3-hydroxystyrene, or a structural unit derived from 3,4-dihydroxystyrene. More preferred.
- “Phenolic hydroxyl group” means not only a hydroxy group directly bonded to a benzene ring but also a general hydroxy group directly bonded to an aromatic ring.
- the content rate of structural unit (I) As a minimum of the content rate of structural unit (I), 5 mol% is preferable with respect to all the structural units which comprise a [A] polymer, 10 mol% is more preferable, 15 mol% is more preferable, and 20 mol% % Is particularly preferred. As an upper limit of the said content rate, 80 mol% is preferable, 70 mol% is more preferable, 60 mol% is further more preferable, 55 mol% is especially preferable. By making the content rate of structural unit (I) into the said range, defect inhibitory property, LWR performance, and a sensitivity can be improved more.
- the structural unit (II) is a structural unit represented by the following formula (2) and containing an acid dissociable group (a).
- the “acid-dissociable group” refers to a group that substitutes a hydrogen atom of an acidic group such as a carboxy group, a phenolic hydroxyl group, or a sulfo group, and that dissociates by the action of an acid.
- the acid dissociable group (a) in the exposed area is dissociated by the action of the first acid generated from the [B] acid generator and the polarity increases.
- the resist pattern can be formed by being easily soluble or hardly soluble in the developer.
- R 3 is a monovalent group having 1 to 20 carbon atoms and containing an acid dissociable group (a).
- Z is a single bond, an oxygen atom or a sulfur atom.
- R 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
- Examples of the monovalent group having 1 to 20 carbon atoms including the acid dissociable group (a) represented by R 3 include a group represented by the following formula (3).
- R 5 is a divalent organic group having 1 to 20 carbon atoms or a single bond.
- X is —COO—, —SO 3 —, —Ar′—O—, or a single bond.
- Ar ′ is a substituted or unsubstituted arenediyl group having 6 to 20 carbon atoms.
- R 6 is a monovalent acid dissociable group.
- Examples of the divalent organic group represented by R 5 include a group in which one hydrogen atom is removed from the group exemplified as the monovalent organic group of R 1 in the above formula (1).
- R 5 is preferably a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably a single bond.
- X is preferably —COO— or a single bond, more preferably a single bond.
- Examples of the monovalent acid dissociable group represented by R 6 include a group represented by the following formula (PG1) and a group represented by the following formula (PG2).
- RPG1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
- R PG2 and R PG3 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a ring member having 3 to This represents a part of the 20 alicyclic structures.
- * Indicates a site bonded to an oxyoxygen atom derived from an acidic group.
- the “number of ring members” refers to the total number of atoms constituting the ring.
- R PG4 and R PG5 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or these groups are combined with each other and bonded together. This represents a part of an alicyclic structure having 3 to 20 ring members and formed with carbon atoms.
- R PG6 is a monovalent hydrocarbon group having 1 to 20 carbon atoms. ** represents a site bonded to an oxyoxygen atom derived from an acidic group.
- Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R PG1 to R PG6 include groups similar to the groups exemplified as the hydrocarbon group for R 1 in the above formula (1).
- Examples of the alicyclic structure having 3 to 20 ring members constituted by R PG2 and R PG3 or R PG4 and R PG5 include a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, a cyclooctane structure, a norbornane structure, an adamantane structure, a tricyclo Examples include a decane structure and a tetracyclododecane structure.
- Examples of the structural unit (II) include a structural unit derived from a (meth) acrylic acid ester having a monovalent acid dissociable group.
- the lower limit of the content ratio of the structural unit (II) is preferably 10 mol%, more preferably 20 mol%, still more preferably 30 mol% with respect to all the structural units constituting the [A] polymer.
- 80 mol% is preferable, 70 mol% is more preferable, and 60 mol% is further more preferable.
- the structural unit (III) is a structural unit including a lactone structure, a cyclic carbonate structure, a sultone structure, or a combination thereof.
- the polymer can moderately adjust the solubility in the developer, and as a result, the defect suppression property, LWR performance and sensitivity can be further improved. In addition, the adhesion between the resist pattern and the substrate can be further improved.
- Examples of the structural unit (III) include a structural unit represented by the following formula.
- R L1 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
- a structural unit containing a lactone structure is preferable, and a structural unit derived from 5-cyanonorbornanelactone-yl (meth) acrylate is more preferable.
- the lower limit of the content ratio of the structural unit (III) is preferably 10 mol%, preferably 20 mol% with respect to all the structural units in the polymer [A]. Is more preferable, and 25 mol% is further more preferable. As an upper limit of the said content rate, 80 mol% is preferable, 50 mol% is more preferable, and 40 mol% is further more preferable.
- the structural unit (IV) is a structural unit containing an alcoholic hydroxyl group. [A] By having the structural unit (IV), the polymer can moderately adjust the solubility in the developer, and as a result, the defect suppression property, LWR performance and sensitivity can be further improved.
- Examples of the structural unit (IV) include a structural unit represented by the following formula.
- R L2 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
- [A] When a polymer has a structural unit (IV), as a minimum of the content rate of a structural unit (IV), 1 mol% is preferable with respect to all the structural units in a [A] polymer, and 5 mol% Is more preferable, and 10 mol% is further more preferable. As an upper limit of the said content rate, 50 mol% is preferable, 40 mol% is more preferable, and 30 mol% is further more preferable.
- [A] polymer can adjust moderately the solubility to a developing solution, As a result, defect suppression property, LWR performance, and sensitivity are more. Can be improved.
- Examples of the other structural unit include a structural unit containing a polar group and a structural unit containing a non-acid dissociable hydrocarbon group (except for those corresponding to structural units (I) to (IV)).
- Examples of the polar group include a hydroxy group, a carboxy group, a nitro group, a cyano group, and a sulfonamide group.
- Examples of the non-acid-dissociable hydrocarbon group include a primary or secondary chain hydrocarbon group in which a carbon atom serving as a bond bonded to an oxyoxygen atom of —COO— is a primary carbon atom, and a carbon atom serving as a bond is primary.
- a secondary alicyclic hydrocarbon group a methyl group, 1-adamantyl group, etc.
- the non-acid-dissociable hydrocarbon group is preferably a secondary alicyclic hydrocarbon group or 1-adamantyl group in which the carbon atom serving as a bond is a secondary bond.
- the content rate of another structural unit 30 mol% is preferable and 10 mol% is more preferable. As a minimum of the above-mentioned content rate, it is 1 mol%, for example.
- the lower limit of the content of the polymer is preferably 50 parts by mass, more preferably 60 parts by mass with respect to all components other than the solvent [D] of the radiation-sensitive resin composition (I). Part by mass is more preferable.
- the said radiation sensitive resin composition (I) can contain 1 type (s) or 2 or more types of [A] polymers.
- the polymer is preferably a living polymerization product, and more preferably a living radical polymerization product.
- the polymer includes, for example, a monomer (i) that gives the structural unit (I), a monomer (ii) that gives the structural unit (II), and, if necessary, a monomer other than these monomers It can be synthesized by polymerizing a monomer composition containing a polymer in a suitable solvent using a polymerization initiator or the like.
- the polymerization method for synthesizing the polymer is preferably living polymerization from the viewpoint of easily and reliably synthesizing a polymer having a small Mw / Mn, and examples thereof include living cationic polymerization, living anionic polymerization, and living radical polymerization. It is done. Among these, living radical polymerization is preferable from the viewpoint of superior polymerization controllability.
- living radical polymerization examples include reversible addition-fragmentation chain transfer (RAFT) polymerization, atom transfer radical polymerization (ATRP), and nitroxide-mediated radical polymerization (NMP).
- RAFT reversible addition-fragmentation chain transfer
- ATRP atom transfer radical polymerization
- NMP nitroxide-mediated radical polymerization
- RAFT polymerization is performed by using a reversible addition-fragmentation chain transfer agent (RAFT agent) together with a radical polymerization initiator.
- RAFT agent reversible addition-fragmentation chain transfer agent
- radical polymerization initiators used in RAFT polymerization include azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis ( Azo radical initiators such as 2-cyclopropylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, And peroxide radical initiators such as benzoyl peroxide, t-butyl hydroperoxide and cumene hydroperoxide. These radical polymerization initiators can be used alone or in combination of two or more.
- RAFT agents include mercaptocarboxylic acids such as mercaptopropionic acid; Mercaptocarboxylic acid esters such as 2-merhexyl 3-mercaptopropionate; Thiols such as 4-mercapto-1-butanol; Disulfides such as 2-hydroxyethyl disulfide; Dithioesters such as cumyl dithiobenzoate; Xanthates such as ethyl ethyl xanthate; Dithiocarbamates such as benzyldiethyldithiocarbamate; And trithiocarbonates such as 2-cyano-2-propyldodecyltrithiocarbonate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid, and cyanomethyldodecyltrithiocarbonate.
- mercaptocarboxylic acids such as mercaptopropionic acid
- ATRP is performed using an atom transfer radical polymerization initiator as a radical polymerization initiator in the presence of a reducing agent and a transition metal catalyst.
