WO2015029690A1 - Procédé de formation de motif, composition de résine sensible à la lumière active ou sensible aux rayonnements, film de réserve l'utilisant, procédé de fabrication de dispositif électronique et dispositif et dispositif électronique - Google Patents

Procédé de formation de motif, composition de résine sensible à la lumière active ou sensible aux rayonnements, film de réserve l'utilisant, procédé de fabrication de dispositif électronique et dispositif et dispositif électronique Download PDF

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Publication number
WO2015029690A1
WO2015029690A1 PCT/JP2014/070191 JP2014070191W WO2015029690A1 WO 2015029690 A1 WO2015029690 A1 WO 2015029690A1 JP 2014070191 W JP2014070191 W JP 2014070191W WO 2015029690 A1 WO2015029690 A1 WO 2015029690A1
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Prior art keywords
group
acid
pattern forming
forming method
sensitive
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PCT/JP2014/070191
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English (en)
Japanese (ja)
Inventor
康介 越島
岩戸　薫
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富士フイルム株式会社
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Publication of WO2015029690A1 publication Critical patent/WO2015029690A1/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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/325—Non-aqueous compositions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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 an actinic ray-sensitive or radiation-sensitive resin composition, a resist film and a pattern forming method using the same, an electronic device manufacturing method, and an electronic device. More specifically, the present invention relates to a pattern forming method, actinic ray sensitive or radiation sensitive suitable for semiconductor manufacturing processes such as IC, circuit boards such as liquid crystal and thermal head, and other photofabrication lithography processes. The present invention relates to a conductive resin composition, a resist film using the same, an electronic device manufacturing method, and an electronic device.
  • the present invention relates to a pattern forming method, actinic ray sensitivity or sensitivity suitable for exposure in an ArF exposure apparatus, an ArF immersion projection exposure apparatus and an EUV exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source.
  • the present invention relates to a radiation resin composition, a resist film using the same, an electronic device manufacturing method, and an electronic device.
  • a pattern formation method using chemical amplification has been used to compensate for sensitivity reduction due to light absorption.
  • a photoacid generator contained in an exposed portion is decomposed by light irradiation to generate an acid.
  • the post-exposure baking (PEB: Post Exposure Bake) process or the like the alkali-insoluble group contained in the photosensitive composition is changed to an alkali-soluble group by the catalytic action of the generated acid.
  • development is performed using, for example, an alkaline solution. Thereby, an exposed part is removed and a desired pattern is obtained.
  • TMAH tetramethylammonium hydroxide aqueous solution
  • the exposure light source has become shorter and the projection lens has a higher numerical aperture (high NA).
  • high NA numerical aperture
  • an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed.
  • immersion liquid a liquid having a high refractive index
  • EUV lithography in which exposure is performed with ultraviolet light having a shorter wavelength (13.5 nm) has also been proposed.
  • a pattern forming method using a negative developer that is, a developer containing an organic solvent
  • a positive resist composition is applied on a substrate, which increases the solubility in a positive developer and decreases the solubility in a negative developer by irradiation with actinic rays or radiation.
  • a pattern forming method including a step, an exposure step, and a step of developing using a negative developer. According to this method, a highly accurate fine pattern can be stably formed.
  • An object of the present invention is to provide a pattern forming method, an actinic ray-sensitive or radiation-sensitive resin composition, a resist film using the same, and a method for producing an electronic device, with less pattern collapse and excellent residual film ratio and pattern shape And providing an electronic device.
  • the present invention is as follows. [1] (I) (A) a resin having a repeating unit having a group capable of decomposing by the action of an acid to generate an alcoholic hydroxyl group and having a weight average molecular weight of more than 11,000, and a compound represented by the following general formula (1) Forming a film using an actinic ray-sensitive or radiation-sensitive resin composition containing (II) exposing the film; and (III) developing the exposed film using a developer containing an organic solvent; A pattern forming method including: R represents an alkyl group, a cycloalkyl group optionally having a carbonyl carbon as a ring member, a lactone structure, a sultone structure, an aryl group, or a group formed by combining two or more thereof.
  • M + represents a monovalent cation.
  • R is a cycloalkyl group optionally having a carbonyl carbon as a ring member, a sultone structure, an aryl group, or a group formed by combining two or more thereof [1].
  • Pattern forming method [3] In the general formula (1), the pattern forming method according to [1] or [2], wherein R is a polycyclic cycloalkyl group having 10 or more carbon atoms, which may have a carbonyl carbon as a ring member. [4] The pattern forming method according to any one of [1] to [3], wherein the resin (A) has a weight average molecular weight of 12,000 or more.
  • the groups and atomic groups that do not explicitly indicate substitution or non-substitution include both those that do not have a substituent and those that have a substituent.
  • an “alkyl group” that does not clearly indicate substitution or unsubstituted is not only an alkyl group that does not have a substituent (unsubstituted alkyl group) but also an alkyl group that has a substituent (substituted alkyl group) Is also included.
  • active light or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV) rays, X rays or electron rays (EB). Yes.
  • light means actinic rays or radiation.
  • exposure means not only light irradiation with a mercury lamp, far ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams, unless otherwise specified. .
  • the pattern forming method includes: (I) a resin having a repeating unit having a group capable of decomposing by the action of an acid to generate an alcoholic hydroxyl group and having a weight average molecular weight of 11,000 or more and a compound represented by the general formula (1) Forming a film using an actinic ray-sensitive or radiation-sensitive resin composition; (II) exposing the film; and (III) developing the exposed film using a developer containing an organic solvent; including.
  • R represents an alkyl group, a cycloalkyl group optionally having a carbonyl carbon as a ring member, a lactone structure, a sultone structure, an aryl group, or a group formed by combining two or more thereof.
  • M + represents a monovalent cation.
  • the actinic ray-sensitive or radiation-sensitive resin composition having less pattern collapse and excellent residual film ratio and pattern shape, resist film and pattern forming method using the same, and electronic device manufacturing method and electronic device It becomes possible to provide.
  • the reason is not clear, but is estimated as follows, for example.
  • the actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of the present invention contains a compound represented by the general formula (1), and is a compound represented by the above general formula (1).
  • the acid strength of (A) has an optimum strength for the decomposition reaction of a resin having a repeating unit having a group that decomposes by the action of an acid to generate an alcoholic hydroxyl group and a weight average molecular weight of 11,000 or more. .
  • the decomposition reaction of the exposed portion occurs efficiently in pattern formation, so that the resin dissolution contrast is improved.
  • the pattern shape becomes rectangular, and pattern collapse is considered to be reduced.
  • the resin has a weight average molecular weight of 11,000 or more, the diffusion of low molecular components represented by the compound represented by the general formula (1) is suppressed, and the low molecular components are added to the developer. Since elution is suppressed, it is considered that film slippage is reduced as a result. Furthermore, since the interaction between the resin and the compound represented by the general formula (1) is strong, it is considered that the above-mentioned reduction in film slip is realized at a higher level.
  • the pattern formation method includes (A) a resin having a repeating unit having a group that decomposes by the action of an acid to generate an alcoholic hydroxyl group, a weight average molecular weight of 11,000 or more, and a general formula (1) And a step of forming a film using an actinic ray-sensitive or radiation-sensitive resin composition containing the compound represented by (hereinafter, also referred to as “step (I)” or “film-forming step”). Further, the pattern forming method according to the present invention includes (II) a step of exposing the film (hereinafter, also referred to as “step (II)” or “exposure step”).
  • PB preheating
  • PEB post-exposure heating
  • the heating temperature is preferably 40 to 130 ° C., more preferably 50 to 120 ° C., and still more preferably 60 to 110 ° C. for both the PB process and the PEB process.
  • the exposure latitude (EL) and the resolving power can be remarkably improved.
  • the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and further preferably 30 to 90 seconds.
  • the step of forming a film of the composition on the substrate, the step of exposing the film, the heating step, and the developing step can be performed by generally known methods.
  • KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F 2 excimer laser (wavelength 157 nm), EUV light irradiation device (wavelength 13.5 nm)
  • an electron beam irradiation apparatus preferably an ArF excimer laser.
  • light in this specification includes electron beams.
  • any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred.
  • a hydrophobic resin which will be described later, may be added to the composition in advance, or after forming a film, an immersion liquid hardly soluble film (hereinafter also referred to as “topcoat”) may be provided thereon. Good.
  • topcoat an immersion liquid hardly soluble film
  • the top coat is preferably a polymer that does not contain abundant aromatics.
  • hydrocarbon polymer acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon And a fluorine-containing polymer.
  • the hydrophobic resin described above is also suitable as a top coat.
  • Commercially available top coat materials can also be used as appropriate.
  • a developer When developing the topcoat after exposure, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. From the viewpoint that the peeling step can be performed simultaneously with the development processing step of the film, it is preferable that the peeling step can be performed with a developer.
  • the substrate on which the film is formed is not particularly limited.
  • a substrate generally used in a semiconductor manufacturing process such as an IC, a manufacturing process of a circuit board such as a liquid crystal and a thermal head, and other photofabrication lithography processes can be used.
  • Examples of such a substrate e.g., silicon, SiN, and SiO 2 or the like of the inorganic substrate, as well, include coating inorganic substrates such as SOG. Further, if necessary, an organic antireflection film may be formed between the film and the substrate.
  • Examples of the developer containing an organic solvent include polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents, and developers containing hydrocarbon solvents. .
  • ketone solvents examples include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, methyl amyl ketone (MAK; 2-heptanone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone.
  • ester solvent examples include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3- Ethoxypropionate (EEP), 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, methyl propionate, propion
  • Examples include ethyl acid and propyl propionate.
  • alkyl acetates such as methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate and amyl acetate or propionate alkyl esters such as methyl propionate, ethyl propionate and propyl propionate are preferred.
  • alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2- Alcohols such as pentanol, n-heptyl alcohol, n-octyl alcohol and n-decanol; glycols such as ethylene glycol, diethylene glycol and triethylene glycol; and ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, Propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoe Glycol ethers such as ether and methoxymethyl butanol.
  • ether solvents include dioxane and tetrahydrofuran in addition to the above glycol ethers.
  • amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone. Can be mentioned.
  • hydrocarbon solvent examples include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
  • the above solvents may be used as a mixture of two or more. Moreover, you may mix and use with solvent and / or water other than the above within the range which can exhibit sufficient performance.
  • the water content of the entire developer is preferably less than 10% by mass, and more preferably the developer does not substantially contain moisture. That is, this developer is preferably a developer substantially consisting of only an organic solvent. Even in this case, the developer may contain a surfactant or a basic compound described later. In this case, the developer may contain unavoidable impurities derived from the atmosphere.
  • the amount of the organic solvent used in the developer is preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and 95% by mass with respect to the total amount of the developer. More preferably, it is 100 mass% or less.
  • the organic solvent contained in the developer is preferably at least one selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent.
  • the vapor pressure of the developer containing the organic solvent is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
  • the vapor pressure of the developing solution is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
  • the developer having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, methyl amyl ketone (MAK; 2-heptanone), 4-heptanone, 2-hexanone, Ketone solvents such as diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone and methylisobutylketone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, Ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propionic acid formate Ester solvents such as ethyl,
  • the developer having a vapor pressure of 2 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, methyl amyl ketone (MAK; 2-heptanone), 4-heptanone, 2-hexanone, Ketone solvents such as diisobutyl ketone, cyclohexanone, methylcyclohexanone and phenylacetone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3- S such as ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate and propyl lactate N-butyl alcohol,
  • glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether
  • glycol ether solvents such as methoxymethylbutanol; N-methyl-2-pyrrolidone, N, N Dimethylacetamide and N, N- dimethylformamide amide solvents; aromatic hydrocarbon solvents such as xylene; and include aliphatic hydrocarbon solvents such as octane and decane.
