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WO2021172173A1 - Procédé de production de composition de résine sensible aux rayons actiniques ou sensible aux rayonnements, procédé de formation de motif et procédé de fabrication de dispositif électronique - Google Patents

Procédé de production de composition de résine sensible aux rayons actiniques ou sensible aux rayonnements, procédé de formation de motif et procédé de fabrication de dispositif électronique Download PDF

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Publication number
WO2021172173A1
WO2021172173A1 PCT/JP2021/006202 JP2021006202W WO2021172173A1 WO 2021172173 A1 WO2021172173 A1 WO 2021172173A1 JP 2021006202 W JP2021006202 W JP 2021006202W WO 2021172173 A1 WO2021172173 A1 WO 2021172173A1
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Prior art keywords
group
sensitive
acid
radiation
resin composition
Prior art date
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Ceased
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PCT/JP2021/006202
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English (en)
Japanese (ja)
Inventor
佑真 楜澤
敬充 冨賀
東　耕平
文博 吉野
田中　匠
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Fujifilm Corp
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Fujifilm Corp
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Priority to KR1020227023526A priority Critical patent/KR102658620B1/ko
Priority to JP2022503316A priority patent/JP7300055B2/ja
Publication of WO2021172173A1 publication Critical patent/WO2021172173A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a method for producing a sensitive light-sensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for producing an electronic device.
  • lithography In the manufacturing process of semiconductor devices such as ICs (Integrated Circuits, integrated circuits) and LSIs (Large Scale Integrated Circuits, large-scale integrated circuits), microfabrication by lithography using sensitive light-sensitive or radiation-sensitive resin compositions is performed. It is done.
  • the lithography method include a method of forming a resist film with an actinic cheilitis or radiation-sensitive resin composition, and then exposing and developing the obtained resist film.
  • the active light-sensitive or radiation-sensitive resin composition a composition containing a resin having a group decomposed by the action of an acid to generate a polar group, a photoacid generator, an acid diffusion control agent, and a solvent is used.
  • the actinic light-sensitive or radiation-sensitive resin composition may contain an acidic compound (see, for example, Patent Document 1 and Patent Document 2).
  • a resin having a group that decomposes by the action of an acid to generate a polar group (acid-degradable resin) and a compound that generates an acid by irradiation with active light or radiation (photoacid generator).
  • the sensitive light-sensitive or radiation-sensitive resin composition containing the acid diffusion control agent, the solvent, and the acidic compound may be obtained depending on the production method thereof. It was found that there are cases where improvement is required for the shape and retention stability of the pattern formed using.
  • plaqueing means to bake (post) after exposing an actinic cheilitis or radiation-sensitive film (typically a resist film) formed by using the actinic cheilitis or radiation-sensitive resin composition.
  • Exposure bake It means to set a time (reservation time) before performing PEB). Further, the CD (critical dimension) of the pattern formed by developing the attracted actinic cheilitis or radiation-sensitive film becomes the CD of the pattern formed by developing without providing the retention time. On the other hand, the fact that there is little fluctuation is said to be "excellent in retention stability.”
  • An object of the present invention is a method for producing a sensitive light-sensitive or radiation-sensitive resin composition, which has a good shape of a pattern to be formed and excellent retention stability, and the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition. It is an object of the present invention to provide a pattern forming method using a manufacturing method of an article, and a manufacturing method of an electronic device.
  • a method for producing a sensitive light-sensitive or radiation-sensitive resin composition which comprises the step (2) in this order.
  • [2] The method for producing a sensitive actinic or radiation-sensitive resin composition according to [1], wherein the step (2) is performed 30 minutes or more after the step (1) is completed. [3] The feeling according to [1] or [2], wherein in the step (2), the amount of the acidic compound added is 0.01 to 5% by mass with respect to the total solid content of the contents in the container.
  • a method for producing an active light-sensitive or radiation-sensitive resin composition [4] W1 / W2, which is the ratio of the mass W1 of the acidic compound in the step (2) to the mass W2 of the acid diffusion control agent in the step (1), is 1.0 to 20, [1] to The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to any one of [3].
  • [5] The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the acidic compound is an organic carboxylic acid or an oxo acid of phosphorus.
  • [6] The sensitive light-sensitive or radiation-sensitive property according to any one of [1] to [5], wherein the first acid dissociation constant pKa of the acidic compound at 25 ° C. is 1.0 ⁇ pKa ⁇ 5.0.
  • a method for producing a resin composition [7] The method for producing a sensitive actinic or radiation-sensitive resin composition according to any one of [1] to [6], wherein the acidic compound is salicylic acid or benzoic acid.