- Examples of the atom transfer radical polymerization initiator include propyl-2-bromopropionate, methyl-2-chloropropionate, ethyl-2-chloropropionate, methyl-2-bromopropionate, ethyl-2- Examples thereof include bromoisobutyrate, methyl-2-bromoisobutyrate, ethylenebis (2-bromoisobutyrate), 1,1,1-tris (2-bromoisobutyloxymethyl) ethane and the like.
- reducing agent used in ATRP examples include ascorbic acid, ascorbic acid ester, organotin (II) compound, sodium sulfite, low oxidation state sulfur compound, sodium hydrogen sulfite, hydrazine hydrate, acetylacetonate, hydroxyacetone, Selected from reducing sugar, monosaccharide, tetrahydrofuran, dihydroanthracene, silane, 2,3-dimethylbutadiene, amine, formamidinesulfinic acid, borane compound, aldehyde, and Fe 2+ , Cr 3+ , Al 3+ , Ti 3+ and Ti 4+ And inorganic compounds or organic compounds selected from the group consisting of inorganic salts containing metals.
- organotin (II) compound organotin (II) compound, sodium sulfite, low oxidation state sulfur compound, sodium hydrogen sulfite, hydrazine hydrate, acetylacetonate, hydroxy
- transition metal catalyst used in ATRP examples include compounds having a transition metal ion and a ligand.
- transition metal examples include Cu, Fe, Co, Cr, Ni, Sm, Mn, Mo, Ag, Zn, Pd, Pt, Re, Rh, Ir, In, Yb, and Ru.
- Examples of the ligand include triphenylphosphane, 2,2-bipyridine, alkyl-2,2-bipyridine, such as 4,4-di- (5-nonyl) -2,2-bipyridine, 4,4-dipyridine.
- -(5-heptyl) -2,2-bipyridine tris (2-aminoethyl) amine (TREN), tris (2-pyridylmethyl) amine (TPMA), N, N, N ', N', N "- Examples include pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, and tetramethylethylenediamine.
- NMP is performed using an NMP initiator as a radical polymerization initiator.
- NMP initiators examples include 2,2,6,6-tetramethylpiperidinoxyl (TEMPO), 2,2,6,6-tetramethylpiperidinoxyl-4-ol (TEMPOL), 2,2, Examples include 6,6-tetramethylpiperidinoxyl-4-ketone (TEMPON).
- Examples of the solvent used for the living radical polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane, Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Halogenated hydrocarbons such as chlorobutane, bromohexane, dichloroethane, hexamethylene dibromide, chlorobenzene, Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate, methyl propionate, Ketones such as acetone, methyl ethyl
- the lower limit of the reaction temperature in living radical polymerization is preferably 40 ° C, more preferably 50 ° C.
- 150 degreeC is preferable and 140 degreeC is more preferable.
- As a minimum of reaction time in living polymerization 1 hour is preferred and 3 hours is more preferred.
- the upper limit of the reaction time is preferably 96 hours, more preferably 48 hours.
- the [A] polymer when at least one of R 1 in the above formula (1) is a hydroxy group, the [A] polymer is represented by the formula (i) as the monomer (i).
- Polymerization is performed using a monomer in which R 1 is an acyloxy group such as an acetoxy group, and the resulting polymer is subjected to a hydrolysis reaction of the acyloxy group in the presence of a base such as triethylamine to produce a hydroxy group.
- a base such as triethylamine
- the acid generator is a first acid that dissociates the acid dissociable group (a) when heated for 1 minute at a temperature of 80 ° C. to 140 ° C. (hereinafter, also referred to as “acid (b)”). Is generated by irradiation with radiation.
- the acid (b) generated from the [B] acid generator in the exposed area by irradiation of radiation heating is performed at a temperature in the range of 80 ° C. to 140 ° C. for 1 minute, for example, post-exposure bake (PEB).
- PEB post-exposure bake
- the lower limit of the above temperature is 80 ° C, preferably 90 ° C, more preferably 100 ° C.
- the upper limit of the temperature is 140 ° C, preferably 135 ° C, and more preferably 130 ° C.
- Examples of the acid (b) include sulfonic acid, imidic acid, amic acid, methide acid, phosphinic acid, carboxylic acid and the like. Of these, sulfonic acid is preferred.
- Examples of the sulfonic acid include a compound represented by the following formula (4) (hereinafter also referred to as “acid (b1)”).
- acid (b1) a compound represented by the following formula (4)
- the acid generator generates an acid (b1) having a ring structure, so that the diffusion length in the resist film is moderately shortened. As a result, defect suppression, LWR performance and sensitivity are further improved. be able to.
- R p1 is a monovalent group containing a ring structure having 5 or more ring members.
- R p2 is a divalent linking group.
- R p3 and R p4 are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
- R p5 and R p6 are each independently a fluorine atom or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
- n p1 is an integer of 0 to 10.
- n p2 is an integer of 0 to 10.
- n p3 is an integer of 0 to 10.
- n p1 + n p2 + n p3 is 1 or more and 30 or less.
- n p1 is 2 or more
- the plurality of R p2 are the same or different.
- n p3 are the same or different, and the plurality of R p4 are the same or different.
- n p3 is 2 or more
- the plurality of R p5 are the same or different, and the plurality of R p6 are the same or different.
- Examples of the monovalent group including a ring structure having 5 or more ring members represented by R p1 include a monovalent group including an alicyclic structure having 5 or more ring members and an aliphatic heterocyclic structure having 5 or more ring members.
- Examples of the alicyclic structure having 5 or more ring members include, for example, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, a cyclooctane structure, a cyclononane structure, a cyclodecane structure, a cyclododecane structure, and the like, Monocyclic cycloalkene structures such as cyclopentene structure, cyclohexene structure, cycloheptene structure, cyclooctene structure, cyclodecene structure, Polycyclic cycloalkane structures such as norbornane structure, adamantane structure, tricyclodecane structure, tetracyclododecane structure, Examples thereof include polycyclic cycloalkene structures such as a norbornene structure and a tricyclodecene structure.
- Examples of the aliphatic heterocyclic structure having 5 or more ring members include a lactone structure such as a hexanolactone structure and a norbornane lactone structure, Hexano sultone structure, sultone structure such as norbornane sultone structure, Oxygen-containing heterocyclic structures such as oxacycloheptane structure and oxanorbornane structure, Nitrogen atom-containing heterocyclic structures such as azacyclohexane structure, diazabicyclooctane structure, Examples thereof include a thicyclohexane structure and a sulfur atom-containing heterocyclic structure having a thianorbornane structure.
- Examples of the aromatic ring structure having 5 or more ring members include a benzene structure, a naphthalene structure, a phenanthrene structure, and an anthracene structure.
- aromatic heterocyclic structures having 5 or more ring members include oxygen atom-containing heterocyclic structures such as furan structure, pyran structure, and benzopyran structure, Examples thereof include a nitrogen atom-containing heterocyclic structure such as a pyridine structure, a pyrimidine structure and an indole structure.
- the lower limit of the number of ring members of the ring structure of R p1 is preferably 6, more preferably 8, more preferably 9, and particularly preferably 10.
- the upper limit of the number of ring members is preferably 15, more preferably 14, more preferably 13, and particularly preferably 12.
- a part or all of the hydrogen atoms contained in the ring structure of R p1 may be substituted with a substituent.
- substituents include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxy group, carboxy group, cyano group, nitro group, alkoxy group, alkoxycarbonyl group, alkoxycarbonyloxy group, acyl group, Examples include an acyloxy group. Of these, a hydroxy group is preferred.
- R p1 is preferably a monovalent group containing an alicyclic structure having 5 or more ring members or a monovalent group containing an aliphatic heterocyclic structure having 5 or more ring members, and 1 containing an alicyclic structure having 9 or more ring members. More preferred are monovalent groups or monovalent groups containing an aliphatic heterocyclic structure having 9 or more ring members, such as an adamantyl group, a hydroxyadamantyl group, a norbornane lactone-yl group, a norbornane sultone-yl group, or a 5-oxo-4-oxa group. A tricyclo [4.3.1.1 3,8 ] undecan-yl group is more preferred, and an adamantyl group is particularly preferred.
- Examples of the divalent linking group represented by R p2 include a carbonyl group, an ether group, a carbonyloxy group, a sulfide group, a thiocarbonyl group, a sulfonyl group, and a divalent hydrocarbon group.
- a carbonyloxy group, a sulfonyl group, an alkanediyl group or a cycloalkanediyl group is preferable, a carbonyloxy group or a cycloalkanediyl group is more preferable, a carbonyloxy group or a norbornanediyl group is further preferable, and a carbonyloxy group is Particularly preferred.
- Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R p3 and R p4 include an alkyl group having 1 to 20 carbon atoms.
- Examples of the monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by R p3 and R p4 include a fluorinated alkyl group having 1 to 20 carbon atoms.
- R p3 and R p4 are preferably a hydrogen atom, a fluorine atom or a fluorinated alkyl group, more preferably a fluorine atom or a perfluoroalkyl group, and even more preferably a fluorine atom or a trifluoromethyl group.