  • a surfactant can be added to the developer as necessary.
  • an ionic or nonionic fluorine type and / or silicon type surfactant can be used.
  • these fluorine and / or silicon surfactants include, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950.
  • This surfactant is preferably nonionic.
  • the nonionic surfactant it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.
  • the amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0% with respect to the total amount of the developer. 0.5% by mass.
  • the developer containing an organic solvent may contain a basic compound.
  • Specific examples and preferred examples of the basic compound that can be contained in the developer used in the present invention are the same as those in the basic compound that can be contained in the actinic ray-sensitive or radiation-sensitive resin composition described later.
  • the pattern forming method according to the present invention includes (III) a step of developing the exposed film using a developer containing an organic solvent (hereinafter also referred to as “step (III)” and “developing step”).
  • a development method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying a developer on the substrate surface (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing). Law).
  • the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is , preferably not more than 2mL / sec / mm 2, more preferably not more than 1.5mL / sec / mm 2, more preferably not more than 1mL / sec / mm 2.
  • the flow rate is preferably 0.2 mL / sec / mm 2 or more.
  • the details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied to the resist film by the developer is reduced, and the resist film and / or resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
  • the developer discharge pressure (mL / sec / mm 2 ) is a value at the developing nozzle outlet in the developing device.
  • Examples of a method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump and a method of adjusting the supply pressure from the pressurized tank. Moreover, you may implement the process of stopping image development, after the process of developing, substituting with another solvent.
  • the pattern forming method according to the present invention preferably includes a rinsing step (a step of cleaning the film using a rinsing liquid containing an organic solvent) after the developing step.
  • the rinsing solution used in the rinsing step is not particularly limited as long as it does not dissolve the pattern after development, and a solution containing a general organic solvent can be used.
  • the rinsing liquid examples include those containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. More preferably, the rinse liquid contains at least one organic solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent, and more preferably an alcohol solvent or an ester. It contains a system solvent.
  • the rinsing liquid preferably contains a monohydric alcohol, and more preferably contains a monohydric alcohol having 5 or more carbon atoms.
  • These monohydric alcohols may be linear, branched, or cyclic. Examples of these monohydric alcohols include 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2- Examples include pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, and 4-octanol. Examples of the monohydric alcohol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, and
  • Each of the above components may be used as a mixture of two or more, or may be used as a mixture with an organic solvent other than the above.
  • the water content of the rinse liquid is preferably less than 10% by mass, preferably less than 5% by mass, and more preferably less than 3% by mass. That is, the amount of the organic solvent used in the rinse liquid is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, based on the total amount of the rinse liquid. It is particularly preferable that the content is not less than 100% by mass. By setting the water content of the rinse liquid to less than 10% by mass, even better development characteristics can be achieved.
  • the vapor pressure of the rinse liquid is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and 0.12 kPa or more and 3 kPa or less at 20 ° C. Is more preferable.
  • the vapor pressure of the rinsing liquid is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and 0.12 kPa or more and 3 kPa or less at 20 ° C. Is more preferable.
  • the developed wafer is cleaned using the above rinsing liquid.
  • the method of the cleaning process is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), and immersing the substrate in a bath filled with the rinse liquid for a certain period of time. Examples thereof include a method (dip method) and a method (spray method) in which a rinse liquid is sprayed onto the substrate surface. Among these, it is preferable to remove the rinse liquid from the substrate by performing a cleaning process by a spin coating method and then rotating the substrate at a rotational speed of 2000 rpm to 4000 rpm.
  • the pattern forming method of the present invention can further include a step of performing development using an alkaline aqueous solution to form a resist pattern (alkali developing step). Thereby, a finer pattern can be formed.
  • alkali developing step a step of performing development using an alkaline aqueous solution to form a resist pattern.
  • a portion with low exposure intensity is removed by the organic solvent development step, but a portion with high exposure strength is also removed by further performing the alkali development step.
  • Alkaline development can be performed either before or after the step of developing using a developer containing an organic solvent, but is more preferably performed before the organic solvent developing step.
  • the type of alkali developer is not particularly limited, but an aqueous solution of tetramethylammonium hydroxide is usually used. An appropriate amount of alcohol and / or surfactant may be added to the alkaline developer.
  • the alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
  • the pH of the alkali developer is usually from 10.0 to 15.0.
  • As the alkali developer it is particularly preferable to use a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.
  • the present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.
  • the electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).
  • the present invention also relates to an actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method.
  • the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as “the actinic ray-sensitive or radiation-sensitive resin composition of the present invention”) used in the pattern forming method according to the present invention will be described.
  • This actinic ray-sensitive or radiation-sensitive resin composition may be used for negative development or positive development. That is, the actinic ray-sensitive or radiation-sensitive resin composition may be used for development using a developer containing an organic solvent, or may be used for development using an alkali developer.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is typically used for negative development, that is, development using a developer containing an organic solvent. That is, the composition according to the present invention is typically a negative actinic ray-sensitive or radiation-sensitive resin composition.
  • the present invention also relates to a resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention has (A) a repeating unit having a group that is decomposed by the action of an acid to generate an alcoholic hydroxyl group, and has a weight average molecular weight of 11,000 or more. Resin (hereinafter also referred to as acid-decomposable resin) is included.
  • acid-decomposable resin each component which an actinic-ray-sensitive or radiation-sensitive resin composition contains or can contain is demonstrated in order.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains an acid-decomposable resin.
  • the acid-decomposable resin contains a repeating unit (P) having a group capable of decomposing by the action of an acid to generate an alcoholic hydroxyl group as an acid-decomposable group.
  • the acid-decomposable group decomposes by the action of an acid to generate a carboxy group
  • sensitivity, limit resolving power, roughness characteristics, exposure latitude (EL), post-exposure heating (PEB) temperature dependency, and focus margin (DOF) are improved as compared with the case of only a group. Yes. The reason for this is not always clear, but the present inventors speculate as follows.
  • the present inventors use a group that decomposes by the action of an acid to generate an alcoholic hydroxyl group as at least a part of the acid-decomposable group, the reactivity of the acid-decomposable resin is improved and the acid-decomposable group is improved. This is considered to be because the polarity change of the resin due to decomposition of the resin increases, and the dissolution contrast with respect to the developer containing the organic solvent is improved.
  • the present invention is a group in which at least a part of the acid-decomposable group is decomposed by the action of an acid to produce an alcoholic hydroxyl group
  • the acid-decomposable group is decomposed by the action of an acid to produce a carboxy group.
  • PEB post-exposure heating
  • the pKa of the alcoholic hydroxyl group that can be generated by the above group being decomposed by the action of an acid is, for example, 12 or more, and typically 12 or more and 20 or less. If this pKa is excessively small, the stability of the composition containing the acid-decomposable resin is lowered, and the variation in resist performance with time may increase.
  • “pKa” is a value calculated using “ACD / pKa DB” manufactured by Fujitsu Limited under an initial setting that is not customized.
  • the above repeating unit (P) preferably has two or more groups that decompose by the action of an acid to generate an alcoholic hydroxyl group. That is, the repeating unit (P) preferably has a structure that decomposes by the action of an acid to generate two or more alcoholic hydroxyl groups. If it carries out like this, the limit resolving power and roughness characteristic of the composition containing acid-decomposable resin can further be improved.
  • the repeating unit (P) is preferably represented by at least one selected from the group consisting of the following general formulas (I-1) to (I-10). This repeating unit is more preferably represented by at least one selected from the group consisting of the following general formulas (I-1) to (I-3), and is represented by the following general formula (I-1) More preferably.
  • Ra independently represents a hydrogen atom, an alkyl group or a group represented by —CH 2 —O—Ra 2 .
  • Ra 2 represents a hydrogen atom, an alkyl group, or an acyl group.
  • R 1 represents a (n + 1) -valent organic group.
  • R 2 independently represents a single bond or an (n + 1) -valent organic group when m ⁇ 2.
  • OP independently represents the above group that decomposes by the action of an acid to produce an alcoholic hydroxyl group. When n ⁇ 2 and / or m ⁇ 2, two or more OPs may be bonded to each other to form a ring.
  • W represents a methylene group, an oxygen atom or a sulfur atom.
  • n and m represent an integer of 1 or more.
  • n is 1 when R 2 represents a single bond.
  • l represents an integer of 0 or more.
  • L 1 represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO 3 — or —SO 2 NH—.
  • Ar represents a divalent aromatic ring group.
  • Each R independently represents a hydrogen atom or an alkyl group.
  • R 0 represents a hydrogen atom or an organic group.
  • L 3 represents a (m + 2) -valent linking group.
  • R L each independently represents an (n + 1) -valent linking group when m ⁇ 2.
  • R S each independently represents a substituent when p ⁇ 2. For p ⁇ 2, plural structured R S may be bonded to each other to form a ring.
  • p represents an integer of 0 to 3.
  • Ra represents a hydrogen atom, an alkyl group, or a group represented by —CH 2 —O—Ra 2 .
  • Ra is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group.
  • W represents a methylene group, an oxygen atom or a sulfur atom. W is preferably a methylene group or an oxygen atom.
  • R 1 represents a (n + 1) -valent organic group.
  • R 1 is preferably a non-aromatic hydrocarbon group.
  • R 1 may be a chain hydrocarbon group or an alicyclic hydrocarbon group.
  • R 1 is more preferably an alicyclic hydrocarbon group.
  • the alicyclic hydrocarbon group may be monocyclic or polycyclic.
  • the alicyclic hydrocarbon group is more preferably polycyclic.
  • R 2 represents a single bond or an (n + 1) valent organic group.
  • R 2 is preferably a single bond or a non-aromatic hydrocarbon group.
  • R 2 may be a chain hydrocarbon group or an alicyclic hydrocarbon group.
  • R 1 and / or R 2 is a chain hydrocarbon group
  • the chain hydrocarbon group may be linear or branched.
  • the chain hydrocarbon group preferably has 1 to 8 carbon atoms.
  • R 1 and / or R 2 is an alkylene group
  • R 1 and / or R 2 is a methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group or sec- A butylene group is preferred.
  • R 1 and / or R 2 is an alicyclic hydrocarbon group
  • the alicyclic hydrocarbon group may be monocyclic or polycyclic.
  • This alicyclic hydrocarbon group has, for example, a monocyclo, bicyclo, tricyclo or tetracyclo structure.
  • the carbon number of the alicyclic hydrocarbon group is usually 5 or more, preferably 6 to 30, and more preferably 7 to 25.
  • Examples of the alicyclic hydrocarbon group include those having the partial structures listed below. Each of these partial structures may have a substituent.
  • the methylene group (—CH 2 —) includes an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl group [—C ( ⁇ O) —], a sulfonyl group [— —S ( ⁇ O) 2 —], sulfinyl group [—S ( ⁇ O) —], or imino group [—N (R) —] (where R is a hydrogen atom or an alkyl group) may be substituted.
  • R 1 and / or R 2 when R 1 and / or R 2 is a cycloalkylene group, R 1 and / or R 2 may be an adamantylene group, a noradamantylene group, a decahydronaphthylene group, a tricyclodecanylene group, a tetracyclododeca group.
  • Nylene group, norbornylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclodecanylene group, or cyclododecanylene group are preferable, and adamantylene group, norbornylene group, cyclohexylene group, cyclopentylene It is more preferable that they are a len group, a tetracyclododecanylene group, or a tricyclodecanylene group.
  • the non-aromatic hydrocarbon group of R 1 and / or R 2 may have a substituent.