  • a method for producing a sensitive light-sensitive or radiation-sensitive resin composition having a good shape of a formed pattern and excellent retention stability the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition. It is possible to provide a pattern forming method using a manufacturing method of an object and a manufacturing method of an electronic device.
  • the schematic diagram of an example of the manufacturing apparatus which can be used in the manufacturing method of the actinic cheilitis or radiation-sensitive resin composition The schematic diagram which showed the step (1), step (1-2), step (2) and step (3) of Example 1, which is an example of the manufacturing method of the actinic cheilitis or radiation-sensitive resin composition.
  • the numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the notation that does not describe substitution or non-substitution includes a group having a substituent as well as a group having no substituent.
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the "organic group” in the present specification means a group containing at least one carbon atom.
  • the bonding direction of the divalent group described in the present specification is not limited unless otherwise specified.
  • (meth) acrylic is a general term including acrylic and methacryl, and means “at least one of acrylic and methacrylic”.
  • (meth) acrylic acid is a general term including acrylic acid and methacrylic acid, and means “at least one of acrylic acid and methacrylic acid”.
  • the weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (also referred to as molecular weight distribution) (Mw / Mn) of the resin are GPC (Gel Permeation Chromatography) apparatus (HLC-manufactured by Toso).
  • the term “active light” or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, and electron beams (EB:). It means Electron Beam) and the like.
  • the term “light” means active light or radiation.
  • exposure refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, EUV, etc., but also electron beams and ions. Includes drawing with particle beams such as beams.
  • the method for producing a sensitive light-sensitive or radiation-sensitive resin composition of the present invention is: A step (1) of putting a resin having a group that decomposes by the action of an acid to generate a polar group, a compound that generates an acid by irradiation with active light or radiation, an acid diffusion control agent, and a solvent into a container, and An acidic compound is added to a container containing a resin having a group that decomposes by the action of the acid to generate a polar group, a compound that generates an acid by irradiation with active light or radiation, an acid diffusion control agent, and a solvent. Step (2) is included in this order.
  • the present inventors first, as a method for producing an active light-sensitive or radiation-sensitive resin composition containing an acid-degradable resin, a photoacid generator, an acid diffusion control agent, a solvent, and an acidic compound. , An acid-degradable resin, a photoacid generator, an acid diffusion control agent, and a solvent are placed in a container, and then an acidic compound is added to the container containing these (that is, a method of post-adding the acidic compound). ), It was found that the shape of the formed pattern and the retention stability are improved.
  • the mechanism by which the production method of the present invention solves the problem of the present invention is not always clear, but the present inventors presume as follows.
  • a sensitive light-sensitive or radiation-sensitive resin composition (typically a resist composition) containing an acid-degradable resin, a photoacid generator, an acid diffusion control agent, and a solvent is an acid diffusion control agent. Due to the influence of basic components such as nitrogen or ammonia in the atmosphere, the desired pattern shape may not be obtained. In order to suppress the influence of these basic components, it is conceivable to add an acidic compound (typically a weak acid) to the actinic light-sensitive or radiation-sensitive resin composition. However, when the acid diffusion control agent and the acidic compound are added at the same time during the preparation of the sensitive light-sensitive or radiation-sensitive resin composition, the acid diffusion control agent and the acidic compound form a salt, and an insoluble matter is generated.
  • an acidic compound typically a weak acid
  • the acid diffusion control agent is put into the container in the step (1), and then the acidic compound is added in the step (2).
  • the acid diffusion control agent contained in the container in the step (1) interacts with other components (for example, interacts with the polar group contained in the acid-degradable resin) to be acidic in the step (2). Even if the compound is added, the formation reaction of the salt between the acid diffusion control agent and the acidic compound is unlikely to occur, and the acidic compound may be present in the originally intended form in the sensitive light-sensitive or radiation-sensitive resin composition. Therefore, it is considered that the effect originally obtained by adding the acidic compound is sufficiently exhibited.
  • a resin having a group that decomposes by the action of an acid to generate a polar group, a photoacid generator that generates an acid by irradiation with active light or radiation, an acid diffusion control agent, and a solvent are added to the container. It is a process to put in.
  • the container in the step (1) is not particularly limited, and for example, a known container used in the production of the actinic cheilitis or radiation-sensitive resin composition can be used.
  • the container may or may not have a lid as long as it can contain each of the above components.
  • the container may be hermetically sealed or hermetically sealed, and may not be hermetically sealed or may not be hermetically sealed.
  • the material of the container is not particularly limited.
  • the size of the container is not limited, and it may be a size suitable for ordinary laboratories or a size suitable for industrial production.
  • the container may be capable of performing operations such as heating, pressurizing, and stirring the components contained therein.