- Examples of the monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by R p5 and R p6 include a fluorinated alkyl group having 1 to 20 carbon atoms.
- R p5 and R p6 are preferably a fluorine atom or a fluorinated alkyl group, more preferably a fluorine atom or a perfluoroalkyl group, still more preferably a fluorine atom or a trifluoromethyl group, and particularly preferably a fluorine atom.
- n p1 is preferably 0 to 5, more preferably 0 to 3, further preferably 0 to 2, and particularly preferably 0 or 1.
- n p2 is preferably 0 to 5, more preferably 0 to 2, still more preferably 0 or 1, and particularly preferably 0.
- n p3 is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 or 2.
- the strength of the acid (b1) generated from the [B] acid generator can be increased.
- the defect-suppressing property of the radiation-sensitive resin composition (I), LWR Performance and sensitivity can be further improved.
- the lower limit of n p1 + n p2 + n p3 is preferably 2 and more preferably 4.
- the upper limit of n p1 + n p2 + n p3 is preferably 20, and more preferably 10.
- the acid generator usually contains a radiation-sensitive cation and an anion which is a conjugate base of the acid (b) (hereinafter also referred to as “anion (b ′)”).
- the anion (b ′) is usually an anion obtained by removing protons from the acid group of the acid (b).
- the acid generator [B] gives acid (b) from protons and anions (b ′) generated by the decomposition of the radiation-sensitive cations by the action of radiation.
- anion (b ′) examples include a sulfonate anion, an imide anion, an amide anion, and a methide anion.
- a radiation-sensitive cation is a cation that decomposes upon irradiation with radiation.
- an acid generator composed of a sulfonate anion and a radiation-sensitive onium cation as an example, in the exposed portion, a sulfonic acid is generated from protons generated by the decomposition of the radiation-sensitive onium cation and the sulfonate anion.
- Examples of the radiation-sensitive onium cation include monovalent cations represented by the following formulas (T-1) to (T-3) (hereinafter referred to as “cations (T-1) to (T-3)”). Also).
- R a1 and R a2 are each independently a monovalent organic group having 1 to 20 carbon atoms.
- k1 is an integer of 0 to 5.
- R a3 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group, or a halogen atom.
- the plurality of R a3 are the same or different and are each a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group, or a halogen atom, or 2 of the plurality of R a3 It represents a part of a ring structure having 4 to 20 ring members constituted by two or more carbon atoms bonded to each other and bonded to each other.
- t1 is an integer of 0 to 3.
- Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R a1 , R a2 and R a3 include the same groups as the organic groups exemplified as R 1 in the above formula (1).
- R a1 and R a2 are preferably a monovalent unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group in which a hydrogen atom is substituted with a substituent, and a monovalent unsubstituted group having 6 to 18 carbon atoms.
- R a1 and R a2 are preferably a monovalent unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group in which a hydrogen atom is substituted with a substituent, and a monovalent unsubstituted group having 6 to 18 carbon atoms.
- an aromatic hydrocarbon group in which a hydrogen atom is substituted with a substituent is more preferable, and a phenyl group is more preferable.
- Examples of the substituent for substituting the hydrogen atom of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R a1 and R a2 include a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, —OSO 2 —R k , —SO 2 —R k , —OR k , —COOR k , —O—CO—R k , —O—R kk —COOR k , —R kk —CO—R k or —S—R k is preferred.
- R k is a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R kk is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms.
- R a3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, —OSO 2 —R k , —SO 2 —R k , —OR k , —COOR k , —O—CO— R k , —O—R kk —COOR k , —R kk —CO—R k or —S—R k is preferred.
- R k is a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R kk is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms.
- k2 is an integer of 0 to 7.
- R a4 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group, or a halogen atom.
- the plurality of R a4 are the same or different and are each a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group, or a halogen atom, or 2 of the plurality of R a4 It represents a part of a ring structure having 4 to 20 ring members constituted by two or more carbon atoms bonded to each other and bonded to each other.
- k3 is an integer of 0-6.
- R a5 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group, or a halogen atom.
- the plurality of R a5 are the same or different and are each a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group, or a halogen atom, or 2 of the plurality of R a5 It represents a part of a ring structure having 3 to 20 ring members constituted by two or more carbon atoms bonded to each other and bonded to each other.
- r is an integer of 0 to 3.
- R a6 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
- t2 is an integer of 0-2.
- R a4 and R a5 are a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, —OR k , —COOR k , —O—CO—R k , —O—R kk —COOR k Or, —R kk —CO—R k is preferable.
- R k is a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R kk is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms.
- k4 is an integer of 0 to 5.
- R a7 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group, or a halogen atom.
- the plurality of R a7 are the same or different and are each a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group, or a halogen atom, or two of the plurality of R a7 It represents a part of a ring structure having 4 to 20 ring members constituted by two or more carbon atoms bonded to each other and bonded to each other.
- k5 is an integer of 0 to 5.
- R a8 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group, or a halogen atom.
- the plurality of R a8 are the same or different and are each a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group, or a halogen atom, or 2 of the plurality of R a8 It represents a part of a ring structure having 4 to 20 ring members constituted by two or more carbon atoms bonded to each other and bonded to each other.
- R a7 and R a8 include a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, —OSO 2 —R k , —SO 2 —R k , —OR k , —COOR k , —O —CO—R k , —O—R kk —COOR k , —R kk —CO—R k or —S—R k or a ring structure in which two or more of these groups are combined with each other is preferable.
- R k is a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R kk is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms.
- Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R a3 , R a4 , R a5 , R a7 and R a8 include the groups exemplified as the hydrocarbon group of R 1 in the above formula (1). And the like groups.
- Examples of the divalent organic group represented by R a6 include groups obtained by removing one hydrogen atom from a monovalent organic group having 1 to 20 carbon atoms exemplified as R 1 in the above formula (1). It is done.
- Examples of the substituent for substituting the hydrogen atom of the hydrocarbon group in R a3 , R a4 , R a5 , R a7 and R a8 include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a hydroxy group, Examples thereof include a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an acyl group, and an acyloxy group. Among these, a halogen atom is preferable and a fluorine atom is more preferable.
- R a3 , R a4 , R a5 , R a7, and R a8 include an unsubstituted linear or branched monovalent alkyl group, a monovalent fluorinated alkyl group, an unsubstituted monovalent aromatic carbonization
- a hydrogen group, —OSO 2 —R k or —SO 2 —R k is preferred, a fluorinated alkyl group or an unsubstituted monovalent aromatic hydrocarbon group is more preferred, and a fluorinated alkyl group is more preferred.
- k1 is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
- K2 in the formula (T-2) is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
- k3 is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
- r is preferably 2 or 3, more preferably 2.
- t2 is preferably 0 or 1, and more preferably 0.
- k4 and k5 are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0.
- the radiation-sensitive onium cation is preferably a cation (T-1) and a cation (T-2), more preferably a cation (T-1), and still more preferably a triphenylsulfonium cation.
- the lower limit of the content of the acid generator is preferably 1 part by weight, more preferably 5 parts by weight, further preferably 10 parts by weight, and 15 parts by weight with respect to 100 parts by weight of the [A] polymer. Particularly preferred. As an upper limit of the said content, 50 mass parts is preferable, 40 mass parts is more preferable, 30 mass parts is further more preferable, 25 mass parts is especially preferable. [B] By making content of an acid generator into the said range, defect inhibitory property, LWR performance, and a sensitivity can be improved more.
- the radiation-sensitive resin composition (I) can contain one or more [B] acid generators.
- the acid generator is a second acid (hereinafter also referred to as “acid (c)” that does not substantially dissociate the acid dissociable group (a) when heated at a temperature of 80 ° C. to 140 ° C. for 1 minute. ”)" Is generated by irradiation of radiation.
- the acid (c) generated from the [C] acid generator in the exposed area by irradiation with radiation it is heated at a temperature in the range of 80 ° C. to 140 ° C. for 1 minute, for example, post-exposure baking (PEB).
- PEB post-exposure baking
- the acid dissociable group (a) of the polymer [A] is not substantially dissociated. That is, the [C] acid generator functions as a highly functional acid diffusion control agent that captures an acid in an unexposed area and does not capture an acid in an exposed area.
- Examples of the acid (c) include carboxylic acid.
- Examples of the carboxylic acid include a compound represented by the following formula (5).
- R ⁇ is a monovalent organic group having 1 to 30 carbon atoms.
- Examples of the monovalent organic group having 1 to 30 carbon atoms represented by R ⁇ include the same groups as those exemplified as the monovalent organic group for R 1 in the above formula (1).
- R ⁇ is preferably a substituted or unsubstituted aryl group or a carbonyloxy hydrocarbon group, more preferably a substituted aryl group or a carbonyloxy alicyclic hydrocarbon group, and a hydroxyphenyl group or an adamantane-1-yloxycarbonyl group. Further preferred.
- the acid generator usually contains a radiation-sensitive cation and an anion (hereinafter also referred to as “anion (c ′)”) which is a conjugate base of the acid (c).
- the anion (c ′) is an anion obtained by removing a proton from the acid group of the acid (c).