  • the substituent include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms.
  • the above alkyl group, alkoxy group and alkoxycarbonyl group may further have a substituent.
  • a hydroxy group, a halogen atom, and an alkoxy group are mentioned, for example.
  • L 1 represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO 3 — or —SO 2 NH—.
  • Ar represents a divalent aromatic ring group.
  • L 1 is preferably a linking group represented by —COO—, —CONH— or —Ar—, and more preferably a linking group represented by —COO— or —CONH—.
  • R represents a hydrogen atom or an alkyl group.
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.
  • R is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • R 0 represents a hydrogen atom or an organic group.
  • the organic group include an alkyl group, a cycloalkyl group, an aryl group, an alkynyl group, and an alkenyl group.
  • R 0 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group.
  • L 3 represents a (m + 2) -valent linking group. That is, L 3 represents a trivalent or higher linking group. Examples of such a linking group include corresponding groups in specific examples described later.
  • R L represents a (n + 1) -valent linking group. That is, R L represents a divalent or higher linking group. Examples of such a linking group include an alkylene group, a cycloalkylene group, and corresponding groups in the specific examples described below. R L may be bonded to each other or bonded to the following R S to form a ring structure.
  • R S represents a substituent.
  • substituents include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, and a halogen atom.
  • N is an integer of 1 or more.
  • n is preferably an integer of 1 to 3, and more preferably 1 or 2.
  • n is 2 or more, it is possible to further improve the dissolution contrast with respect to a developer containing an organic solvent. Accordingly, in this way, the limit resolution and roughness characteristics can be further improved.
  • n is an integer of 1 or more. m is preferably an integer of 1 to 3, and more preferably 1 or 2. l is an integer of 0 or more. l is preferably 0 or 1. p is an integer of 0 to 3.
  • Ra and OP have the same meanings as in general formulas (I-1) to (I-3).
  • the corresponding ring structure is represented as “OPO” for convenience.
  • the group that decomposes by the action of an acid to produce an alcoholic hydroxyl group is preferably represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-4).
  • R 3 each independently represents a hydrogen atom or a monovalent organic group.
  • R 3 may be bonded to each other to form a ring.
  • R 4 each independently represents a monovalent organic group.
  • R 4 may be bonded to each other to form a ring.
  • R 3 and R 4 may be bonded to each other to form a ring.
  • R 5 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. At least two R 5 may be bonded to each other to form a ring. However, when one or two of the three R 5 are hydrogen atoms, at least one of the remaining R 5 represents an aryl group, an alkenyl group, or an alkynyl group.
  • the group that decomposes by the action of an acid to produce an alcoholic hydroxyl group is also preferably represented by at least one selected from the group consisting of the following general formulas (II-5) to (II-9).
  • R 4 has the same meaning as in formulas (II-1) to (II-3).
  • R 6 each independently represents a hydrogen atom or a monovalent organic group. R 6 may be bonded to each other to form a ring.
  • the group that decomposes by the action of an acid to produce an alcoholic hydroxyl group is more preferably represented by at least one selected from general formulas (II-1) to (II-3). ) Or (II-3) is more preferable, and the general formula (II-1) is particularly preferable.
  • R 3 represents a hydrogen atom or a monovalent organic group as described above.
  • R 3 is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group.
  • the alkyl group for R 3 may be linear or branched.
  • the number of carbon atoms of the alkyl group represented by R 3 is preferably 1 to 10, and more preferably 1 to 3.
  • Examples of the alkyl group for R 3 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • the cycloalkyl group for R 3 may be monocyclic or polycyclic.
  • the number of carbon atoms of the cycloalkyl group represented by R 3 is preferably 3 to 10, and more preferably 4 to 8.
  • Examples of the cycloalkyl group represented by R 3 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.
  • At least one of R 3 is preferably a monovalent organic group. When such a configuration is employed, particularly high sensitivity can be achieved.
  • R 4 represents a monovalent organic group.
  • R 4 is preferably an alkyl group or a cycloalkyl group, and more preferably an alkyl group. These alkyl groups and cycloalkyl groups may have a substituent.
  • the alkyl group represented by R 4 preferably has no substituent, or preferably has one or more aryl groups and / or one or more silyl groups as substituents.
  • the carbon number of the unsubstituted alkyl group is preferably 1-20.
  • the alkyl group moiety in the alkyl group substituted with one or more aryl groups preferably has 1 to 25 carbon atoms.
  • the number of carbon atoms of the alkyl group moiety in the alkyl group substituted with one or more silyl groups is preferably 1-30. Further, when the cycloalkyl group of R 4 has no substituent, the carbon number thereof is preferably 3-20.
  • R 5 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. However, when one or two of the three R 5 are hydrogen atoms, at least one of the remaining R 5 represents an aryl group, an alkenyl group, or an alkynyl group.
  • R 5 is preferably a hydrogen atom or an alkyl group.
  • the alkyl group may have a substituent or may not have a substituent. When the alkyl group does not have a substituent, the carbon number thereof is preferably 1 to 6, and preferably 1 to 3.
  • R 6 represents a hydrogen atom or a monovalent organic group as described above.
  • R 6 is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or an alkyl group having no substituent.
  • R 6 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and having no substituent.
  • Examples of the alkyl group and cycloalkyl group of R 4 , R 5, and R 6 include the same as those described above for R 3 .
  • the repeating unit (P) is particularly preferably represented by the general formula (I-1). Further, the group that decomposes by the action of an acid to produce an alcoholic hydroxyl group is particularly preferably represented by the general formula (II-1). That is, the repeating unit (P) is particularly preferably represented by the following general formula (III).
  • R 1 , Ra, R 3 , R 4 , and n are as defined in general formulas (I-1) and (II-1).
  • the repeating unit (P) preferably has a structure that is decomposed by the action of an acid to generate two or more alcoholic hydroxyl groups.
  • Examples of such a repeating unit (P) include those having a partial structure represented by the following general formula (D-1).
  • L D1 represents a single bond or a divalent or higher valent linking group.
  • R D each independently represents a hydrogen atom, an alkyl group, or a cycloalkyl group. At least two of the three R D are bonded to each other, they may form a ring.
  • X D1 represents a single bond or a linking group having 1 or more carbon atoms.
  • L D1 , R D and X D1 may be bonded to each other to form a ring. Further, at least one of L D1 , R D and X D1 may be bonded to a carbon atom constituting the main chain of the polymer to form a ring.
  • R D1 each independently represents a hydrogen atom, an alkyl group, or a cycloalkyl group. Two R D1 may be bonded to each other to form a ring.
  • Examples of the divalent or higher valent linking group represented by L D1 include —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO 3 —, —SO 2 NH—, and an alkylene group. , A cycloalkylene group, or a linking group represented by a combination of two or more thereof.
  • Ar represents a divalent aromatic ring group.
  • L D1 contains an alkylene group
  • the alkylene group may be linear or branched.
  • the alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon atom.
  • Examples of such an alkylene group include a methylene group, an ethylene group, and a propylene group.
  • the cycloalkylene group preferably has 3 to 10 carbon atoms, and more preferably 5 to 7 carbon atoms.
  • Examples of such a cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.
  • Each of these alkylene groups and cycloalkylene groups may have a substituent.
  • substituents include halogen atoms such as fluorine atom, chlorine atom and bromine atom; mercapto group; hydroxy group; methoxy group, ethoxy group, isopropoxy group, t-butoxy group and alkoxy group of benzyloxy group; Cycloalkyl groups such as propyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl; cyano group; nitro group; sulfonyl group; silyl group; ester group; acyl group; vinyl group;
  • L D1 preferably contains —COO—, more preferably a linking group represented by a combination of —COO— and an alkylene group, represented by —COO— (CH 2 ) n —. More preferably, it is a linking group.
  • n represents a natural number, preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1.
  • L D1 is a linking group represented by a combination of —COO— and an alkylene group
  • an embodiment in which the alkylene group and RD are bonded to each other to form a ring is also preferable.
  • the alkyl group represented by RD may be linear or branched.
  • the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.
  • the cycloalkyl group represented by RD may be monocyclic or polycyclic.
  • Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group, and an adamantyl group.
  • Ring at least two that can formed by bonding of the three R D is preferably from 5 to 7-membered ring, more preferably a 6-membered ring.
  • the number of carbon atoms represented by X D1 are as one or more linking groups, for example, alkylene group.
  • This alkylene group may be linear or branched.
  • the alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon atom. Examples of such an alkylene group include a methylene group, an ethylene group, and a propylene group.
  • the alkyl group represented by R D1 may be linear or branched.
  • the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.
  • the cycloalkyl group represented by R D1 may be monocyclic or polycyclic. Examples of the cycloalkyl group include those described above as the cycloalkyl group represented by RD .
  • the ring that can be formed by bonding two R D1 to each other may be monocyclic or polycyclic, but may be monocyclic from the viewpoint of solubility in a solvent. More preferred.
  • the ring is preferably a 5- to 7-membered ring, more preferably a 6-membered ring.
  • the repeating unit (P) represented by the general formula (D-1) typically has a structure represented by the following general formula (D-2).
  • Ra has the same meaning as that in formula (I-1).
  • Ra is particularly preferably a methyl group.
  • L D1 , R D , X D1 and R D1 have the same meanings as those in formula (D-1).
  • repeating unit (P) represented by the general formula (D-1) are given below.
  • the acid-decomposable resin may contain two or more types of repeating units (P) having a group that decomposes by the action of an acid to generate an alcoholic hydroxyl group.
  • P repeating units
  • the content of the repeating unit having a group capable of decomposing by the action of an acid to generate an alcoholic hydroxyl group is preferably in the range of 10 mol% to 100 mol%, more preferably, based on all repeating units of the acid-decomposable resin. It is within the range of 30 mol% to 90 mol%, more preferably within the range of 50 mol% to 80 mol%.
  • the acid-decomposable resin may further contain other repeating units in addition to the repeating unit (P). Examples of other repeating units include those described below.
  • the acid-decomposable resin preferably further contains a repeating unit (A) having a polar group. If it carries out like this, the sensitivity of the composition containing acid-decomposable resin can further be improved, for example.
  • Examples of the “polar group” that the repeating unit (A) can contain include the following (1) to (4).
  • “electronegativity” means a value by Pauling.
  • Examples of such a polar group include a hydroxy group and the like.
  • Functional group including a structure in which two atoms having electronegativity different by 0.5 or more are bonded by a double bond or a triple bond.
  • Examples of the functional group such polar groups having an ionic sites, for example, a group having a moiety represented by N + or S +.
  • the “polar group” that the repeating unit (A) can contain includes, for example, (I) hydroxy group, (II) cyano group, (III) lactone group, (IV) carboxylic acid group or sulfonic acid group, (V) amide group , A group corresponding to a sulfonamide group or a derivative thereof, (VI) an ammonium group or a sulfonium group, and at least one selected from the group consisting of a combination of two or more thereof.
  • This polar group is particularly preferably an alcoholic hydroxyl group, a cyano group, a lactone group, or a group containing a cyanolactone structure.
  • the acid-decomposable resin further contains a repeating unit having an alcoholic hydroxyl group
  • the exposure latitude (EL) of the composition containing the acid-decomposable resin can be further improved.
  • the acid-decomposable resin further contains a repeating unit having a cyano group
  • the sensitivity of the composition containing the acid-decomposable resin can be further improved.
  • the acid-decomposable resin further contains a repeating unit having a lactone group
  • the dissolution contrast with respect to the developer containing an organic solvent can be further improved. This also makes it possible to further improve the dry etching resistance, coating properties, and adhesion to the substrate of the composition containing the acid-decomposable resin.