  • a reaction vessel for example, a kettle (for example, a reaction kettle), a tank (for example, a stirring tank), or the like can be used as a container.
  • the container has a mechanism for putting each component into the container (for example, introduction pipe), a mechanism for discharging from the container (for example, discharge pipe), and a mechanism for reintroducing what is discharged from the container into the container (circulation mechanism). ) Etc. may be provided.
  • the production method of the present invention can be carried out using an apparatus for producing a sensitive light-sensitive or radiation-sensitive resin composition, and the container of the step (1) is preferably a sensitive light-sensitive or radiation-sensitive resin composition.
  • a stirring tank in a product manufacturing apparatus can be used.
  • the apparatus for producing the actinic light-sensitive or radiation-sensitive resin composition that can be used in the present invention is not particularly limited, and a known production apparatus can be used.
  • FIG. 1 shows a schematic view of an example of a manufacturing apparatus that can be used in the method for manufacturing a sensitive light-sensitive or radiation-sensitive resin composition of the present invention.
  • the manufacturing apparatus 100 has a stirring tank 10, a stirring shaft 12 rotatably mounted in the stirring tank 10, a stirring blade 14 mounted on the stirring shaft 12, and a bottom and one end of the stirring tank 10.
  • the circulation pipe 16 which is connected and the other end is connected to the upper part of the stirring tank 10, the filter 18 arranged in the middle of the circulation pipe 16, the discharge pipe 20 connected to the circulation pipe 16, and the end of the discharge pipe 20. It has a discharge nozzle 22 arranged in the portion.
  • the liquid contact portion (the portion in contact with the liquid) in the apparatus is lined or coated with a fluororesin or the like.
  • the stirring tank 10 is particularly a stirring tank capable of containing a resin having a group that decomposes by the action of an acid to generate a polar group, a compound that generates an acid by irradiation with active light or radiation, an acid diffusion control agent, a solvent, and the like.
  • Examples thereof include known stirring tanks without limitation.
  • the shape of the bottom of the stirring tank 10 is not particularly limited, and examples thereof include a dish-shaped end plate shape, a semi-elliptical end plate shape, a flat end plate shape, a conical end plate shape, and the like, and a dish-shaped end plate shape or a semi-elliptical end plate shape is preferable.
  • a baffle plate may be installed in the stirring tank 10 in order to improve the stirring efficiency.
  • the number of baffle plates is not particularly limited, and 2 to 8 plates are preferable.
  • the width of the baffle plate is not particularly limited, and is preferably 1/8 to 1/2 of the diameter of the stirring tank.
  • the length of the baffle plate in the height direction of the stirring tank is not particularly limited, but is preferably 1/2 or more, more preferably 2/3 or more of the height from the bottom of the stirring tank to the liquid level of the component to be charged. 3/4 or more is more preferable.
  • a drive source for example, a motor or the like
  • the stirring blade 14 is rotated, and each component put into the stirring tank 10 is stirred.
  • the shape of the stirring blade 14 is not particularly limited, and examples thereof include a paddle blade, a propeller blade, and a turbine blade.
  • the stirring tank 10 may have a material charging port for charging various materials into the stirring tank.
  • the stirring tank 10 may have a gas introduction port for introducing gas into the stirring tank 10.
  • the stirring tank 10 may have a gas discharge port for discharging the gas inside the stirring tank 10 to the outside of the stirring tank.
  • a cleaning nozzle for example, a spray ball
  • a spray ball may be arranged in the upper part of the tank.
  • the configuration of the apparatus for producing the sensitive light-sensitive or radiation-sensitive resin composition is not limited to FIG. 1, and at least a container (preferably a stirring tank) may be provided.
  • the inside of the container may or may not be agitated.
  • the stirring method is not particularly limited, but for example, it is preferably performed by the above-mentioned stirring blade.
  • the method of putting each component in the container in the step (1) is not particularly limited.
  • a method of charging each component from the material input port of the stirring tank can be mentioned.
  • each component may be added sequentially or collectively. Further, when adding one kind of component, it may be added at once, or it may be added in a plurality of times. Further, when each component is sequentially charged into the container, the order in which each component is charged is not particularly limited.
  • Resin having a group that decomposes by the action of acid to produce a polar group A resin having a group which is decomposed by the action of an acid to generate a polar group (also referred to as “resin (A)”) will be described.
  • the resin (A) preferably has a repeating unit (Aa) having an acid-degradable group (hereinafter, also simply referred to as "repeating unit (Aa)").
  • An acid-degradable group is a group that is decomposed by the action of an acid to produce a polar group.
  • the acid-degradable group preferably has a structure in which the polar group is protected by a leaving group that is eliminated by the action of an acid. That is, it is preferable that the resin (A) has a repeating unit (Aa) having a group which is decomposed by the action of an acid to generate a polar group.