- the acid generator may have a betaine structure in which a carboxylate group or the like derived from an anion (c ′) is bonded to a hydrocarbon group or the like of a radiation-sensitive cation.
- the [C] acid generator gives acid (c) from protons and anions (c ′) generated by the decomposition of the radiation-sensitive cations by the action of radiation.
- the acid (c) does not substantially dissociate the acid dissociable group (a) in the polymer [A] when heated for 1 minute at a temperature of 80 ° C. or higher and 140 ° C. or lower. Therefore, the [C] acid generator exhibits a function as an acid diffusion controller in the resist film.
- anion (c ′) examples include a carboxylate anion.
- Examples of the radiation-sensitive cation of [C] acid generator include the same cations as those exemplified as the radiation-sensitive cation of [B] acid generator.
- the lower limit of the content of the acid generator is preferably 0.1 mol%, more preferably 0.5 mol%, still more preferably 1 mol% with respect to 100 mol% of the [B] acid generator. 2 mol% is particularly preferred. As an upper limit of the said content, 50 mol% is preferable, 30 mol% is more preferable, 15 mol% is further more preferable, and 10 mol% is especially preferable.
- the lower limit of the content of the acid generator is preferably 0.02 parts by mass, more preferably 0.1 parts by mass, and further 0.2 parts by mass with respect to 100 parts by mass of the polymer [A]. 0.4 parts by mass is preferable.
- 10 mass parts is preferable, 6 mass parts is more preferable, 3 mass parts is further more preferable, 2 mass parts is especially preferable.
- the radiation sensitive resin composition (I) can contain one or more [C] acid generators.
- the radiation-sensitive resin composition (I) usually contains a [D] solvent.
- the solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing at least the [A] polymer, the [B] acid generator, the [C] acid generator, and other optional components.
- Examples of the solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, and the like.
- alcohol solvents examples include aliphatic monoalcohol solvents having 1 to 18 carbon atoms such as 4-methyl-2-pentanol and n-hexanol; An alicyclic monoalcohol solvent having 3 to 18 carbon atoms such as cyclohexanol; A polyhydric alcohol solvent having 2 to 18 carbon atoms such as propylene glycol; Examples thereof include polyhydric alcohol partial ether solvents having 3 to 19 carbon atoms such as propylene glycol monomethyl ether.
- ether solvents examples include dialkyl ether solvents having 4 to 14 carbon atoms such as diethyl ether; Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; And aromatic ring-containing ether solvents such as diphenyl ether and anisole.
- ketone solvents examples include chain ketone solvents having 3 to 12 carbon atoms such as acetone, methyl ethyl ketone, methyl-iso-butyl ketone, 2-heptanone; Cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone; Examples include 2,4-pentanedione, acetonylacetone, acetophenone, and the like.
- amide solvent examples include cyclic amide solvents such as N, N′-dimethylimidazolidinone and N-methylpyrrolidone; Examples thereof include chain amide solvents such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpropionamide.
- cyclic amide solvents such as N, N′-dimethylimidazolidinone and N-methylpyrrolidone
- chain amide solvents such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpropionamide.
- ester solvent examples include monocarboxylic acid ester solvents such as acetate ester solvents such as n-butyl acetate and amyl acetate, and propionate solvents such as ethyl propionate; Hydroxycarboxylic acid ester solvents such as ethyl lactate and n-butyl glycolate; Polyhydric alcohol carboxylate solvents such as propylene glycol acetate; Polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate; Polycarboxylic acid diester solvents such as diethyl oxalate; Lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone; Examples thereof include carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate.
- monocarboxylic acid ester solvents such as acetate ester solvents such as n-butyl acetate and amyl a
- hydrocarbon solvent examples include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as n-pentane and n-hexane; Examples thereof include aromatic hydrocarbon solvents having 6 to 16 carbon atoms such as toluene and xylene.
- the radiation sensitive resin composition (I) may contain one or more [D] solvents.
- ⁇ Other optional components examples include surfactants, alicyclic skeleton-containing compounds, and sensitizers.
- the method for producing the radiation sensitive resin composition (I) includes a monomer (monomer (i)) represented by the following formula (i) and an acid dissociable group represented by the following formula (ii).
- a step of living polymerizing a monomer composition containing a monomer (monomer (ii)) (hereinafter also referred to as “polymerization step”), and Mw / Mn formed by the polymerization step is 1.5.
- a step of obtaining a mixture containing a smaller [A] polymer, [B] acid generator and [C] acid generator hereinafter also referred to as “mixing step”).
- Ar is a group obtained by removing (n + 1) hydrogen atoms from an arene having 6 to 20 carbon atoms.
- R 1 is a hydroxy group, a sulfanyl group or a monovalent organic group having 1 to 20 carbon atoms.
- n is an integer of 0 to 11. When n is 2 or more, the plurality of R 1 are the same or different.
- R 2 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
- R 3 is a monovalent group having 1 to 20 carbon atoms including the acid dissociable group.
- Z is a single bond, an oxygen atom or a sulfur atom.
- R 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
- the said radiation sensitive resin composition (I) which is excellent in defect suppression property, LWR performance, and a sensitivity can be manufactured simply and reliably.
- Ar, R 1 and R 2 in the above formula (i) and R 3 , Z and R 4 in the above formula (ii) are, for example, Ar, R 1 and R 2 in the above formula (1) in the [A] polymer. And the group etc. similar to the group illustrated as R ⁇ 3 >, Z, and R ⁇ 4 > of the said Formula (2) are mentioned.
- the living polymerization can be carried out, for example, by the method described as living polymerization in the above-described method for synthesizing [A] polymer.
- a mixture containing the [A] polymer, [B] acid generator and [C] acid generator formed in the polymerization step is obtained.
- the mixing method of each component in this mixing is not particularly limited, and the three components [A] to [C] may be mixed at one time, or obtained by mixing two components of [A] to [C]. The remaining mixture may be mixed with the resulting mixture.
- the solvent [D] and other optional components as required can be mixed in a predetermined ratio.
- the obtained mixed solution is preferably filtered through, for example, a filter having a pore size of about 0.2 ⁇ m.
- the lower limit of the concentration of the radiation sensitive resin composition (I) is preferably 0.1% by mass, more preferably 0.5% by mass, and even more preferably 1% by mass.
- concentration 50 mass% is preferable, 30 mass% is more preferable, and 20 mass% is further more preferable.
- the radiation sensitive resin composition (II) contains a [A ′] polymer, a [B] acid generator, and a [C] acid generator.
- the said radiation sensitive resin composition (II) may contain the [D] solvent as a suitable component, and may contain the other arbitrary components in the range which does not impair the effect of this invention.
- the radiation sensitive resin composition (II) contains a [A ′] polymer, a [B] acid generator and a [C] acid generator, and the [A ′] polymer is a living polymerization product. And excellent in defect suppression, LWR performance and sensitivity.
- the [A ′] polymer that is a living polymerization product has already been described in the description of the case where the [A] polymer is a living polymerization product.
- the radiation-sensitive resin composition (II) is the same as the radiation-sensitive resin composition (I) except that it contains an [A ′] polymer instead of the [A] polymer.
- the said radiation sensitive resin composition (II) can be prepared similarly to the said radiation sensitive resin composition (I).
- ⁇ Resist pattern formation method> a step of coating the radiation-sensitive resin composition directly or indirectly on a substrate (hereinafter, also referred to as “coating step”) and a resist film formed by the coating step are exposed. And a step of developing the exposed resist film (hereinafter also referred to as “developing step”).
- the radiation sensitive resin composition described above since the radiation sensitive resin composition described above is used, it is possible to form a resist pattern with good sensitivity, few defects, and low LWR.
- the radiation sensitive resin composition (I) or the radiation sensitive resin composition (II) is applied directly or indirectly to the substrate. That is, the radiation sensitive resin composition is applied to the substrate directly or through another layer such as an organic underlayer film. Examples of the substrate include a silicon wafer and a wafer coated with aluminum.
- a resist film is formed by applying the radiation sensitive resin composition on the substrate. Although it does not specifically limit as a coating method of the said radiation sensitive resin composition, For example, well-known methods, such as a spin coat method, etc. are mentioned.
- the amount of the radiation sensitive resin composition to be applied is adjusted so that the resist film to be formed has a desired thickness.
- PB prebaking
- 30 degreeC is preferable and 50 degreeC is more preferable.
- 200 degreeC is preferable and 150 degreeC is more preferable.
- the lower limit of the PB time is preferably 10 seconds, and more preferably 30 seconds.
- the upper limit of the PB time is preferably 600 seconds, and more preferably 300 seconds.
- the lower limit of the average thickness of the resist film is preferably 10 nm, more preferably 20 nm, and even more preferably 40 nm.
- the upper limit of the average thickness is preferably 1,000 nm, more preferably 200 nm, and even more preferably 100 nm.
- a protective film can be provided on the resist film as disclosed in, for example, JP-A-5-188598.
- the resist film formed by the coating step is exposed.
- this exposure is performed by irradiating with radiation through a mask having a predetermined pattern through an immersion exposure liquid such as water.