  • the acid-decomposable resin further contains a repeating unit having a group containing a lactone structure having a cyano group
  • the dissolution contrast with respect to a developer containing an organic solvent can be further improved.
  • This also makes it possible to further improve the sensitivity, dry etching resistance, applicability, and adhesion to the substrate of the composition containing the acid-decomposable resin.
  • this makes it possible for a single repeating unit to have a function attributable to each of the cyano group and the lactone group, thereby further increasing the degree of freedom in designing the acid-decomposable resin.
  • Preferable repeating unit (A) includes, for example, those obtained by substituting “alcoholic hydroxyl group” in the above repeating unit (P) for “a group that decomposes by the action of an acid to generate an alcoholic hydroxyl group”. It is done.
  • Such a repeating unit (A) preferably has a structure in which “OP” is replaced with “OH” in each of the above general formulas (I-1) to (I-10). That is, this repeating unit is preferably represented by at least one selected from the group consisting of the following general formulas (I-1H) to (I-10H). In particular, the repeating unit (A) is more preferably represented by at least one selected from the group consisting of the following general formulas (I-1H) to (I-3H). More preferably, it is represented by 1H).
  • Ra, R 1 , R 2 , W, n, m, l, L 1 , R, R 0 , L 3 , R L , R S and p are represented by the general formulas (I-1) to (I ⁇ It is synonymous with each of 10).
  • a repeating unit having a group that decomposes by the action of an acid to generate an alcoholic hydroxyl group and a repeating unit represented by at least one selected from the group consisting of the above general formulas (I-1H) to (I-10H)
  • EL can be improved.
  • the repeating unit (A) in which the “group that generates an alcoholic hydroxyl group by the action of an acid” is replaced with “alcoholic hydroxyl group” is represented by the following general formula (D- Those containing a partial structure represented by 1H) or those represented by the following general formula (D-2H) may be used. That is, in the above general formula (D-1) or (D-2), the repeating unit (A) is replaced with “alcoholic hydroxyl group” from “a group that generates an alcoholic hydroxyl group by being decomposed by the action of an acid”. It may be substituted.
  • L D1 , R D , X D1 and Ra have the same meanings as in general formulas (D-1) and (D-2).
  • the content of the repeating unit (A) in which “the group that generates an alcoholic hydroxyl group by decomposition by the action of an acid” is replaced with “alcoholic hydroxyl group” is the acid-decomposable resin content.
  • the content is preferably 5 to 100 mol%, more preferably 10 to 90 mol%, still more preferably 20 to 80 mol%, based on all repeating units.
  • repeating units (A) include, for example, repeating units having a hydroxy group or a cyano group. This improves the substrate adhesion and developer compatibility.
  • the repeating unit having a hydroxy group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxy group or a cyano group, and preferably has no acid-decomposable group.
  • the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxy group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group.
  • Preferable alicyclic hydrocarbon structures substituted with a hydroxy group or a cyano group are partial structures represented by the following general formulas (VIIa) to (VIId).
  • R 2 c to R 4 c each independently represents a hydrogen atom, a hydroxy group or a cyano group. However, at least one of R 2 c to R 4 c represents a hydroxy group or a cyano group. Preferably, one or two of R 2 c to R 4 c are a hydroxy group and the rest are hydrogen atoms. In general formula (VIIa), it is more preferable that two members out of R 2 c to R 4 c are hydroxy groups and the remaining are hydrogen atoms.
  • repeating unit having a partial structure represented by general formulas (VIIa) to (VIId) examples include repeating units represented by the following general formulas (AIIa) to (AIId).
  • R 1 c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
  • R 2 c ⁇ R 4 c is in the general formula (VIIa) ⁇ (VIIc), the same meanings as R 2 c ⁇ R 4 c.
  • the content of the repeating unit having a hydroxy group or a cyano group is preferably from 5 to 70 mol%, more preferably from 5 to 60 mol%, still more preferably from 10 to 50 mol%, based on all repeating units in the acid-decomposable resin. .
  • repeating unit having a hydroxy group or a cyano group are listed below, but the present invention is not limited thereto.
  • repeating units (A) include, for example, repeating units having a lactone structure.
  • the repeating unit having a lactone structure preferably has a 5- to 7-membered lactone structure, and other ring structures are condensed to form a bicyclo structure or a spiro structure on the 5- to 7-membered lactone structure.
  • a ring is more preferable.
  • a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-17) can be given.
  • Preferred lactone structures include (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17). .
  • line edge roughness and development defects can be further reduced.
  • Rb 2 represents a substituent, and n 2 represents an integer of 0 to 4. n 2 is preferably an integer of 0 to 2.
  • Preferred examples of Rb 2 include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, carboxy groups, halogens Examples include an atom, a hydroxy group, a cyano group, and an acid-decomposable group described later. Of these, an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-decomposable group is particularly preferable.
  • the plurality of Rb 2 may be the same as each other or different from each other. In addition, the plurality of Rb 2 may be bonded to each other to form a ring.
  • repeating unit having a lactone structure examples include a repeating unit represented by the following general formula (AII ′).
  • Rb 0 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.
  • substituents that the alkyl group of Rb 0 may have include a hydroxy group and a halogen atom.
  • the halogen atom for Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Preferred are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom and a methyl group are particularly preferred.
  • V represents a group having a structure represented by any one of the general formulas (LC1-1) to (LC1-17).
  • repeating unit having a lactone structure examples include but not limited thereto.
  • the repeating unit having a lactone structure include the following repeating units.
  • an optimal lactone group for example, the pattern profile and / or density dependence can be optimized.
  • the repeating unit having a lactone structure usually has an optical isomer, but as described above, any optical isomer may be used.
  • One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
  • the optical purity is preferably 90% ee or more, and more preferably 95% ee or more.
  • the repeating unit having a lactone structure may be a repeating unit represented by the following general formula (1).
  • A represents an ester bond or an amide bond.
  • R 0 independently represents an alkylene group, a cycloalkylene group, or a combination thereof when n S ⁇ 2.
  • Z is each independently n s ⁇ 2, ether bond, ester bond, amide bond, urethane bond,
  • R represents, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
  • R 8 represents a monovalent organic group having a lactone structure.
  • n S represents an integer of 1 to 5.
  • n S is preferably 1.
  • R 7 represents a hydrogen atom, an alkyl group or a halogen atom. This alkyl group may have a substituent.
  • R 7 preferably represents a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.
  • R 0 represents an alkylene group, a cycloalkylene group, or a combination thereof.
  • the alkylene group as R 0 may be linear or branched.
  • the alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. Examples of such an alkylene group include a methylene group, an ethylene group, and a propylene group.
  • the cycloalkylene group as R 0 preferably has 3 to 10 carbon atoms, and more preferably 5 to 7 carbon atoms.
  • Examples of such a cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.
  • Each of these alkylene groups and cycloalkylene groups may have a substituent.
  • substituents include halogen atoms such as fluorine atom, chlorine atom and bromine atom; mercapto group; hydroxy group; methoxy group, ethoxy group, isopropoxy group, t-butoxy group and alkoxy group of benzyloxy group; Cycloalkyl groups such as propyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl; cyano group; nitro group; sulfonyl group; silyl group; ester group; acyl group; vinyl group;
  • Z represents an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond as described above.
  • Z is preferably an ether bond or an ester bond, and particularly preferably represents an ester bond.
  • R 8 represents a monovalent organic group having a lactone structure as described above.
  • This organic group has, for example, a lactone structure represented by any of the above general formulas (LC1-1) to (LC1-17).
  • a structure represented by the general formula (LC1-4), (LC1-5) or (LC1-17) is more preferable, and a structure represented by the general formula (LC1-4) is particularly preferable.
  • R 8 preferably has an unsubstituted lactone structure or a lactone structure having a methyl group, a cyano group, or an alkoxycarbonyl group as a substituent.
  • R 8 is preferably a monovalent organic group having a lactone structure having a cyano group as a substituent (that is, a cyanolactone structure).
  • R represents a hydrogen atom, an alkyl group or a halogen atom. This alkyl group may have a substituent. R preferably represents a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.
  • the repeating unit represented by the general formula (1) is preferably a repeating unit represented by the following general formula (2).
  • R 7 , A, R 0 , Z and n S have the same meaning as in general formula (1).
  • Rb independently represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxy group, or an alkoxy group when m ⁇ 2. When m ⁇ 2, two or more Rb may be bonded to each other to form a ring.
  • X represents an alkylene group, an oxygen atom, or a sulfur atom.
  • m represents an integer of 0 to 5. m is preferably 0 or 1.
  • the alkyl group for Rb is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
  • Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups.
  • Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-butoxy group, and a t-butoxy group.
  • the alkyl group, cycloalkyl group, alkoxycarbonyl group and alkoxy group of Rb may have a substituent.
  • substituents include an alkoxy group such as a hydroxy group, a methoxy group and an ethoxy group; a cyano group; and a halogen atom such as a fluorine atom.
  • Rb is more preferably a methyl group, a cyano group or an alkoxycarbonyl group, and even more preferably a cyano group.
  • At least one Rb is preferably substituted at the ⁇ -position or ⁇ -position of the carbonyl group of the lactone.
  • Rb is preferably substituted at the ⁇ -position of the lactone carbonyl group.
  • alkylene group of X examples include a methylene group and an ethylene group.
  • X is preferably an oxygen atom or a methylene group, and more preferably a methylene group.
  • R represents a hydrogen atom, an alkyl group or a halogen atom. This alkyl group may have a substituent. R preferably represents a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.
  • two or more lactone repeating units selected from general formula (1) can be used in combination.
  • n S to select a combination of two or more kinds of repeating units is 1.
  • the content of the repeating unit having a lactone structure is preferably 10 to 80 mol%, more preferably 15 to 70 mol%, and more preferably 20 to 60 mol%, based on all repeating units in the resin. Further preferred.
  • the resin (A) may have a repeating unit having a sultone structure, and the sultone groups possessed by the resin (A) are preferably the following general formulas (SL-1) and (SL-2).
  • Rb 2 and n 2 have the same meanings as in the general formulas (LC1-1) to (LC1-17) described above.
  • repeating unit having a sultone structure that the resin (A) has one obtained by substituting the lactone structure in the repeating unit having the lactone structure described above with a sultone structure is preferable.
  • Other preferable repeating units (A) include, for example, a carboxy group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, or an aliphatic alcohol group in which the ⁇ -position is substituted with an electron withdrawing group (for example, hexafluoro And those having an isopropanol group).
  • This repeating unit (A) more preferably comprises a carboxy group.
  • repeating unit (A) examples include a repeating unit in which the above group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or the above main group of the resin through a linking group.
  • a repeating unit to which a group is bonded, or a polymerization initiator or chain transfer agent having the above group is introduced at the end of the polymer chain during polymerization, and the linking group is a monocyclic or polycyclic cyclic carbonization. It may have a hydrogen structure.
  • Particularly preferred are repeating units of acrylic acid or methacrylic acid.
  • the content of the repeating unit (A) having the above group is preferably from 0 to 20 mol%, more preferably from 3 to 15 mol%, still more preferably from 5 to 10 mol%, based on all repeating units in the acid-decomposable resin. .
  • Rx represents H, CH 3 , CH 2 OH, or CF 3 .
  • the acid-decomposable resin has a group that decomposes by the action of an acid to generate a polar group other than an alcoholic hydroxyl group. It is preferable that the repeating unit (B) is further included.
  • the acid-decomposable resin preferably further includes a repeating unit having a group that decomposes by the action of an acid to generate a carboxy group. In this case, the focus margin (DOF) of the composition containing the acid-decomposable resin can be further improved.
  • the repeating unit (B) preferably has a structure in which a polar group is protected by a group that decomposes and leaves under the action of an acid.