  • the polarity of the resin having the repeating unit (Aa) is increased by the action of the acid, the solubility in the alkaline developer is increased, and the solubility in the organic solvent is decreased.
  • an alkali-soluble group is preferable, and for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonylamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (alkyl).
  • Sulfonyl) (alkylcarbonyl) imide group bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and ,
  • An acidic group such as a tris (alkylsulfonyl) methylene group, and an alcoholic hydroxyl group.
  • polar group a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable.
  • Rx 1 to Rx 3 independently represent an alkyl group (linear or branched chain) or a cycloalkyl group (monocyclic or polycyclic), respectively.
  • Rx 1 to Rx 3 are alkyl groups (linear or branched chain)
  • Rx 1 to Rx 3 preferably independently represent a linear or branched alkyl group
  • Rx 1 to Rx 3 may independently represent a linear alkyl group. More preferred. Two of Rx 1 to Rx 3 may be combined to form a monocyclic ring or a polycyclic ring.
  • Examples of the alkyl group of Rx 1 to Rx 3 include 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, and a t-butyl group. preferable.
  • Examples of the cycloalkyl groups of Rx 1 to Rx 3 include a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • the polycyclic cycloalkyl group of is preferred.
  • Examples of the cycloalkyl group formed by combining two of Rx 1 to Rx 3 include a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, and a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca.
  • a polycyclic cycloalkyl group such as an nyl group and an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
  • the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced.
  • the group represented by the formula (Y1) or the formula (Y2) is, for example, an embodiment in which Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl group. Is preferable.
  • R 36 to R 38 each independently represent a hydrogen atom or a monovalent substituent.
  • R 37 and R 38 may be combined with each other to form a ring.
  • the monovalent substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like. It is also preferable that R 36 is a hydrogen atom.
  • L 1 and L 2 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which these are combined (for example, a group in which an alkyl group and an aryl group are combined).
  • .. M represents a single bond or a divalent linking group.
  • Q is an alkyl group which may have a hetero atom, a cycloalkyl group which may have a hetero atom, an aryl group which may have a hetero atom, an amino group, an ammonium group, a mercapto group, or a cyano.
  • the alkyl group and the cycloalkyl group for example, one of the methylene groups may be replaced with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.
  • one of L 1 and L 2 is a hydrogen atom and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
  • L 2 is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group.
  • the secondary alkyl group include an isopropyl group, a cyclohexyl group and a norbornyl group
  • examples of the tertiary alkyl group include a tert-butyl group and an adamantan ring group.
  • Tg glass transition temperature
  • activation energy are high, so that in addition to ensuring the film strength, fog can be suppressed.
  • Ar represents an aromatic ring group.
  • Rn represents an alkyl group, a cycloalkyl group or an aryl group.
  • Rn and Ar may be combined with each other to form a non-aromatic ring.
  • Ar is more preferably an aryl group.
  • repeating unit (Aa) the repeating unit represented by the formula (Aa1) is also preferable.
  • L 1 represents a divalent linking group which may have a fluorine atom or an iodine atom
  • R 1 is an alkyl group which may have a hydrogen atom, a fluorine atom, an iodine atom, a fluorine atom or an iodine atom.
  • it represents an aryl group which may have a fluorine atom or an iodine atom
  • R 2 represents a desorbing group which is eliminated by the action of an acid and may have a fluorine atom or an iodine atom.
  • at least one of L 1 , R 1 , and R 2 has a fluorine atom or an iodine atom.
  • L 1 represents a divalent linking group which may have a fluorine atom or an iodine atom.
  • the fluorine atom or a linking group may divalent have a iodine atom, -CO -, - O -, - S -, - SO -, - SO 2 -, have a fluorine atom or an iodine atom Examples thereof include a hydrocarbon group which may be used (for example, an alkylene group, a cycloalkylene group, an alkaneylene group, an arylene group, etc.), a linking group in which a plurality of these groups are linked, and the like.
  • the L 1, -CO-, or, - arylene - alkylene group having a fluorine atom or iodine atom - are preferred.
  • the arylene group a phenylene group is preferable.
  • the alkylene group may be linear or branched. The number of carbon atoms of the alkylene group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable.
  • the total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but 2 or more is preferable, 2 to 10 is more preferable, and 3 to 10 is more preferable in that the effect of the present invention is more excellent. 6 is more preferable.
  • R 1 represents an alkyl group which may have a hydrogen atom, a fluorine atom, an iodine atom, a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom.
  • the alkyl group may be linear or branched.
  • the number of carbon atoms of the alkyl group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable.