- the immersion exposure liquid a liquid having a refractive index larger than that of air is usually used. Specific examples include pure water, long-chain or cyclic aliphatic compounds, and the like.
- the exposure apparatus irradiates radiation, and the resist film is formed through a mask having a predetermined pattern. Exposure.
- the radiation examples include deep ultraviolet rays such as visible light, ultraviolet rays, ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), EUV (13 .5 nm), electromagnetic waves such as X-rays, charged particle beams such as electron beams and ⁇ rays, and the like, and among these, ArF excimer laser light, KrF excimer laser light, EUV, X-ray or An electron beam is preferable, and ArF excimer laser light, EUV, or an electron beam is more preferable.
- exposure conditions such as exposure amount, can be suitably selected according to the compounding composition of the said radiation sensitive resin composition, the kind of additive, etc.
- PEB post-exposure bake
- the heating condition of PEB is appropriately adjusted depending on the composition of the radiation sensitive resin composition, but the lower limit of the temperature of PEB is preferably 30 ° C, more preferably 50 ° C, further preferably 70 ° C, and more preferably 80 ° C. Particularly preferred.
- As an upper limit of the temperature of PEB 200 degreeC is preferable, 160 degreeC is more preferable, and 140 degreeC is further more preferable.
- the lower limit of the PEB time is preferably 10 seconds, more preferably 30 seconds, and even more preferably 1 minute.
- the upper limit of the PEB time is preferably 10 minutes, more preferably 5 minutes, and even more preferably 2 minutes.
- the exposed resist film is developed.
- the developer used for the development include an alkali developer and an organic solvent developer. Thereby, a predetermined resist pattern is formed.
- alkali developer examples include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, Ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3. 0] -5-nonene, and an alkaline aqueous solution in which at least one alkaline compound is dissolved.
- TMAH aqueous solution is preferable and a 2.38 mass% TMAH aqueous solution is more preferable.
- organic solvent developer examples include organic solvents such as hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, alcohol solvents, and liquids containing organic solvents.
- organic solvent examples include one or more of the solvents exemplified as the [D] solvent of the above-described radiation-sensitive resin composition.
- an ester solvent or a ketone solvent is preferable.
- the ester solvent is preferably an acetate solvent, more preferably amyl acetate or n-butyl acetate.
- the ketone solvent is preferably a chain ketone, more preferably 2-heptanone.
- the lower limit of the content of the organic solvent in the organic solvent developer is preferably 80% by mass, more preferably 90% by mass, further preferably 95% by mass, and particularly preferably 99% by mass.
- components other than the organic solvent in the organic solvent developer include water and silicone oil.
- These developers may be used alone or in combination of two or more.
- the substrate is washed with water or an alcohol solvent and dried.
- the numerical value of parts by mass is a value in which the total mass of the monomers used is 100 parts by mass.
- the polymerization reaction solution was cooled with water and cooled to 30 ° C. or lower.
- the cooled polymerization reaction liquid was put into hexane (500 parts by mass with respect to 100 parts by mass of the polymerization reaction liquid), and the precipitated white powder was separated by filtration.
- the filtered white powder was washed twice with 100 parts by mass of hexane with respect to the polymerization reaction solution, filtered, and dissolved in 300 parts by mass of 1-methoxy-2-propanol.
- the polymerization reaction solution was cooled with water and cooled to 30 ° C. or lower.
- the cooled polymerization reaction liquid was put into hexane (500 parts by mass with respect to the polymerization reaction liquid), and the precipitated white powder was filtered off.
- the filtered white powder was washed twice with 100 parts by mass of hexane with respect to the polymerization reaction solution, filtered, and dissolved in 300 parts by mass of 1-methoxy-2-propanol.
- B-1 Triphenylsulfonium 2- (adamantan-1-ylcarbonyloxy) -1,1,3,3,3-pentafluoropropane-1-sulfonate
- B-2 Triphenylsulfonium norbornane sultone-2-yloxy Carbonyl difluoromethanesulfonate
- B-3 Triphenylsulfonium 3- (piperidin-1-ylsulfonyl) -1,1,2,2,3,3-hexafluoropropane-1-sulfonate
- B-4 Triphenylsulfonium adamantane 1-yloxycarbonyldifluoromethanesulfonate
- C-1 Triphenylsulfonium salicylate
- C-2 Triphenylsulfonium 1-adamantyl oxalate
- CC-1 N- (n-undecan-1-ylcarbonyloxyethyl) morpholine
- [Example 1] [A] 100 parts by mass of the polymer (A-1), [B] 20 parts by mass of (B-1) as an acid generator, and [C] (C-1) as an acid generator (B-1) 5 mol%, and (D-1) 4,800 parts by mass and (D-2) 2,000 parts by mass as a [D] solvent were blended to give a radiation-sensitive resin composition (R-1 ) Was prepared.
- PEB was performed at 110 ° C. for 60 seconds, and then cooled at 23 ° C. for 30 seconds. Subsequently, development was performed at 23 ° C. for 30 seconds using a 2.38 mass% TMAH aqueous solution to form a positive 32 nm line and space pattern.
- defect suppression The formed line and space pattern was subjected to defect inspection using a defect inspection apparatus (“KLA2925” manufactured by KLA), and the defect density (pieces / cm 2 ) was measured. It shows that defect suppression property is so favorable that this defect density is small. Defect suppression property, if the defect density is 60 / cm 2 or less as "good”, if more than 60 / cm 2 can be evaluated as “poor”. “> 500” in Comparative Examples 16 and 17 indicates that the measurable range of the defect inspection apparatus was exceeded.
- sensitivity In the formation of the line and space pattern (LS), when a 32 nm LS formation mask was used, the exposure amount at which 32 nm LS was formed was defined as the optimum exposure amount, and this optimum exposure amount was defined as sensitivity (mJ / cm 2 ).
- LWR performance The formed line and space pattern was observed from above the pattern using the scanning electron microscope. A total of 50 line widths were measured at arbitrary points, and a 3-sigma value was obtained from the distribution of the measured values, and this was defined as LWR performance (nm). The LWR performance indicates that the smaller the value, the smaller the line width variation. When the LWR performance is 3.2 nm or less, it can be judged as “good”, and when it exceeds 3.2 nm, it can be judged as “bad”.
- the radiation-sensitive resin composition and the resist pattern forming method of the present invention a resist pattern with improved sensitivity, fewer defects, and smaller LWR can be formed.
- the manufacturing method of the radiation sensitive resin composition of this invention the said radiation sensitive resin composition can be manufactured simply and reliably. Accordingly, these can be suitably used for semiconductor device processing processes and the like that are expected to be further miniaturized in the future.