  • the polar group include a phenolic hydroxy group, a carboxy group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, an (alkylsulfonyl) (alkylcarbonyl) imide group, Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. It is done.
  • Preferred polar groups include a carb
  • a preferable group as the acid-decomposable group is a group in which the hydrogen atom of these polar groups is substituted with a group capable of leaving with an acid.
  • Examples of the group leaving with an acid include —C (R 36 ) (R 37 ) (R 38 ), —C (R 36 ) (R 37 ) (OR 39 ), —C (R 01 ) (R 02 ). ) (OR 39 ) and the like.
  • R 36 to R 39 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • R 36 and R 37 may be bonded to each other to form a ring.
  • R 01 to R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • the acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.
  • the repeating unit having an acid-decomposable group that can be contained in the acid-decomposable resin is preferably a repeating unit represented by the following general formula (AI).
  • Xa 1 represents a hydrogen atom, an optionally substituted methyl group, or a group represented by —CH 2 —R 9 .
  • R 9 represents a hydroxy group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group.
  • Xa 1 preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
  • Rx 1 to Rx 3 each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). At least two members out of Rx 1 to Rx 3 may combine to form a cycloalkyl group (monocyclic or polycyclic).
  • Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like.
  • Rt represents an alkylene group or a cycloalkylene group.
  • T is preferably a single bond or a —COO—Rt— group.
  • Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH 2 — group or a — (CH 2 ) 3 — group.
  • the alkyl group of Rx 1 to Rx 3 is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.
  • Examples of the cycloalkyl group of Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. Groups are preferred.
  • Examples of the cycloalkyl group formed by combining at least two of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, A polycyclic cycloalkyl group such as an adamantyl group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.
  • Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-described cycloalkyl group is preferable.
  • Each of the above groups may have a substituent.
  • substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxy group, an alkoxy group (preferably 1 to 4 carbon atoms), Examples thereof include a carboxy group and an alkoxycarbonyl group (preferably having 2 to 6 carbon atoms), and preferably having 8 or less carbon atoms.
  • the acid-decomposable resin preferably has a repeating unit represented by the general formula (I) and / or a repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). .
  • R 1 and R 3 each independently represent a hydrogen atom, an optionally substituted methyl group or a group represented by —CH 2 —R 9 .
  • R 9 represents a monovalent organic group.
  • R 2 , R 4 , R 5 and R 6 each independently represents an alkyl group or a cycloalkyl group.
  • R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.
  • R 1 preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
  • the alkyl group in R 2 may be linear or branched, and may have a substituent.
  • the cycloalkyl group in R 2 may be monocyclic or polycyclic and may have a substituent. The case where the cycloalkyl group in R 2 is a monocyclic cycloalkyl group is preferable because acid decomposability is improved.
  • R 2 is preferably an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group.
  • the alkyl group as R 2 may be either linear or branched, but a branched alkyl group is preferable because acid decomposability is improved.
  • R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.
  • the alicyclic structure formed by R is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 3 to 7, more preferably 5 or 6.
  • R 3 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
  • the alkyl group in R 4 , R 5 , and R 6 may be linear or branched and may have a substituent.
  • the alkyl group those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group are preferable.
  • the cycloalkyl group in R 4 , R 5 and R 6 may be monocyclic or polycyclic and may have a substituent.
  • the cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.
  • Examples of the repeating unit represented by the general formula (I) include a repeating unit represented by the following general formula (1-a).
  • R 1 and R 2 have the same meanings as those in formula (I).
  • the repeating unit represented by the general formula (II) is more preferably a repeating unit represented by the following general formula (II-1).
  • R 3 to R 5 have the same meanings as in general formula (II).
  • R 10 represents a substituent containing a polar group. When a plurality of R 10 are present, they may be the same as or different from each other.
  • the substituent containing a polar group include a linear or branched alkyl group or cycloalkyl group having a hydroxy group, a cyano group, an amino group, an alkylamide group or a sulfonamido group, and preferably a hydroxy group. It is an alkyl group having As the branched alkyl group, an isopropyl group is particularly preferable.
  • P represents an integer from 0 to 15. p is preferably 0 to 2, more preferably 0 or 1.
  • the acid-decomposable resin is a resin containing at least one of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferably. In another embodiment, a resin containing at least two kinds of repeating units represented by the general formula (I) as the repeating unit represented by the general formula (AI) is more preferable.
  • the total content is preferably 3 to 50 mol%, more preferably 5 to 40 mol%, more preferably 7 to 30 mol, based on all repeating units in the resin. % Is more preferable.
  • the molar ratio of the repeating unit (B) to the repeating unit (P) is preferably 5:95 to 70:30, more preferably 7:93 to 50:50, 10 : 90 to 30:70 is particularly preferable.
  • Rx and Xa 1 represent a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
  • Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms.
  • Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent.
  • p represents 0 or a positive integer.
  • each R independently represents a hydrogen atom or a methyl group.
  • Acid-decomposable resin has an alicyclic hydrocarbon structure having no polar group and has acid decomposability. It may further contain a repeating unit (C) not shown. Examples of the repeating unit (C) include a repeating unit represented by the general formula (IV).
  • R 5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
  • Ra represents a hydrogen atom, an alkyl group or -CH 2 -O-Ra 2 group.
  • Ra 2 represents a hydrogen atom, an alkyl group, or an acyl group.
  • Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
  • the cyclic structure possessed by R 5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group.
  • the monocyclic hydrocarbon group include a cycloalkenyl group having 3 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like, and a cycloalkyl group having 3 to 12 carbon atoms and a cyclohexenyl group.
  • Preferable monocyclic hydrocarbon groups are monocyclic hydrocarbon groups having 3 to 7 carbon atoms, and more preferable examples include a cyclopentyl group and a cyclohexyl group.
  • the polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group.
  • the bridged cyclic hydrocarbon ring for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.)
  • Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, tricyclo [4.3.1.1 2,5 ] undecane ring, tetracyclo [ 4.4.0.1 2,5 .
  • the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene.
  • a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.
  • Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.
  • These alicyclic hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino group protected with a protecting group, and the like. It is done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups.
  • the above alkyl group may further have a substituent, and the substituent which may further have a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino protected with a protecting group The group can be mentioned.
  • Examples of the protecting group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group.
  • Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms
  • preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups.
  • acyl groups include aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl and pivaloyl groups, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.
  • the content thereof is preferably 1 to 40 mol%, more preferably 1 to 20 mol%, based on all repeating units in the acid-decomposable resin.
  • Specific examples of the repeating unit (C) are shown below, but the present invention is not limited thereto.
  • Ra represents H, CH 3 , CH 2 OH, or CF 3 .
  • the acid-decomposable resin preferably contains a repeating unit (D) having a cyclic structure having at least one group selected from an ether group, a carbonyl group and a carbonate group as a ring skeleton. Of the ether group, carbonyl group and carbonate group, an ether group is particularly preferred.
  • the repeating unit (D) preferably contains neither a group decomposing by the action of an acid or a group decomposing by the action of an alkali.
  • the acid-decomposable resin contains a repeating unit (D)
  • the content thereof is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, based on all repeating units in the acid-decomposable resin. Particularly preferred is 10 to 40 mol%. Specific examples of the repeating unit (D) are shown below, but the present invention is not limited thereto.
  • Ra represents H, CH 3 , CH 2 OH, or CF 3 .
  • the acid-decomposable resin has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolving power, which is a general necessary characteristic of resist, Various repeating structural units can be included for the purpose of adjusting heat resistance, sensitivity, and the like.
  • repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.
  • a monomer for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.
  • any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.
  • the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general resist performance required for resolving power and heat resistance. In order to adjust the sensitivity and the like, it is set as appropriate.
  • the acid-decomposable resin preferably has no aromatic group from the viewpoint of transparency to ArF light.
  • the acid-decomposable resin preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
  • an acid-decomposable resin does not contain a fluorine atom and a silicon atom from a compatible viewpoint with the hydrophobic resin mentioned later.
  • the acid-decomposable resin is preferably one in which all of the repeating units are composed of (meth) acrylate-based repeating units.
  • all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units.
  • the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.
  • the acid-decomposable resin When the composition according to the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, high energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the acid-decomposable resin further contains a hydroxystyrene-based repeating unit. It is preferable to have. More preferably, it has a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected with an acid-decomposable group, and an acid-decomposable repeating unit such as a (meth) acrylic acid tertiary alkyl ester.
  • a hydroxystyrene-based repeating unit It is preferable to have. More preferably, it has a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected with an acid-decomposable group, and an acid-decomposable repeating unit such
  • repeating unit having a preferable acid-decomposable group based on hydroxystyrene examples include, for example, a repeating unit of t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, (meth) acrylic acid tertiary alkyl ester, and the like. More preferred are repeating units of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.
  • the acid-decomposable resin of the present invention can be synthesized according to a conventional method (for example, radical polymerization).
  • a conventional method for example, radical polymerization
  • a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours.
  • the dropping polymerization method is added, and the dropping polymerization method is preferable.
  • reaction solvent examples include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt
  • the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
  • a polymerization initiator a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization.
  • azo initiator an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxy group is preferable.
  • Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like.
  • an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery.
  • the concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass.
  • the reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.
  • the weight average molecular weight of the acid-decomposable resin of the present invention is 11,000 or more, preferably 12,000 or more, more preferably 13,000 or more, and still more preferably as a polystyrene conversion value by GPC method. Is 14,000 or more, and particularly preferably 15,000 or more. By making a weight average molecular weight into the said range, pattern collapse can be reduced and a residual film rate and pattern shape can be improved.
  • the weight average molecular weight of the acid-decomposable resin of the present invention is usually 30000 or less as a polystyrene conversion value by GPC method.
  • the weight average molecular weight and dispersity (weight average molecular weight / number average molecular weight) of the resin (A) are defined as polystyrene converted values by GPC measurement.
  • HLC-8120 manufactured by Tosoh Corp.
  • TSK gel Multipore HXL-M manufactured by Tosoh Corp., 7.8 mm ID ⁇ 30.0 cm
  • the degree of dispersion is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2.0, and particularly preferably 1.4 to 2.0. .
  • the blending ratio of the acid-decomposable resin in the whole composition is preferably 30 to 99% by mass, more preferably 60 to 95% by mass in the total solid content.
  • the resins of the present invention may be used alone or in combination.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a compound represented by the following general formula (1).
  • R represents an alkyl group, a cycloalkyl group optionally having a carbonyl carbon as a ring member, a lactone structure, a sultone structure, an aryl group, or a group formed by combining two or more thereof.
  • M + represents a monovalent cation.
  • the alkyl group for R is preferably an alkyl group having 4 or more carbon atoms, more preferably an alkyl group having 6 or more carbon atoms, and still more preferably an alkyl group having 10 or more carbon atoms.
  • Specific examples of the alkyl group of R include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-pentyl group, neopentyl group, An n-hexyl group, a 2-ethylhexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, and the like can be given.
  • the alkyl group for R is preferably a decanyl group or a t-butyl group.
  • the cycloalkyl group as R may be monocyclic or polycyclic, is preferably a cycloalkyl group having 6 or more carbon atoms, and is a cycloalkyl group having 10 or more carbon atoms. Is more preferable, and a polycyclic cycloalkyl group having 10 or more carbon atoms is more preferable.
  • cycloalkyl group examples include, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, decahydronaphthyl group, cyclodecyl group, 1-adamantyl group, 2-adamantyl group, Examples thereof include a 1-norbornyl group, a bicyclo [2.2.1] hepten-2-yl group, a group having a steroid skeleton, and a 2-norbornyl group.