  • the total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited, but 1 or more is preferable, 1 to 5 is more preferable, and 1 to 1 to 5 is preferable in that the effect of the present invention is more excellent. 3 is more preferable.
  • the alkyl group may have a hetero atom such as an oxygen atom other than the halogen atom.
  • R 2 represents a leaving group that is eliminated by the action of an acid and may have a fluorine atom or an iodine atom.
  • Rx 11 to Rx 13 are alkyl groups (linear or branched) or fluorine atoms which may independently have a fluorine atom or an iodine atom, respectively. Represents a cycloalkyl group (monocyclic or polycyclic) that may have an iodine atom. When all of Rx 11 to Rx 13 are alkyl groups (linear or branched chain), it is preferable that at least two of Rx 11 to Rx 13 are methyl groups.
  • Rx 11 to Rx 13 are the same as Rx 1 to Rx 3 in (Y1) and (Y2) described above, except that they may have a fluorine atom or an iodine atom, and are an alkyl group and a cycloalkyl group. It is the same as the definition and the preferable range of.
  • R 136 to R 138 each independently represent a hydrogen atom, or a monovalent substituent that may have a fluorine atom or an iodine atom.
  • R 137 and R 138 may be combined with each other to form a ring.
  • the monovalent substituent which may have a fluorine atom or an iodine atom includes an alkyl group which may have a fluorine atom or an iodine atom, and a cycloalkyl group which may have a fluorine atom or an iodine atom.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a hetero atom such as an oxygen atom in addition to the fluorine atom and the iodine atom.
  • alkyl group cycloalkyl group, aryl group, and aralkyl group, for example, even if one of the methylene groups is replaced with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group. good.
  • L 11 and L 12 independently have an alkyl group selected from the group consisting of a hydrogen atom; a fluorine atom, an iodine atom and an oxygen atom; a fluorine atom, an iodine atom and an alkyl group.
  • a cycloalkyl group which may have a hetero atom selected from the group consisting of oxygen atoms; an aryl group which may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; or , A group in which these are combined (for example, a group in which an alkyl group and a cycloalkyl group are combined, which may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom).
  • M 1 represents a single bond or a divalent linking group.
  • Q 1 represents a fluorine atom, an alkyl group which may have a hetero atom selected from the group consisting of iodine atoms and an oxygen atom; Yes fluorine atom, a hetero atom selected from the group consisting of iodine atoms and an oxygen atom May have a cycloalkyl group; may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; an amino group; an ammonium group; a mercapto group; a cyano group; an aldehyde group.
  • Ar 1 represents an aromatic ring group which may have a fluorine atom or an iodine atom.
  • Rn 1 may have an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, or an aryl which may have a fluorine atom or an iodine atom.
  • Rn 1 and Ar 1 may be combined with each other to form a non-aromatic ring.
  • repeating unit (Aa) a repeating unit represented by the general formula (AI) is also preferable.
  • Xa 1 represents a hydrogen atom or an alkyl group.
  • T represents a single bond or a divalent linking group.
  • Rx 1 to Rx 3 independently represent an alkyl group (linear or branched chain) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched chain), it is preferable that at least two of Rx 1 to Rx 3 are methyl groups. Two of Rx 1 to Rx 3 may be bonded to form a cycloalkyl group (monocyclic or polycyclic).
  • the alkyl group represented by Xa 1 may have a substituent.
  • the alkyl group include groups represented by methyl group or -CH 2 -R 11.
  • R 11 represents a halogen atom (fluorine atom or the like), a hydroxyl group or a monovalent substituent.
  • the halogen atom may be substituted, an alkyl group having 5 or less carbon atoms, or a halogen atom may be substituted.
  • Examples thereof include an acyl group having 5 or less carbon atoms and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkyl group having 3 or less carbon atoms is preferable, and a methyl group is more preferable.
  • Xa 1 a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferable.
  • Examples of the divalent linking group of T include an alkylene group, an aromatic ring group, an -COO-Rt- group, an -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, and is preferably a -CH 2- group,- (CH 2 ) 2- group, or- (CH 2 ) 3- Groups are more preferred.
  • Examples of the alkyl group of Rx 1 to Rx 3 include 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, and a t-butyl group. preferable.
  • Examples of the cycloalkyl group of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • the polycyclic cycloalkyl group of is preferred.
  • a cyclopentyl group and a monocyclic cycloalkyl group such as a cyclohexyl group are preferable, and in addition, a norbornyl group and a tetracyclodecanyl group are used.
  • Tetracyclododecanyl group, and polycyclic cycloalkyl group such as adamantyl group are preferable.
  • a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable.
  • the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced.
  • the repeating unit represented by the general formula (AI) for example, it is preferable that Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl group.