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Abstract
Description
式(2)中、R3は、上記酸解離性基(a)を含む炭素数1~20の1価の基である。Zは、単結合、酸素原子又は硫黄原子である。R4は、水素原子、フッ素原子、メチル基又はトリフルオロメチル基である。)
式(2)中、R3は、上記酸解離性基を含む炭素数1~20の1価の基である。Zは、単結合、酸素原子又は硫黄原子である。R4は、水素原子、フッ素原子、メチル基又はトリフルオロメチル基である。)
式(ii)中、R3は、上記酸解離性基(a)を含む炭素数1~20の1価の基である。Zは、単結合、酸素原子又は硫黄原子である。R4は、水素原子、フッ素原子、メチル基又はトリフルオロメチル基である。)
当該感放射線性樹脂組成物(I)は、[A]重合体と、[B]酸発生剤と、[C]酸発生剤とを含有する。当該感放射線性樹脂組成物(I)は、好適成分として、[D]溶媒を含有していてもよく、本発明の効果を損なわない範囲において、その他の任意成分を含有していてもよい。
以下、各成分について説明する。
[A]重合体は、構造単位(I)及び構造単位(II)を有し、ゲルパーミエーションクロマトグラフィー(GPC)により測定されるポリスチレン換算の重量平均分子量(Mw)の数平均分子量(Mn)に対する比(Mw/Mn)が1.5より小さい重合体である。当該感放射線性樹脂組成物(I)は、[A]重合体を1種又は2種以上含有していてもよい。
GPCカラム:東ソー(株)の「G2000HXL」2本、「G3000HXL」1本及び「G4000HXL」1本
カラム温度:40℃
溶出溶媒:テトラヒドロフラン(和光純薬工業(株))
流速:1.0mL/分
試料濃度:1.0質量%
試料注入量:100μL
検出器:示差屈折計
標準物質:単分散ポリスチレン
構造単位(I)は、下記式(1)で表される構造単位である。
メチル基、エチル基、n-プロピル基、i-プロピル基、t-ブチル基等のアルキル基;
エテニル基、プロペニル基、ブテニル基等のアルケニル基;
エチニル基、プロピニル基、ブチニル基等のアルキニル基などが挙げられる。
シクロペンチル基、シクロヘキシル基等の単環の脂環式飽和炭化水素基;
シクロペンテニル基、シクロヘキセニル基等の単環の脂環式不飽和炭化水素基;
ノルボルニル基、アダマンチル基、トリシクロデシル基等の多環の脂環式飽和炭化水素基;
ノルボルネニル基、トリシクロデセニル基等の多環の脂環式不飽和炭化水素基などが挙げられる。
フェニル基、トリル基、キシリル基、ナフチル基、アントリル基等のアリール基;
ベンジル基、フェネチル基、ナフチルメチル基、アントリルメチル基等のアラルキル基などが挙げられる。
構造単位(II)は、下記式(2)で表され、酸解離性基(a)を含む構造単位である。「酸解離性基」とは、カルボキシ基、フェノール性水酸基、スルホ基等の酸性基の水素原子を置換する基であって、酸の作用により解離する基をいう。[A]重合体が構造単位(II)を有することで、露光部における酸解離性基(a)が[B]酸発生剤から発生した第1酸等の作用により解離して極性が増大し、現像液に対して易溶又は難溶となることによりレジストパターンを形成することができる。
構造単位(III)は、ラクトン構造、環状カーボネート構造、スルトン構造又はこれらの組み合わせを含む構造単位である。[A]重合体は、構造単位(III)を有することで現像液への溶解性を適度に調整することができ、その結果、欠陥抑制性、LWR性能及び感度をより向上させることができる。また、レジストパターンと基板との密着性をより向上させることができる。
構造単位(IV)は、アルコール性水酸基を含む構造単位である。[A]重合体は、構造単位(IV)を有することで現像液への溶解性を適度に調整することができ、その結果、欠陥抑制性、LWR性能及び感度をより向上させることができる。
その他の構造単位としては、例えば極性基を含む構造単位、非酸解離性の炭化水素基を含む構造単位等が挙げられる(但し、構造単位(I)~(IV)に該当するものを除く)。極性基としては、例えばヒドロキシ基、カルボキシ基、ニトロ基、シアノ基、スルホンアミド基等が挙げられる。非酸解離性の炭化水素基としては、例えば-COO-のオキシ酸素原子に結合する結合手となる炭素原子が1級又は2級の鎖状炭化水素基、結合手となる炭素原子が1級又は2級の脂環式炭化水素基、メチル基、1-アダマンチル基等が挙げられる。非酸解離性の炭化水素基としては、これらの中で、結合手となる炭素原子が2級の脂環式炭化水素基又は1-アダマンチル基が好ましい。[A]重合体がその他の構造単位を有する場合、その他の構造単位の含有割合の上限としては、30モル%が好ましく、10モル%がより好ましい。上記含有割合の下限としては、例えば1モル%である。
[A]重合体は、例えば構造単位(I)を与える単量体(i)、構造単位(II)を与える単量体(ii)及び必要に応じてこれらの単量体以外の単量体を含む単量体組成物を重合開始剤等を用い、適当な溶媒中で重合することにより合成することができる。
アゾビスイソブチロニトリル(AIBN)、2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、2,2’-アゾビス(2-シクロプロピルプロピオニトリル)、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、ジメチル2,2’-アゾビスイソブチレート等のアゾ系ラジカル開始剤、
ベンゾイルパーオキサイド、t-ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド等の過酸化物系ラジカル開始剤などが挙げられる。これらのラジカル重合開始剤は1種単独又は2種以上を混合して用いることができる。
メルカプトプロピオン酸等のメルカプトカルボン酸;
3-メルカプトプロピオン酸2-エチルヘキシル等のメルカプトカルボン酸エステル;
4-メルカプト-1-ブタノール等のチオール;
2-ヒドロキシエチルジスルフィド等のジスルフィド;
ジチオ安息香酸クミル等のジチオエステル;
エチルキサントゲン酸エチル等のキサンタート;
ベンジルジエチルジチオカルバメート等のジチオカルバメート;
2-シアノ-2-プロピルドデシルトリチオカルボナート、4-シアノ-4-[(ドデジルスルファニルチオカルボニル)スルファニル]ペンタン酸、シアノメチルドデシルトリチオカルボナート等のトリチオカルボナートなどが挙げられる。
n-ペンタン、n-ヘキサン、n-ヘプタン、n-オクタン、n-ノナン、n-デカン等のアルカン、
シクロヘキサン、シクロヘプタン、シクロオクタン、デカリン、ノルボルナン等のシクロアルカン、
ベンゼン、トルエン、キシレン、エチルベンゼン、クメン等の芳香族炭化水素;
クロロブタン、ブロモヘキサン、ジクロロエタン、ヘキサメチレンジブロミド、クロロベンゼン等のハロゲン化炭化水素、
酢酸エチル、酢酸n-ブチル、酢酸i-ブチル、プロピオン酸メチル、等の飽和カルボン酸エステル、
アセトン、メチルエチルケトン、4-メチル-2-ペンタノン、2-ヘプタノン等のケトン、
テトラヒドロフラン、ジメトキシエタン類、ジエトキシエタン類等のエーテル、
メタノール、エタノール、1-プロパノール、2-プロパノール、4-メチル-2-ペンタノール等のアルコールなどが挙げられる。これらの重合に使用される溶媒は、1種単独で又は2種以上を併用してもよい。
[B]酸発生剤は、80℃以上140℃以下の温度条件で1分間加熱した際に上記酸解離性基(a)を解離させる第1酸(以下、「酸(b)ともいう」)を放射線の照射により発生する。放射線の照射により露光部において[B]酸発生剤から発生する酸(b)の作用によって、80℃~140℃の範囲の温度で1分の時間、例えばポストエクスポージャーベーク(PEB)等において加熱を行うことにより、[A]重合体の酸解離性基(a)が解離する。これにより、露光部における[A]重合体の現像液への溶解性が変化して、レジストパターンを形成することができる。
シクロペンタン構造、シクロヘキサン構造、シクロヘプタン構造、シクロオクタン構造、シクロノナン構造、シクロデカン構造、シクロドデカン構造等の単環のシクロアルカン構造、
シクロペンテン構造、シクロヘキセン構造、シクロヘプテン構造、シクロオクテン構造、シクロデセン構造等の単環のシクロアルケン構造、
ノルボルナン構造、アダマンタン構造、トリシクロデカン構造、テトラシクロドデカン構造等の多環のシクロアルカン構造、
ノルボルネン構造、トリシクロデセン構造等の多環のシクロアルケン構造などが挙げられる。
ヘキサノラクトン構造、ノルボルナンラクトン構造等のラクトン構造、
ヘキサノスルトン構造、ノルボルナンスルトン構造等のスルトン構造、
オキサシクロヘプタン構造、オキサノルボルナン構造等の酸素原子含有複素環構造、
アザシクロヘキサン構造、ジアザビシクロオクタン構造等の窒素原子含有複素環構造、
チアシクロヘキサン構造、チアノルボルナン構造の硫黄原子含有複素環構造などが挙げられる。
ベンゼン構造、ナフタレン構造、フェナントレン構造、アントラセン構造等が挙げられる。
フラン構造、ピラン構造、ベンゾピラン構造等の酸素原子含有複素環構造、
ピリジン構造、ピリミジン構造、インドール構造等の窒素原子含有複素環構造などが挙げられる。
[C]酸発生剤は、80℃以上140℃以下の温度条件で1分間加熱した際に上記酸解離性基(a)を実質的に解離させない第2酸(以下、「酸(c)ともいう」)を放射線の照射により発生する。放射線の照射により露光部において[C]酸発生剤から発生する酸(c)の作用によっては、80℃~140℃の範囲の温度で1分の時間、例えばポストエクスポージャーベーク(PEB)等において加熱を行っても、[A]重合体の酸解離性基(a)は実質的に解離しない。すなわち、[C]酸発生剤は、未露光部においては酸を捕捉し、露光部においては酸を捕捉しない高機能の酸拡散制御剤として機能する。