  • the cycloalkyl group is preferably a cyclopropyl group, a cyclopentyl group, a group having a steroid skeleton, or a cyclohexyl group.
  • lactone structure and sultone structure of R are the same as those in the lactone structure and sultone structure that the resin (A) may have.
  • a skeleton in which the carbon skeleton shown below is substituted with a skeleton such as a hydroxyl group a skeleton in which a carbon atom as a ring member in the carbon skeleton shown below is substituted with a carbonyl carbon atom, or the like Is mentioned.
  • the aryl group as R is preferably an aryl group having 6 to 15 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and a plurality of aromatic rings are connected to each other via a single bond. Structures (for example, biphenyl group, terphenyl group) are also included. Specific examples of the aryl group include a phenyl group, a 4-methoxyphenyl group, a 4-tert-butylphenyl group, a 4-biphenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthranyl group, a biphenyl group, and a terphenyl. Groups and the like. The aryl group is preferably a phenyl group or a naphthyl group.
  • R is preferably a cycloalkyl group, a sultone structure, an aryl group, or a group formed by combining two or more thereof.
  • R is more preferably a cycloalkyl group, further preferably a polycyclic cycloalkyl group, more preferably a polycyclic cycloalkyl group having 10 or more carbon atoms, an adamantyl group or a steroid.
  • a group having a skeleton is particularly preferable.
  • the above group may have a carbonyl carbon as a ring member.
  • the alkyl group, cycloalkyl group, or aryl group as R may further have a substituent, and examples of the substituent that may be further included include an alkyl group, a cycloalkyl group, an aryl group, an amino group, and an amide.
  • substituent examples include an alkyl group, a cycloalkyl group, an aryl group, an amino group, and an amide.
  • M + represents a monovalent cation
  • examples of the monovalent cation include monovalent cations used in known photoacid generators.
  • Preferable monovalent cations include cations represented by the following general formula (ZI) or (ZII).
  • R 201 , R 202 and R 203 each independently represents an organic group.
  • the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
  • the acid generator may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of R 201 ⁇ R 203 of the compound represented by formula (ZI), the coupling structure to at least one of the general formulas (ZI) of another compound represented by R 201 ⁇ R 203 It may be a compound.
  • (ZI) component examples include cations represented by the following general formula (ZI-1), (ZI-2), (ZI-3) or (ZI-4).
  • the cation represented by the general formula (ZI-1) is an arylsulfonium cation in which at least one of R 201 to R 203 in the general formula (ZI) is an aryl group.
  • the cation represented by the general formula (ZI-2) is a cation in which R 201 to R 203 in the formula (ZI) each independently represents an organic group having no aromatic ring.
  • the aromatic ring includes an aromatic ring containing a hetero atom.
  • R 1c to R 5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a halogen atom or a phenylthio group.
  • R 6c and R 7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
  • R x and R y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
  • R 1c to R 5c , R 6c and R 7c , and R x and R y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom, a sulfur atom , An ester bond and an amide bond may be included.
  • R 13 represents a hydrogen atom, a fluorine atom, a hydroxy group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent.
  • R 15 each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R 15 may be bonded to each other to form a ring. These groups may have a substituent.
  • L represents an integer of 0-2.
  • R represents an integer from 0 to 8.
  • R 204 and R 205 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
  • the compound represented by General formula (1) can be used individually by 1 type or in combination of 2 or more types.
  • the content of the compound represented by the general formula (1) in the composition is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, still more preferably based on the total solid content of the composition. Is 5 to 20% by mass.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain an acid generator different from the compound represented by the general formula (1).
  • an acid generator (hereinafter also referred to as “combination acid generator”) that may be further contained in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, a photoinitiator for photocationic polymerization, a photoradical polymerization Photoinitiators, photodecolorants of dyes, photochromic agents, or known compounds that generate acids upon irradiation with actinic rays or radiation used in microresists, etc., and mixtures thereof are appropriately selected and used can do.
  • the combined acid generator is not particularly limited as long as it is a publicly known acid generator, but upon irradiation with actinic rays or radiation, at least an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, or tris (alkylsulfonyl) methide is used. Compounds that generate either are preferred.
  • the compound (B) that generates an acid upon irradiation with actinic rays or radiation may be in the form of a low molecular compound or may be incorporated in a part of a polymer, but may be in the form of a low molecular compound.
  • the form of the low molecular compound and the form incorporated in a part of the polymer may be used in combination.
  • the molecular weight is preferably 3000 or less, more preferably 2000 or less, and 1000 or less. Is more preferable.
  • the compound (B) that generates an acid upon irradiation with actinic rays or radiation is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the acid-decomposable resin described above. It may be incorporated in a resin different from the resin.
  • the compound represented by the following general formula (ZI '), (ZII') or (ZIII ') can be mentioned.
  • the compound represented by the following general formula (ZI '), (ZII'), or (ZIII ') can be mentioned.
  • R ′ 201 , R ′ 202 and R ′ 203 each independently represents an organic group.
  • the organic group as R ′ 201 , R ′ 202 and R ′ 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • Two of R ′ 201 to R ′ 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
  • Examples of the group formed by combining two of R ′ 201 to R ′ 203 include an alkylene group (eg, butylene group, pentylene group).
  • Z '- represents a non-nucleophilic anion.
  • Z '- as, for example, a sulfonic acid anion (aliphatic sulfonate anion, aromatic sulfonate anion and camphorsulfonate anion), a carboxylate anion (aliphatic carboxylate anion, aromatic carboxylate anion, an aralkyl carboxylic acid Anions, etc.), sulfonylimide anions, bis (alkylsulfonyl) imide anions, tris (alkylsulfonyl) methide anions and the like.
  • a sulfonic acid anion aliphatic sulfonate anion, aromatic sulfonate anion and camphorsulfonate anion
  • a carboxylate anion aliphatic carboxylate anion, aromatic carboxylate anion, an aralkyl carboxylic acid Anions, etc.
  • sulfonylimide anions bis (alkylsulfonyl) imide an
  • the aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. Examples include 3 to 30 cycloalkyl groups.
  • the aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
  • the alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms).
  • an alkylthio group preferably 1 to 15 carbon atoms
  • an alkylsulfonyl group preferably 1 to 15 carbon atoms
  • an alkyliminosulfonyl group preferably 2 to 15 carbon atoms
  • an aryloxysulfonyl group preferably a carbon atom Number 6 to 20
  • alkylaryloxysulfonyl group preferably having 7 to 20 carbon atoms
  • cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like.
  • examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).
  • the aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group and the like.
  • Examples of the sulfonylimide anion include saccharin anion.
  • the alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
  • substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like.
  • a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
  • Z '- can include fluorinated phosphorus, fluorinated boron and fluorinated antimony.
  • Z '- as is substituted at least ⁇ -position by an aliphatic sulfonate anion substituted with a fluorine atom, a fluorine atom or a fluorine atom is substituted with a group having a aromatic sulfonate anion of a sulfonic acid, an alkyl group with a fluorine atom
  • Preferred are bis (alkylsulfonyl) imide anions and tris (alkylsulfonyl) methide anions in which the alkyl group is substituted with a fluorine atom.
  • the non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane.
  • the pKa of the generated acid is preferably ⁇ 1 or less in order to improve sensitivity.
  • Examples of the organic group for R ′ 201 , R ′ 202 and R ′ 203 include an aryl group (preferably having 6 to 15 carbon atoms), a linear or branched alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group ( And preferably having 3 to 15 carbon atoms).
  • R ′ 201 , R ′ 202 and R ′ 203 at least one is preferably an aryl group, more preferably all three are aryl groups.
  • a heteroaryl group such as an indole residue and a pyrrole residue can be used.
  • aryl groups may further have a substituent.
  • substituents include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.
  • R ′ 201 , R ′ 202 and R ′ 203 may be bonded via a single bond or a linking group.
  • the linking group include an alkylene group (preferably having 1 to 3 carbon atoms), —O—, —S—, —CO—, —SO 2 — and the like, but are not limited thereto.
  • R ′ 201 , R ′ 202 and R ′ 203 are not an aryl group
  • R ′ 201 , R ′ 202 and R ′ 203 is not an aryl group
  • Compounds shown as formulas (I-1) to (I-70) in US2003 / 0224288A1 and formulas (IA-1) to (IA-54) in US2003 / 0077540A1 Mention may be made, for example, of cation structures such as the compounds exemplified as (IB-1) to (IB-24).
  • R ′ 204 to R ′ 207 each independently represents an aryl group, an alkyl group or a cycloalkyl group.
  • the aryl group described as the aryl group, alkyl group, and cycloalkyl group of R ′ 201 to R ′ 203 in the aforementioned compound (ZI ′) It is the same.
  • the aryl group, alkyl group and cycloalkyl group of R ′ 204 to R ′ 207 may have a substituent. Examples of the substituent include those that the aryl group, alkyl group, and cycloalkyl group of R ′ 201 to R ′ 203 in the compound represented by the general formula (ZI ′) may have.
  • Z ′ ⁇ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ⁇ in formula (ZI ′).
  • Examples of the combined acid generator further include compounds represented by the following general formulas (ZIV ′), (ZV ′), and (ZVI ′).
  • Ar 3 and Ar 4 each independently represents an aryl group.
  • R 208 , R 209 and R 210 each independently represents an alkyl group, a cycloalkyl group or an aryl group.
  • A represents an alkylene group, an alkenylene group or an arylene group.
  • the combined acid generator can be used alone or in combination of two or more.
  • the actinic ray-sensitive or radiation-sensitive resin composition used in the present invention may or may not contain a combined acid generator, but when it is included, the content of the combined acid generator in the composition is The content is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 7% by mass, based on the total solid content of the composition.
  • the resist composition according to the present invention may further contain a basic compound.
  • the basic compound is preferably a compound having a structure represented by the following formulas (A) to (E).
  • R 200 , R 201 and R 202 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (having 6 to 6 carbon atoms). 20). R 201 and R 202 may be bonded to each other to form a ring. R 203 , R 204 , R 205 and R 206 each independently represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. These alkyl groups are more preferably unsubstituted.
  • Preferred basic compounds include guanidine, dioctylamine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine and piperidine. More preferable basic compounds include compounds having an imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, and alkylamine derivatives having a hydroxy group and / or an ether bond. And aniline derivatives having a hydroxy group and / or an ether bond.
  • Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and 2-phenylbenzimidazole.
  • Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene and 1,8-diazabicyclo [5, 4,0] Undecar 7-ene.
  • Examples of the compound having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group. More specifically, triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide and 2-oxopropylthiophenium hydroxy Do.
  • Examples of the compound having an onium carboxylate structure include a compound having an onium hydroxide structure having a carboxylate as an anion.
  • Examples of the carboxylate include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate.
  • Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
  • aniline compounds examples include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, and N, N-dihexylaniline.
  • alkylamine derivative having a hydroxy group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris (methoxyethoxyethyl) amine.
  • aniline derivatives having a hydroxy group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline.
  • Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.
  • At least one alkyl group is bonded to a nitrogen atom. Further, it is more preferable that an oxygen atom is contained in the chain of the alkyl group to form an oxyalkylene group.
  • the number of oxyalkylene groups is preferably one or more in the molecule, more preferably 3 to 9, and still more preferably 4 to 6. Of these oxyalkylene groups, -CH 2 CH 2 O -, - CH (CH 3) CH 2 O- or -CH 2 CH 2 CH 2 O- by a group represented are especially preferred.
  • the total amount of the basic compound is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the composition.
  • the molar ratio of the total amount of the acid generator to the total amount of the basic compound is preferably 2.5 to 300, more preferably 5.0 to 200, still more preferably 7.0 to 150. If this molar ratio is too small, sensitivity and / or resolution may be reduced. If this molar ratio is excessively large, pattern thickening may occur between exposure and heating (post-bake).