  • the substituents include, for example, an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms) and the like.
  • the number of carbon atoms in the substituent is preferably 8 or less.
  • the repeating unit represented by the general formula (AI) is preferably an acid-degradable (meth) acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T is a single bond. It is a repeating unit that represents.
  • the resin (A) may have one type of repeating unit (Aa) alone, or may have two or more types.
  • the content of the repeating unit (Aa) (total content when two or more repeating units (Aa) are present) is 15 to 80 mol% with respect to all the repeating units in the resin (A). Is preferable, and 20 to 70 mol% is more preferable.
  • the resin (A) has at least one repeating unit selected as the repeating unit (Aa) from the group consisting of the repeating units represented by the following general formulas (A-VIII) to (A-XII). Is preferable.
  • R 5 represents a tert-butyl group, a 1,1'-dimethylpropyl group, or a -CO-O- (tert-butyl) group.
  • R 6 and R 7 each independently represent a monovalent substituent. Examples of the monovalent substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like.
  • p represents 1 or 2.
  • R 8 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 9 represents an alkyl group having 1 to 3 carbon atoms
  • R 10 represents an alkyl group having 1 to 3 carbon atoms or an adamantyl group.
  • the resin (A) may have a repeating unit having a polar group such as an acid group, a lactone structure, a sultone structure, a carbonate structure, and a hydroxyadamantan structure, in addition to the repeating unit (Aa) having an acid-degradable group. preferable. Since the resin (A) has a repeating unit having a polar group, the polar group in the resin (A) put in the container in the step (1) and the acid diffusion control agent interact with each other to cause the step (2). ), It is considered that the acid diffusion control agent and the acidic compound are less likely to react with each other when the acidic compound is added, and the obtained pattern shape and retention stability are more likely to be improved.
  • a polar group such as an acid group, a lactone structure, a sultone structure, a carbonate structure, and a hydroxyadamantan structure
  • the resin (A) may have a repeating unit having an acid group.
  • a repeating unit represented by the following general formula (B) is preferable.
  • R 3 represents a hydrogen atom or a monovalent substituent which may have a fluorine atom or an iodine atom.
  • the fluorine atom or an iodine atom monovalent substituent which may have a group represented by -L 4 -R 8 are preferred.
  • L 4 represents a single bond or an ester group.
  • R 8 is an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, and the like. Alternatively, a group combining these can be mentioned.
  • R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.
  • L 2 represents a single bond or an ester group.
  • L 3 represents a (n + m + 1) -valent aromatic hydrocarbon ring group or a (n + m + 1) -valent alicyclic hydrocarbon ring group.
  • the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group.
  • the alicyclic hydrocarbon ring group may be monocyclic or polycyclic, and examples thereof include cycloalkyl ring groups.
  • R 6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group).
  • L 3 is preferably an aromatic hydrocarbon ring group having a (n + m + 1) valence.
  • R 7 represents a halogen atom.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • m represents an integer of 1 or more.
  • m is preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.
  • n represents an integer of 0 or 1 or more.
  • n is preferably an integer of 1 to 4.
  • (n + m + 1) is preferably an integer of 1 to 5.
  • repeating unit having an acid group a repeating unit represented by the following general formula (I) is also preferable.
  • R 41 , R 42 and R 43 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 42 may be bonded to Ar 4 to form a ring, in which case R 42 represents a single bond or an alkylene group.
  • X 4 represents a single bond, -COO-, or -CONR 64-
  • R 64 represents a hydrogen atom or an alkyl group.
  • L 4 represents a single bond or an alkylene group.
  • Ar 4 represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when combined with R 42 to form a ring.
  • n represents an integer from 1 to 5.
  • the alkyl groups of R 41 , R 42 , and R 43 in the general formula (I) include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, and 2-ethylhexyl.
  • Alkyl groups having 20 or less carbon atoms such as groups, octyl groups, and dodecyl groups are preferable, alkyl groups having 8 or less carbon atoms are more preferable, and alkyl groups having 3 or less carbon atoms are further preferable.
  • the cycloalkyl groups of R 41 , R 42 , and R 43 in the general formula (I) may be monocyclic or polycyclic. Of these, a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group is preferable.
  • Examples of the halogen atoms of R 41 , R 42 , and R 43 in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group contained in the alkoxycarbonyl group of R 41 , R 42 , and R 43 in the general formula (I) is preferably the same as the alkyl group in R 41 , R 42 , and R 43.
  • Ar 4 represents an (n + 1) -valent aromatic ring group.
  • the divalent aromatic ring group when n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylen group, a naphthylene group, and an anthracenylene group.