当該感放射線性樹脂組成物(I)は、通常[D]溶媒を含有する。[D]溶媒は、少なくとも[A]重合体、[B]酸発生剤、[C]酸発生剤及びその他の任意成分を溶解又は分散可能な溶媒であれば特に限定されない。
4-メチル-2-ペンタノール、n-ヘキサノール等の炭素数1~18の脂肪族モノアルコール系溶媒;
シクロヘキサノール等の炭素数3~18の脂環式モノアルコール系溶媒;
プロピレングリコール等の炭素数2~18の多価アルコール系溶媒;
プロピレングリコールモノメチルエーテル等の炭素数3~19の多価アルコール部分エーテル系溶媒などが挙げられる。
ジエチルエーテル等の炭素数4~14のジアルキルエーテル系溶媒;
テトラヒドロフラン、テトラヒドロピラン等の環状エーテル系溶媒;
ジフェニルエーテル、アニソール等の芳香環含有エーテル系溶媒などが挙げられる。
アセトン、メチルエチルケトン、メチル-iso-ブチルケトン、2-ヘプタノン等の炭素数3~12の鎖状ケトン系溶媒;
シクロペンタノン、シクロヘキサノン、シクロヘプタノン、シクロオクタノン、メチルシクロヘキサノン等の環状ケトン系溶媒;
2,4-ペンタンジオン、アセトニルアセトン、アセトフェノン等が挙げられる。
N,N’-ジメチルイミダゾリジノン、N-メチルピロリドン等の環状アミド系溶媒;
N-メチルホルムアミド、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、アセトアミド、N-メチルアセトアミド、N,N-ジメチルアセトアミド、N-メチルプロピオンアミド等の鎖状アミド系溶媒などが挙げられる。
酢酸n-ブチル、酢酸アミル等の酢酸エステル系溶媒、プロピオン酸エチル等のプロピオン酸エステル系溶媒などのモノカルボン酸エステル系溶媒;
エチルラクテート、グリコール酸n-ブチル等のヒドロキシカルボン酸エステル系溶媒;
プロピレングリコールアセテート等の多価アルコールカルボキシレート系溶媒;
酢酸プロピレングリコールモノメチルエーテル等の多価アルコール部分エーテルカルボキシレート系溶媒;
シュウ酸ジエチル等の多価カルボン酸ジエステル系溶媒;
γ-ブチロラクトン、δ-バレロラクトン等のラクトン系溶媒;
ジメチルカーボネート、ジエチルカーボネート、エチレンカーボネート、プロピレンカーボネート等のカーボネート系溶媒などが挙げられる。
n-ペンタン、n-ヘキサン等の炭素数5~12の脂肪族炭化水素系溶媒;
トルエン、キシレン等の炭素数6~16の芳香族炭化水素系溶媒等が挙げられる。
その他の任意成分としては、例えば界面活性剤、脂環式骨格含有化合物、増感剤等が挙げられる。
当該感放射線性樹脂組成物(I)の製造方法は、下記式(i)で表される単量体(単量体(i))と下記式(ii)で表され酸解離性基を含む単量体(単量体(ii))とを含む単量体組成物をリビング重合する工程(以下、「重合工程」ともいう)と、上記重合工程により形成されたMw/Mnが1.5より小さい[A]重合体、[B]酸発生剤及び[C]酸発生剤を含む混合物を得る工程(以下、「混合工程」ともいう)とを備える。
上記式(ii)中、R3は、上記酸解離性基を含む炭素数1~20の1価の基である。Zは、単結合、酸素原子又は硫黄原子である。R4は、水素原子、フッ素原子、メチル基又はトリフルオロメチル基である。
本工程では、単量体(i)と単量体(ii)とを含む単量体組成物をリビング重合する。
本工程では、上記重合工程で形成された[A]重合体、[B]酸発生剤及び[C]酸発生剤を含む混合物を得る。この混合における各成分の混合方法は特に限定されず、[A]~[C]の3成分を一度に混合してもよく、[A]~[C]のうちの2成分を混合して得られた混合物に、残りの1成分を混合してもよい。この混合では[A]~[C]成分に加え、[D]溶媒、必要に応じてその他の任意成分を所定の割合で混合することができる。得られた混合液は、例えば孔径0.2μm程度のフィルター等でろ過することが好ましい。当該感放射線性樹脂組成物(I)の濃度の下限としては、0.1質量%が好ましく、0.5質量%がより好ましく、1質量%がさらに好ましい。上記濃度の上限としては、50質量%が好ましく、30質量%がより好ましく、20質量%がさらに好ましい。
当該感放射線性樹脂組成物(II)は、[A’]重合体と、[B]酸発生剤と、[C]酸発生剤とを含有する。当該感放射線性樹脂組成物(II)は、好適成分として、[D]溶媒を含有していてもよく、本発明の効果を損なわない範囲において、その他の任意成分を含有していてもよい。
当該レジストパターン形成方法は、基板に直接又は間接に当該感放射線性樹脂組成物を塗工する工程(以下、「塗工工程」ともいう)と、上記塗工工程により形成されたレジスト膜を露光する工程(以下、「露光工程」ともいう)と、上記露光されたレジスト膜を現像する工程(以下、「現像工程」ともいう)とを備える。
本工程では、基板に直接又は間接に当該感放射線性樹脂組成物(I)又は感放射線性樹脂組成物(II)を塗工する。つまり、基板に直接又は有機下層膜等の他の層を介して当該感放射線性樹脂組成物を塗工する。基板としては、例えばシリコンウェハ、アルミニウムで被覆したウェハ等が挙げられる。この基板上に当該感放射線性樹脂組成物を塗工することによりレジスト膜が形成される。当該感放射線性樹脂組成物の塗工方法としては、特に限定されないが、例えばスピンコート法等の公知の方法等が挙げられる。当該感放射線性樹脂組成物を塗工する際には、形成されるレジスト膜が所望の厚みとなるように、塗工する当該感放射線性樹脂組成物の量を調整する。なお当該感放射線性樹脂組成物を基板上に塗工した後、溶媒を揮発させるためにプレベーク(以下、「PB」ともいう)を行ってもよい。PBの温度の下限としては、30℃が好ましく、50℃がより好ましい。PBの温度の上限としては、200℃が好ましく、150℃がより好ましい。PBの時間の下限としては、10秒が好ましく、30秒がより好ましい。PBの時間の上限としては、600秒が好ましく、300秒がより好ましい。レジスト膜の平均厚さの下限としては、10nmが好ましく、20nmがより好ましく、40nmがさらに好ましい。上記平均厚さの上限としては、1,000nmが好ましく、200nmがより好ましく、100nmがさらに好ましい。
本工程では上記塗工工程により形成されたレジスト膜を露光する。この露光は、場合によっては、水等の液浸露光液を介し、所定のパターンを有するマスクを介して放射線を照射することにより行う。
本工程では、上記露光されたレジスト膜を現像する。この現像に用いる現像液としては、例えばアルカリ現像液、有機溶媒現像液等が挙げられる。これにより、所定のレジストパターンが形成される。
東ソー(株)製GPCカラム(G2000HXL:2本、G3000HXL:1本、G4000HXL:1本)を用い、流量:1.0mL/分、溶出溶媒:テトラヒドロフラン、試料濃度:1.0質量%、試料注入量:100μL、カラム温度:40℃、検出器:示差屈折計の分析条件で、単分散ポリスチレンを標準とするゲルパーミエーションクロマトグラフィ(GPC)により測定した。また、分散度(Mw/Mn)は、Mw及びMnの測定結果より算出した。
[A]重合体の合成に用いた単量体を以下に示す。
化合物(M-5)、化合物(M-6)及び化合物(M-7)をモル比率が35/45/20となるよう1-メトキシ-2-プロパノール60質量部に溶解した。次に、連鎖移動剤としての2-シアノ-2-プロピルドデシルトリチオカルボナートを全単量体に対して3.5モル%、開始剤としてのAIBNを全単量体に対して0.7モル%添加し、単量体溶液を調製した。反応容器を30分窒素パージした後、上記単量体溶液を加えた。その後、攪拌しながら80℃に加熱し、重合液の温度が80℃となった時間を重合反応の開始時間とし、重合反応を6時間実施した。重合反応終了後、重合反応液を水冷して30℃以下に冷却した。ヘキサン(重合反応液100質量部に対して500質量部)中に冷却した重合反応液を投入し、析出した白色粉末をろ別した。ろ別した白色粉末を重合反応液に対して100質量部のヘキサンで2回洗浄した後、ろ別し、1-メトキシ-2-プロパノール300質量部に溶解した。次に、メタノール500質量部、トリエチルアミン50質量部及び超純水10質量部を加え、撹拌しながら70℃で6時間加水分解反応を実施した。反応終了後、残溶媒を留去し、得られた固体をアセトン100質量部に溶解させた。500質量部の水中に滴下して重合体を凝固させ、得られた固体をろ別し、50℃、12時間乾燥させて白色粉末状の重合体(A-1)を合成した。
下記表1に示す種類及び使用量の単量体を用いた以外は、合成例1と同様にして、重合体(A-2)~(A-9)を合成した。
用いる連鎖移動剤を2-(ドデシルチオカルボノチオイルチオ)-2-メチルプロピオン酸メチルに、開始剤を2,2’-アゾビス(イソ酪酸メチル)に変更した以外は、合成例2と同様にして、重合体(A-10)を合成した。