  • Examples of the basic compound include the compounds described above, and among them, a basic compound containing at least one oxygen atom is preferable.
  • a basic compound containing at least one oxygen atom is hydrophilic, has a repeating unit having a group that decomposes by the action of the acid of the present invention to generate an alcoholic hydroxyl group, and has a weight average molecular weight of more than 11,000 Is also hydrophilic, so that the affinity between the two is increased. As a result, the basic compound is uniformly dispersed in the resist film, and the pattern shape is considered to be improved.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain a solvent.
  • the solvent include alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), and monoketones optionally containing a ring.
  • organic solvents such as compounds (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.
  • alkylene glycol monoalkyl ether carboxylate examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl
  • alkylene glycol monoalkyl ether examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.
  • Examples of the lactic acid alkyl ester include methyl lactate, ethyl lactate, propyl lactate, and butyl lactate.
  • alkyl alkoxypropionate examples include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-methoxypropionate.
  • Examples of the cyclic lactone include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, and ⁇ -octano. And iclactone and ⁇ -hydroxy- ⁇ -butyrolactone.
  • Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one 3-penten-2-one, cyclopentanone
  • alkylene carbonate examples include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
  • Alkoxyacetic acid alkyls include, for example, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy acetate -2-propyl.
  • alkyl pyruvate examples include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
  • a solvent having a boiling point of 130 ° C. or higher under normal temperature and pressure it is preferable to use a solvent having a boiling point of 130 ° C. or higher under normal temperature and pressure.
  • a solvent having a boiling point of 130 ° C. or higher under normal temperature and pressure.
  • solvents may be used alone or in combination of two or more. In the latter case, it is preferable to use a mixed solvent of a solvent containing a hydroxy group and a solvent not containing a hydroxy group.
  • Examples of the solvent containing a hydroxy group include alkylene glycol monoalkyl ether and alkyl lactate. Of these, propylene glycol monomethyl ether or ethyl lactate is more preferable.
  • alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone and alkyl acetate are preferable.
  • propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone or butyl acetate are more preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate or 2-heptanone is particularly preferred. .
  • the mass ratio thereof is preferably 1/99 to 99/1, more preferably 10/90 to 90/10. And more preferably 20/80 to 60/40.
  • the solvent is preferably a mixed solvent of propylene glycol monomethyl ether acetate and at least one other solvent.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably further comprises a hydrophobic resin.
  • the hydrophobic resin is unevenly distributed in the surface layer of the resist film, and the receding contact angle of the film with respect to the immersion liquid can be improved when water is used as the immersion medium. Thereby, the immersion liquid followability of a film
  • the receding contact angle of the film after baking and before exposure is preferably 60 ° to 90 ° at a temperature of 23 ⁇ 3 ° C. and a humidity of 45 ⁇ 5%, more preferably 65 ° or more, still more preferably 70 ° or more, particularly preferably. It is 75 ° or more.
  • the hydrophobic resin is unevenly distributed at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule and contributes to uniform mixing of polar / nonpolar substances. It is not necessary.
  • the hydrophobic resin (HR) is preferably a resin having at least one of a fluorine atom and a silicon atom.
  • the fluorine atom or silicon atom in the hydrophobic resin (HR) may be contained in the main chain of the resin or may be substituted on the side chain.
  • the hydrophobic resin (HR) is preferably a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
  • the alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, It may have a substituent.
  • the cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another substituent.
  • aryl group having a fluorine atom examples include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and the aryl group may further have another substituent.
  • alkyl group having a fluorine atom examples include groups represented by the following general formulas (F2) to (F4).
  • the present invention is not limited to this.
  • R 57 to R 68 each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R 57 to R 61 , R 62 to R 64 and R 65 to R 68 is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably having a carbon number of 1 To 4). All of R 57 to R 61 and R 65 to R 67 are preferably fluorine atoms.
  • R 62 , R 63 and R 68 are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R 62 and R 63 may be connected to each other to form a ring.
  • Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
  • Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like.
  • Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
  • Specific examples of the group represented by the general formula (F4) include, for example, —C (CF 3 ) 2 OH, —C (C 2 F 5 ) 2 OH, —C (CF 3 ) (CH 3 ) OH, —CH (CF 3 ) OH and the like are mentioned, and —C (CF 3 ) 2 OH is preferable.
  • Suitable repeating units having a fluorine atom include those shown below.
  • each of R 10 and R 11 independently represents a hydrogen atom, a fluorine atom, or an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and as an alkyl group having a substituent, Fluorinated alkyl group can be mentioned).
  • W 3 to W 6 each independently represents an organic group containing at least one fluorine atom. Specific examples include groups represented by the general formulas (F2) to (F4). Moreover, you may have a unit as shown below as a repeating unit which has a fluorine atom besides these.
  • R 4 to R 7 are each independently a hydrogen atom, a fluorine atom, or an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms. In particular, a fluorinated alkyl group can be mentioned).
  • R 4 to R 7 represents a fluorine atom.
  • R 4 and R 5 or R 6 and R 7 may form a ring.
  • W 2 represents an organic group containing at least one fluorine atom.
  • the atomic groups (F2) to (F4) are mentioned.
  • Q represents an alicyclic structure.
  • the alicyclic structure may have a substituent and may be monocyclic or polycyclic.
  • a bridge type may be used.
  • the monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group.
  • Examples of the polycyclic type include groups having a bicyclo, tricyclo or tetracyclo structure having 5 or more carbon atoms, and preferably a cycloalkyl group having 6 to 20 carbon atoms, such as an adamantyl group, norbornyl group, dicyclopentyl group. , Tricyclodecanyl group, tetracyclododecyl group and the like. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
  • L 2 represents a single bond or a divalent linking group.
  • the divalent linking group include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, —O—, —SO 2 —, —CO—, —N (R )-(Wherein R represents a hydrogen atom or an alkyl group), —NHSO 2 —, or a divalent linking group formed by combining a plurality of these.
  • the hydrophobic resin (HR) may contain a silicon atom.
  • the partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
  • alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).
  • R 12 to R 26 each independently represents a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
  • L 3 to L 5 each represents a single bond or a divalent linking group.
  • the divalent linking group include an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a urea group, or a single group of two or more groups.
  • n represents an integer of 1 to 5.
  • n is preferably an integer of 2 to 4.
  • Examples of the repeating unit containing a fluorine atom or a silicon atom include the examples described in paragraphs [0418] to [0421] of JP2012-27438A.
  • the hydrophobic resin (HR) may have at least one group selected from the following (x) and (z).
  • (X) a polar group;
  • (Z) A group that decomposes by the action of an acid.
  • polar groups include phenolic hydroxy groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) ) And a methylene group.
  • Preferred polar groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (carbonyl) methylene groups.
  • repeating unit having a polar group (x) a repeating unit in which a polar group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or the main chain of the resin through a linking group Examples thereof include a repeating unit to which a polar group is bonded. Furthermore, a polymerization initiator or a chain transfer agent having a polar group can be introduced at the end of the polymer chain at the time of polymerization.
  • the content of the repeating unit having a polar group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol%, based on all repeating units in the hydrophobic resin.
  • repeating unit having a polar group (x) include those described in paragraph [0426] of JP 2012-27438 A.
  • examples of the repeating unit having a group (z) that is decomposed by the action of an acid include the same repeating units having an acid-decomposable group as mentioned above for the acid-decomposable resin. .
  • the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably based on all repeating units in the hydrophobic resin. It is 10 to 80 mol%, more preferably 20 to 60 mol%.
  • the hydrophobic resin (HR) may further have a repeating unit represented by the following general formula (VI).
  • R c31 represents a hydrogen atom, an alkyl group that may be substituted with fluorine, a cyano group, or a —CH 2 —O—Rac 2 group.
  • Rac 2 represents a hydrogen atom, an alkyl group or an acyl group.
  • R c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
  • R c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a fluorine atom or a silicon atom.
  • L c3 represents a single bond or a divalent linking group.
  • the alkyl group represented by R c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
  • the cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
  • the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
  • the cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
  • the aryl group is preferably a phenyl group or naphthyl group having 6 to 20 carbon atoms, and these may have a substituent.
  • R c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
  • the divalent linking group of L c3 is preferably an alkylene group (preferably having a carbon number of 1 to 5), an oxy group, a phenylene group, or an ester bond (a group represented by —COO—).
  • the hydrophobic resin (HR) may contain a repeating unit represented by the following general formula (VII) or (VIII) as the repeating unit represented by the general formula (VI).
  • R c5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxy group nor a cyano group.
  • Rac represents a hydrogen atom, an alkyl group which may be substituted with a fluorine atom, a cyano group or a —CH 2 —O—Rac 2 group.
  • Rac 2 represents a hydrogen atom, an alkyl group or an acyl group.
  • Rac is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
  • the cyclic structure possessed by R c5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group.
  • the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms and a cycloalkenyl group having 3 to 12 carbon atoms.
  • a preferable monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms.
  • the polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group.
  • the bridged cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring.
  • the bridged cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring (for example, a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed).
  • Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.
  • These alicyclic hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino group protected with a protecting group, and the like. It is done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups.
  • the above alkyl group may further have a substituent, and the substituent which may further have a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino protected with a protecting group The group can be mentioned.
  • Examples of the protecting group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group.
  • Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms
  • preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups.
  • acyl groups include aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl and pivaloyl groups, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.
  • R c6 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxycarbonyl group, or an alkylcarbonyloxy group. These groups may be substituted with a fluorine atom or a silicon atom.
  • the alkyl group for R c6 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms.
  • the cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
  • the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
  • the cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
  • the alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms.
  • the alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 20 carbon atoms.
  • n represents an integer of 0 to 5.
  • the plurality of R c6 may be the same or different.
  • R c6 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom, and particularly preferably a trifluoromethyl group or a t-butyl group.
  • the hydrophobic resin (HR) preferably further has a repeating unit represented by the following general formula (CII-AB).
  • R c11 ′ and R c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
  • Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).
  • the general formula (CII-AB) is more preferably the following general formula (CII-AB1) or general formula (CII-AB2).
  • Rc 13 ′ to Rc 16 ′ each independently represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group. Further, at least two members out of Rc 13 ′ to Rc 16 ′ may combine to form a ring. n represents 0 or 1. Specific examples of the repeating unit represented by the general formula (VI) or (CII-AB) include those described in paragraph [0439] of JP 2012-27438 A.
  • hydrophobic resin HR
  • Tables 1 and 2 below show the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.
  • the fluorine atom content is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the molecular weight of the resin (HR).
  • the repeating unit containing a fluorine atom is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, based on all repeating units in the resin (HR).
  • the content of the silicon atom is preferably 2 to 50% by mass and more preferably 2 to 30% by mass with respect to the molecular weight of the resin (HR).
  • the repeating unit containing a silicon atom is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass with respect to all the repeating units of the resin (HR).
  • the weight average molecular weight of the resin (HR) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.
  • Hydrophobic resins can be used alone or in combination of two or more.
  • the content of the resin (HR) in the actinic ray-sensitive or radiation-sensitive resin composition can be appropriately adjusted and used so that the receding contact angle of the resist film falls within the above range.
  • the amount is preferably 0.01 to 10% by mass, more preferably 0.1 to 9% by mass, and still more preferably 0.5 to 8% by mass, based on the total solid content of the resin composition.
  • the resin (HR) is naturally low in impurities such as metals, and the residual monomer or oligomer component is preferably 0 to 10% by mass, more preferably 0 to 5% by mass and 0 to 1% by mass are even more preferable. Thereby, a resist having no change over time such as foreign matter in liquid or sensitivity can be obtained.