  • an aromatic containing a heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrol ring, a triazine ring, an imidazole ring, a benzoimidazole ring, a triazole ring, a thiazazole ring, and a thiazole ring. Ring groups are preferred.
  • (n + 1) -valent aromatic ring group when n is an integer of 2 or more, (n-1) arbitrary hydrogen atoms are removed from the above-mentioned specific example of the divalent aromatic ring group. There is a group that is made up of.
  • the (n + 1) -valent aromatic ring group may further have a substituent.
  • Examples of the substituents that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1) -valent aromatic ring group can have include R 41 , R 42 , and R 41 in the general formula (I). , R 43 , an alkoxy group such as an alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; an aryl group such as a phenyl group; and the like.
  • R 64 represents a hydrogen atom or an alkyl group
  • the alkyl group for R 64 in, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, sec- Examples thereof include alkyl groups having 20 or less carbon atoms such as a butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and an alkyl group having 8 or less carbon atoms is preferable.
  • X 4 a single bond, -COO-, or -CONH- is preferable, and a single bond or -COO- is more preferable.
  • the alkylene group for L 4, a methylene group, an ethylene group, a propylene group, butylene group, hexylene group, and is preferably an alkylene group having 1 to 8 carbon atoms such as octylene group.
  • Ar 4 an aromatic ring group having 6 to 18 carbon atoms is preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are more preferable.
  • a 1, 2 or 3.
  • the resin (A) preferably has a repeating unit (A-1) derived from hydroxystyrene as a repeating unit having an acid group.
  • the repeating unit (A-1) derived from hydroxystyrene include a repeating unit represented by the following general formula (1).
  • A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
  • R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group or an aryloxycarbonyl group, and there are a plurality of them. In some cases, they may be the same or different. When having a plurality of Rs, they may form a ring jointly with each other.
  • a hydrogen atom is preferable as R.
  • a represents an integer of 1 to 3
  • b represents an integer of 0 to (5-a).
  • repeating unit (A-1) a repeating unit represented by the following general formula (AI) is preferable.
  • a resist composition containing a resin (A) having a repeating unit (A-1) is preferable for KrF exposure, EB exposure, or EUV exposure.
  • the content of the repeating unit (A-1) is preferably 30 to 99 mol%, more preferably 40 to 99 mol%, and 50 to 99 mol% with respect to all the repeating units in the resin (A). Is more preferable.
  • the resin (A) may have a repeating unit (A-2) having at least one selected from the group consisting of a lactone structure, a carbonate structure, a sultone structure, and a hydroxyadamantane structure.
  • the lactone structure or sultone structure in the repeating unit having a lactone structure or sultone structure is not particularly limited, but a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable, and the 5- to 7-membered ring lactone structure is a bicyclo structure.
  • the other ring structure is fused in the form of forming a spiro structure, or the other ring structure is fused in the form of a bicyclo structure or a spiro structure in a 5- to 7-membered sultone structure. Is more preferable.
  • Examples of the repeating unit having a lactone structure or a sultone structure include the repeating units described in paragraphs 0094 to 0107 of WO2016 / 136354.
  • the resin (A) may have a repeating unit having a carbonate structure.
  • the carbonate structure is preferably a cyclic carbonate structure.
  • Examples of the repeating unit having a carbonate structure include the repeating unit described in paragraphs 0106 to 0108 of WO2019 / 054311.
  • the resin (A) may have a repeating unit having a hydroxyadamantane structure.
  • Examples of the repeating unit having a hydroxyadamantane structure include a repeating unit represented by the following general formula (AIIA).
  • R 1 c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
  • R 2 c to R 4 c each independently represent a hydrogen atom or a hydroxyl group. However, at least one of R 2 c to R 4 c represents a hydroxyl group. It is preferable that one or two of R 2 c to R 4 c are hydroxyl groups and the rest are hydrogen atoms.
  • the resin (A) may have a repeating unit having a fluorine atom or an iodine atom.
  • Examples of the repeating unit having a fluorine atom or an iodine atom include the repeating unit described in paragraphs 0080 to 0081 of JP-A-2019-045864.
  • the resin (A) may have a repeating unit having a group that generates an acid by irradiation with radiation as a repeating unit other than the above.
  • Examples of the repeating unit having a fluorine atom or an iodine atom include the repeating unit described in paragraphs 0092 to 0906 of JP-A-2019-045864.
  • the resin (A) may have a repeating unit having an alkali-soluble group.
  • the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol in which the ⁇ -position is substituted with an electron-withdrawing group (for example, a hexafluoroisopropanol group).
  • a carboxyl group is preferred. Since the resin (A) has a repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased.