化合物(M-5)、化合物(M-6)及び化合物(M-7)をモル比率が35/45/20となるよう1-メトキシ-2-プロパノール(全単量体に対して200質量部)に溶解した。次に、開始剤としてのAIBNを全単量体に対して5モル%を添加し、単量体溶液を調製した。反応容器を30分窒素パージした後、1-メトキシ-2-プロパノール(全単量体に対して100質量部)を加え、攪拌しながら80℃に加熱した。次に、上記調製した単量体溶液を3時間かけて滴下し、その後、80℃でさらに3時間加熱し、重合反応を合計6時間実施した。重合反応終了後、重合反応液を水冷して30℃以下に冷却した。ヘキサン(重合反応液に対して500質量部)中に冷却した重合反応液を投入し、析出した白色粉末をろ別した。ろ別した白色粉末を重合反応液に対して100質量部のヘキサンで2回洗浄した後、ろ別し、1-メトキシ-2-プロパノール300質量部に溶解した。次に、メタノール500質量部、トリエチルアミン50質量部及び超純水10質量部を加え、撹拌しながら70℃で6時間加水分解反応を実施した。反応終了後、残溶媒を留去し、得られた固体をアセトン100質量部に溶解させた。500質量部の水中に滴下して重合体を凝固させ、得られた固体をろ別し、50℃、12時間乾燥させて白色粉末状の重合体(a-1)を合成した。
下記表2に示す種類及び使用量の単量体を用いた以外は、合成例11と同様にして、重合体(a-2)~(a-9)を合成した。
下記表2に示す種類及び使用量の単量体を用い、開始剤を2,2’-アゾビス(イソ酪酸メチル)に変更した以外は、合成例11と同様にして、重合体(a-10)を合成した。
感放射線性樹脂組成物の調製に用いた[B]酸発生剤、[C]酸発生剤及び[D]溶媒について以下に示す。
各構造式を以下に示す。
B-1:トリフェニルスルホニウム2-(アダマンタン-1-イルカルボニルオキシ)-1,1,3,3,3-ペンタフルオロプロパン-1-スルホネート
B-2:トリフェニルスルホニウムノルボルナンスルトン-2-イルオキシカルボニルジフルオロメタンスルホネート
B-3:トリフェニルスルホニウム3-(ピペリジン-1-イルスルホニル)-1,1,2,2,3,3-ヘキサフルオロプロパン-1-スルホネート
B-4:トリフェニルスルホニウムアダマンタン-1-イルオキシカルボニルジフルオロメタンスルホネート
各構造式を以下に示す。
C-1:トリフェニルスルホニウムサリチレート
C-2:トリフェニルスルホニウム1-アダマンチルオキサレート
CC-1:N-(n-ウンデカン-1-イルカルボニルオキシエチル)モルホリン
D-1:酢酸プロピレングリコールモノメチルエーテル
D-2:シクロヘキサノン
[A]重合体(A-1)100質量部、[B]酸発生剤としての(B-1)20質量部、[C]酸発生剤としての(C-1)を(B-1)に対して5モル%、並びに[D]溶媒としての(D-1)4,800質量部及び(D-2)2,000質量部を配合して、感放射線性樹脂組成物(R-1)を調製した。
下記表2に示す種類及び含有量の各成分を用いた以外は、実施例1と同様にして、感放射線性樹脂組成物(R-2)~(R-14)及び(CR-1)~(CR-16)を調製した。
20nmのAL412(ブルーワーサイエンス社)を塗工した12インチのシリコンウェハ表面にスピンコーター(東京エレクトロン(株)の「CLEAN TRACK ACT8」)を使用して、上記調製した感放射線性樹脂組成物を塗工し、130℃で60秒間PBを行った後、23℃で30秒間冷却し、平均厚み55nmのレジスト膜を形成した。次に、このレジスト膜に、EUV露光機(ASML社の型式「NXE3300」、NA=0.33、照明条件:Conventional s=0.89、マスクimecDEFECT32FFR02)を用いてEUV光を照射した。その後、110℃で60秒間PEBを行った後、23℃で30秒間冷却した。次いで、2.38質量%のTMAH水溶液を用い、23℃で30秒間現像し、ポジ型の32nmラインアンドスペースパターンを形成した。
上記調製した感放射線性樹脂組成物の欠陥抑制性、感度及びLWR性能を、下記方法に従い評価した。感度及びLWR性能の評価におけるラインアンドスペースパターンの測長には、走査型電子顕微鏡((株)日立ハイテクノロジーズの「CG5000」)を用いた。評価結果を下記表3に示す。
上記形成したラインアンドスペースパターンについて、欠陥検査装置(KLA社の「KLA2925」)を用いて欠陥検査を行い、欠陥密度(個/cm2)を測定した。この欠陥密度が小さいほど、欠陥抑制性が良好であることを示す。欠陥抑制性は、欠陥密度が60個/cm2以下の場合は「良好」と、60個/cm2を超える場合は「不良」と評価できる。比較例16及び17における「>500」は、欠陥検査装置の測定可能範囲を超えたことを示す。
上記ラインアンドスペースパターン(LS)の形成において、32nmLS形成用マスクを用いた場合に、32nmLSが形成される露光量を最適露光量とし、この最適露光量を感度(mJ/cm2)とした。
上記形成したラインアンドスペースパターンを、上記走査型電子顕微鏡を用い、パターン上部から観察した。線幅を任意のポイントで計50点測定し、その測定値の分布から3シグマ値を求め、これをLWR性能(nm)とした。LWR性能は、その値が小さいほど、線幅のばらつが小さく良いことを示す。LWR性能は、3.2nm以下の場合は「良好」と、3.2nmを超える場合は「不良」と判断できる。
Claims (10)
- 下記式(1)で表される第1構造単位及び下記式(2)で表され酸解離性基を含む第2構造単位を有する重合体と、
放射線の照射により第1酸を発生する第1酸発生剤と、
放射線の照射により第2酸を発生する第2酸発生剤と
を含有し、
上記第1酸発生剤から発生する第1酸が、80℃以上140℃以下の温度条件で1分間加熱した際に上記重合体中の上記酸解離性基を解離させる酸であり、
上記第2酸発生剤から発生する第2酸が、上記条件下で実質的に上記酸解離性基を解離させない酸であり、
上記重合体のゲルパーミエーションクロマトグラフィーにより測定されるポリスチレン換算の重量平均分子量の数平均分子量に対する比(Mw/Mn)が、1.5より小さい感放射線性樹脂組成物。
式(2)中、R3は、上記酸解離性基を含む炭素数1~20の1価の基である。Zは、単結合、酸素原子又は硫黄原子である。R4は、水素原子、フッ素原子、メチル基又はトリフルオロメチル基である。) - 上記重合体がリビング重合生成物である請求項1に記載の感放射線性樹脂組成物。
- 上記重合体のMw/Mnが1.35より小さい請求項1又は請求項2に記載の感放射線性樹脂組成物。
- 上記式(1)におけるR1の少なくとも1つがヒドロキシ基である請求項1、請求項2又は請求項3に記載の感放射線性樹脂組成物。
- 下記式(1)で表される第1構造単位及び下記式(2)で表され酸解離性基を含む第2構造単位を有する重合体と、
放射線の照射により第1酸を発生する第1酸発生剤と、
放射線の照射により第2酸を発生する第2酸発生剤と
を含有し、
上記第1酸発生剤から発生する第1酸が、80℃以上140℃以下の温度条件で1分間加熱した際に上記重合体中の上記酸解離性基を解離させる酸であり、
上記第2酸発生剤から発生する第2酸が、上記条件下で実質的に上記酸解離性基を解離させない酸であり、
上記重合体がリビング重合生成物である感放射線性樹脂組成物。
式(2)中、R3は、上記酸解離性基を含む炭素数1~20の1価の基である。Zは、単結合、酸素原子又は硫黄原子である。R4は、水素原子、フッ素原子、メチル基又はトリフルオロメチル基である。) - 上記重合体のゲルパーミエーションクロマトグラフィーにより測定されるポリスチレン換算の重量平均分子量の数平均分子量に対する比(Mw/Mn)が、1.5より小さい請求項5に記載の感放射線性樹脂組成物。
- 上記重合体のMw/Mnが1.35より小さい請求項6に記載の感放射線性樹脂組成物。
- 上記式(1)におけるR1の少なくとも1つがヒドロキシ基である請求項5、請求項6又は請求項7に記載の感放射線性樹脂組成物。
- 基板に直接又は間接に請求項1から請求項8のいずれか1項に記載の感放射線性樹脂組成物を塗工する工程と、
上記塗工工程により形成されたレジスト膜を露光する工程と、
上記露光されたレジスト膜を現像する工程と
を備えるレジストパターン形成方法。 - 下記式(i)で表される単量体及び下記式(ii)で表され酸解離性基を有する単量体を含む単量体組成物をリビング重合する工程と、
上記リビング重合工程により形成されたゲルパーミエーションクロマトグラフィーにより測定されるポリスチレン換算の重量平均分子量の数平均分子量に対する比(Mw/Mn)が1.5より小さい重合体、放射線の照射により第1酸を発生する第1酸発生剤及び放射線の照射により第2酸を発生する第2酸発生剤を含む混合物を得る工程と
を備え、
上記第1酸発生剤から発生する第1酸が、80℃以上140℃以下の温度条件で1分間加熱した際に上記重合体中の上記酸解離性基を解離させる酸であり、上記第2酸発生剤から発生する第2酸が、上記条件下で実質的に上記酸解離性基を解離させない酸である感放射線性樹脂組成物の製造方法。
式(ii)中、R3は、上記酸解離性基を含む炭素数1~20の1価の基である。Zは、単結合、酸素原子又は硫黄原子である。R4は、水素原子、フッ素原子、メチル基又はトリフルオロメチル基である。)
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US20130000171A1 (en) * | 2010-01-15 | 2013-01-03 | Forjas Taurus S/A | Pistol with firing mechanism that can easily be adapted to various modes of operation |
JP2015034963A (ja) * | 2013-07-10 | 2015-02-19 | 富士フイルム株式会社 | 化合物、感活性光線性又は感放射線性樹脂組成物、それを用いたレジスト膜、レジスト塗布マスクブランクス、フォトマスク及びパターン形成方法、並びに、電子デバイスの製造方法及び電子デバイス |
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