  • the molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 3, more preferably 1 to 2, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is in the range of 1 to 1.8, most preferably 1 to 1.5.
  • the resin (HR) various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization).
  • a conventional method for example, radical polymerization
  • a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours.
  • the dropping polymerization method is added, and the dropping polymerization method is preferable.
  • reaction solvent examples include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt
  • ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether
  • ketones such as methyl ethyl ketone and methyl isobutyl ketone
  • ester solvents such as ethyl acetate
  • amide solvents such as dimethylformamide and dimethylacetamide
  • the polymerization is performed using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, generation
  • the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
  • a polymerization initiator a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization.
  • azo initiator an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxy group is preferable.
  • Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like.
  • the concentration of the reaction is usually 5 to 50% by mass, preferably 30 to 50% by mass.
  • the reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.
  • Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less.
  • Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent
  • a normal method such as a method can be applied.
  • the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.
  • the solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer.
  • a compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use.
  • a precipitation or reprecipitation solvent a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.
  • the amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally, 100 to 10,000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300 to 1000 parts by mass.
  • the temperature at the time of precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.).
  • the precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.
  • Precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).
  • the resin may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).
  • a liquid (immersion medium) having a higher refractive index than air is interposed between the film and the lens when irradiated with actinic rays or radiation.
  • the immersion medium to be used any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred.
  • the immersion liquid used for the immersion exposure will be described below.
  • the immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the resist film.
  • Is an ArF excimer laser (wavelength; 193 nm) it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-mentioned viewpoints.
  • a medium having a refractive index of 1.5 or more can be used in that the refractive index can be further improved.
  • This medium may be an aqueous solution or an organic solvent.
  • the additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specifically includes methyl alcohol, ethyl alcohol, isopropyl alcohol and the like.
  • the electric resistance of water is preferably 18.3 M ⁇ cm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed. Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive that increases the refractive index may be added to water, or heavy water (D 2 O) may be used instead of water.
  • topcoat An immersion liquid poorly soluble film (hereinafter also referred to as “topcoat”) may be provided between the film of the composition of the present invention and the immersion liquid so that the film does not directly contact the immersion liquid. Good.
  • the necessary functions for the top coat are suitability for application to the upper layer of the resist, radiation, especially transparency to 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist and can be uniformly applied to the upper layer of the resist.
  • the top coat is preferably a polymer that does not contain abundant aromatics.
  • the polymer contains a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, and silicon. Examples thereof include a polymer and a fluorine-containing polymer.
  • the aforementioned hydrophobic resin (HR) is also suitable as a top coat. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.
  • a developer When removing the topcoat, a developer may be used, or a separate release agent may be used.
  • a release agent a solvent having low penetration into the film is preferable. From the viewpoint that the peeling step can be performed at the same time as the film development processing step, it is preferable that the peeling step can be performed with a developer containing an organic solvent.
  • the resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid.
  • the top coat for ArF immersion exposure is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.
  • the top coat is not mixed with the film and further not mixed with the immersion liquid.
  • the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the composition of the present invention.
  • the topcoat may be water-soluble or water-insoluble.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain a surfactant.
  • a surfactant when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, it is possible to form a pattern with less adhesion and development defects with good sensitivity and resolution. Become.
  • the surfactant it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.
  • fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425.
  • KH-20 manufactured by Asahi Glass Co., Ltd.
  • PolyFox PF-6320 manufactured by OMNOVA Solutions Inc.
  • F-top EF301 or EF303 manufactured by Shin-Akita Kasei Co., Ltd.
  • Florard FC430, 431 or 4430 Suditomo 3M ( MfAck F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (Asahi Glass) Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toagosei Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); Top EF121, EF122A, EF12 B,
  • the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). You may synthesize. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.
  • the polymer having a fluoroaliphatic group is preferably a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate or methacrylate and / or (poly (oxyalkylene)) methacrylate. Even if it distributes, block copolymerization may be sufficient.
  • poly (oxyalkylene) group examples include a poly (oxyethylene) group, a poly (oxypropylene) group, and a poly (oxybutylene) group.
  • units having different chain length alkylene in the same chain such as poly (block connection body of oxyethylene, oxypropylene, and oxyethylene) and poly (block connection body of oxyethylene and oxypropylene) Also good.
  • a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate or methacrylate is composed of a monomer having two or more different fluoroaliphatic groups and two or more different (poly (oxyalkylene). )) It may be a ternary or higher copolymer obtained by copolymerizing acrylate or methacrylate simultaneously.
  • Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by DIC Corporation). Further, a copolymer of an acrylate or methacrylate having a C 6 F 13 group and (poly (oxyalkylene)) acrylate or methacrylate, an acrylate or methacrylate having a C 6 F 13 group and (poly (oxyethylene)) acrylate or methacrylate And a copolymer of (poly (oxypropylene)) acrylate or methacrylate, a copolymer of an acrylate or methacrylate having a C 8 F 17 group and (poly (oxyalkylene)) acrylate or methacrylate, and C 8 F 17 Copolymerization of a group-containing acrylate or methacrylate with (poly (oxyethylene)) acrylate or methacrylate and (poly (oxypropylene)) acrylate or
  • surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 may be used.
  • One of these surfactants may be used alone, or two or more thereof may be used in combination.
  • the content thereof is preferably 0 to 2% by mass, more preferably based on the total solid content of the composition. Is 0.0001 to 2 mass%, more preferably 0.0005 to 1 mass%.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention has solubility in dissolution inhibiting compounds, dyes, plasticizers, photosensitizers, light absorbers, and / or developers.
  • a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxy group may be further included.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain a dissolution inhibiting compound.
  • the “dissolution inhibiting compound” is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce the solubility in a developer containing an organic solvent.
  • acid degradation such as cholic acid derivatives containing acid-decomposable groups described in Proceeding of SPIE, 2724, 355 (1996) does not reduce the transmittance with respect to light having a wavelength of 220 nm or less.
  • An alicyclic or aliphatic compound containing a functional group is preferred. Examples of the acid-decomposable group and the alicyclic structure include the same ones as described above.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, the phenolic hydroxy group of the phenol compound is an acid.
  • a compound containing a structure substituted with a decomposing group is preferred.
  • the phenol compound preferably contains 1 to 9 phenol skeletons, more preferably 2 to 6 phenol skeletons.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a dissolution inhibiting compound, its content is preferably 3 to 50% by mass based on the total solid content of the composition, More preferably, it is 5 to 40% by mass.
  • a phenol compound having a molecular weight of 1000 or less can be easily obtained by referring to the methods described in, for example, JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, and European Patent 219294. Can be synthesized.
  • Examples of alicyclic or aliphatic compounds containing a carboxy group include carboxylic acid derivatives containing steroid structures such as cholic acid, deoxycholic acid and lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, And cyclohexanedicarboxylic acid.
  • SL-1 Propylene glycol monomethyl ether acetate (PGMEA)
  • SL-2 Propylene glycol monomethyl ether propionate
  • SL-3 2-heptanone
  • SL-4 Ethyl lactate
  • SL-5 Propylene glycol monomethyl ether
  • SL-6 cyclohexanone
  • SL-7 ⁇ -butyrolactone
  • SL-8 propylene carbonate
  • W-1 Megafuck F176 (DIC Corporation; Fluorine)
  • W-2 Megafuck R08 (DIC Corporation; fluorine and silicon)
  • W-3 Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
  • W-4 Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
  • W-5 KH-20 (Asahi Glass Co., Ltd.)
  • W-6 PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc .; fluorine system)
  • Examples 1 to 16 and Comparative Examples 1 to 3 The components shown in the following table are dissolved in a solvent, and a solution with a solid content of 4% by mass is prepared for each, and this is filtered through a polyethylene filter having a pore size of 0.05 ⁇ m, and the active light-sensitive or radiation-sensitive resin composition. (Hereinafter also referred to as a resist composition) was prepared.
  • the actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the following method, and the results are shown in the table.
  • An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. On top of that, the resist composition prepared above was applied and baked at 95 ° C. for 60 seconds to form a resist film having a thickness of 100 nm.
  • Examples 1 to 16 using the pattern forming method according to the present invention are actinic ray sensitive or resin containing a resin having a weight average molecular weight of 11,000 or less.
  • Comparative Example 1 using a radiation-sensitive resin composition Comparative Example 2 using an actinic ray-sensitive or radiation-sensitive resin composition not containing the compound represented by the general formula (1), and the action of an acid As compared with Comparative Example 3 using a resin that does not have a repeating unit having a group that decomposes to generate an alcoholic hydroxyl group, it is clear that there is less pattern collapse and the remaining film ratio and pattern shape are excellent.
  • Examples 2 to 15 using the actinic ray-sensitive or radiation-sensitive resin composition containing a resin having a weight average molecular weight of 12,000 or more have particularly little pattern collapse.
  • a resin having a weight average molecular weight of 15,000 or more, a compound represented by the general formula (1) and a group having a polycyclic alicyclic structure having a carbon number R of 10 or more, and an oxygen atom Examples 9, 12 and 13 using an actinic ray-sensitive or radiation-sensitive resin composition containing a basic compound containing at least one of these compounds have particularly little pattern collapse and are particularly excellent in the remaining film ratio and pattern shape. Is clear.

Abstract

L'invention concerne un procédé de formation de motif qui comprend : (I) une étape de formation d'un film utilisant une composition de résine sensible à la lumière active ou sensible aux rayonnements qui contient un composé représenté par la formule générale (1) et une résine ayant une masse moléculaire moyenne en poids de 11 000 ou plus et contenant une unité de répétition ayant un groupe qui est décomposé par l'action d'un acide et génère un groupe hydroxyle alcoolique; (II) une étape d'exposition du film; et (III) une étape de développement du film exposé par utilisation d'un liquide révélateur qui contient un solvant organique. Ce procédé de formation de motif a une excellente sensibilité, une excellente résolution de limitation, d'excellentes caractéristiques de rugosité, une excellente latitude d'exposition (EL), une excellente dépendance à la température de cuisson post-exposition (PEB) et une excellente profondeur de foyer. L'invention concerne également : une composition de résine sensible à la lumière active ou sensible aux rayonnements qui est utilisée dans le procédé de formation de motif; un film de réserve utilisant la composition de résine sensible à la lumière active ou sensible aux rayonnements; un procédé de fabrication d'un dispositif électronique utilisant le procédé de formation de motif; et un dispositif électronique. Dans la formule (1), R représente un groupe alkyle, un groupe cycloalkyle qui peut avoir un carbone de carbonyle comme chaînon de cycle, une structure de lactone, une structure de sultone, un groupe aryle ou un groupe qui est obtenu par combinaison d'au moins deux des groupes susmentionnés; et M+ représente un cation monovalent.
PCT/JP2014/070191 2013-08-27 2014-07-31 Procédé de formation de motif, composition de résine sensible à la lumière active ou sensible aux rayonnements, film de réserve l'utilisant, procédé de fabrication de dispositif électronique et dispositif et dispositif électronique WO2015029690A1 (fr)

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JP6846127B2 (ja) 2016-06-28 2021-03-24 東京応化工業株式会社 レジスト組成物及びレジストパターン形成方法
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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JP2013092723A (ja) * 2011-10-27 2013-05-16 Shin Etsu Chem Co Ltd パターン形成方法及びレジスト組成物
JP2013163652A (ja) * 2012-02-10 2013-08-22 Shin-Etsu Chemical Co Ltd 単量体、高分子化合物、レジスト材料及びパターン形成方法

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