  • the repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit made of acrylic acid and methacrylic acid, or a repeating unit in which the alkali-soluble group is directly bonded to the main chain of the resin via a linking group. Repeat units to which an alkali-soluble group is attached can be mentioned.
  • the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure.
  • a repeating unit made of acrylic acid or methacrylic acid is preferable.
  • the resin (A) may further have a repeating unit that has neither an acid-degradable group nor a polar group.
  • the repeating unit having neither an acid-decomposable group nor a polar group preferably has an alicyclic hydrocarbon structure.
  • Examples of the repeating unit having neither an acid-degradable group nor a polar group include the repeating unit described in paragraphs 0236 to 0237 of U.S. Patent Application Publication No. 2016/0026083, and the U.S. Patent Application Publication No. The repeating unit described in paragraph 0433 of the specification of 2016/0070167 is mentioned.
  • the resin (A) contains various repeating structural units for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like. You may have.
  • the resin (A) is composed of repeating units in which all the repeating units are derived from a (meth) acrylate-based monomer (a monomer having a (meth) acrylic group).
  • any resin may be used: one in which all the repeating units are derived from a methacrylate-based monomer, one in which all the repeating units are derived from an acrylate-based monomer, and one in which all the repeating units are derived from a methacrylate-based monomer and an acrylate-based monomer. be able to.
  • the repeating unit derived from the acrylate-based monomer is preferably 50 mol% or less based on all the repeating units in the resin (A).
  • the resin (A) does not have a repeating unit having a silicon atom, and preferably has a repeating unit derived from a monomer having a (meth) acrylic group.
  • the resin (A) is substantially aromatic from the viewpoint of the transmission of ArF light. It is preferable not to have a group group. More specifically, the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally, based on all the repeating units of the resin (A). Is more preferably 0 mol%, i.e. not having a repeating unit having an aromatic group.
  • the resin (A) may have a monocyclic or polycyclic alicyclic hydrocarbon structure. It is preferable, and it is preferable that neither a fluorine atom nor a silicon atom is contained.
  • the resin (A) is an aromatic hydrocarbon group. It is preferable to have a repeating unit having a phenolic hydroxyl group, and more preferably to have a repeating unit having a phenolic hydroxyl group. Examples of the repeating unit having a phenolic hydroxyl group include the repeating unit derived from hydroxystyrene (A-1) and the repeating unit derived from hydroxystyrene (meth) acrylate.
  • the resin (A) is a phenolic hydroxyl group hydrogen atom. It is also preferable to have a repeating unit having a structure protected by a group (leaving group) that decomposes and desorbs by the action of an acid.
  • the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is for KrF exposure, EB exposure or EUV exposure, it has an aromatic hydrocarbon group contained in the resin (A).
  • the content of the repeating unit is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, still more preferably 50 to 100 mol%, based on all the repeating units in the resin (A).
  • the resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
  • the weight average molecular weight (Mw) of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of the resin (A) is a polystyrene-equivalent value measured by the above-mentioned GPC method.
  • the dispersity (molecular weight distribution) of the resin (A) is usually 1 to 5, preferably 1 to 3, and more preferably 1.1 to 2.0. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the side wall of the pattern, and the better the roughness.
  • the content of the resin (A) is 50 with respect to the total solid content of the sensitive light-sensitive or radiation-sensitive resin composition. It is preferably from 99.9% by mass, more preferably from 60 to 99.0% by mass. Therefore, the resin (A) to be put into the container in the step (1) so that the content of the resin (A) in the actinic light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is within the above range. It is preferable to adjust the amount of.
  • the resin (A) may be used alone or in combination of two or more.
  • the solid content means a component other than the solvent. Even if the properties of the components other than the solvent are liquid, they are treated as solids.
  • the total solid content means the sum of all the solid content.
  • a compound that generates an acid by irradiation with active light or radiation (also referred to as “photoacid generator (C)”) will be described.
  • the photoacid generator (C) is not particularly limited as long as it is a compound that generates an acid by being irradiated with active light or radiation.
  • the photoacid generator (C) may be in the form of a small molecule compound or may be incorporated in a part of the polymer. Further, the form of the small molecule compound and the form incorporated in a part of the polymer may be used in combination.
  • the weight average molecular weight (Mw) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less. ..
  • the photoacid generator (C) may be incorporated in a part of the resin (A), or may be incorporated in a resin different from the resin (A).
  • the photoacid generator (C) is preferably in the form of a small molecule compound.
  • the photoacid generator (C) is preferably a compound that generates an organic acid by irradiation with active light or radiation, a compound that generates an organic acid by irradiation with active light or radiation, and a fluorine atom in the molecule. Alternatively, it is more preferably a compound having an iodine atom.
  • the organic acid include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphor sulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkylcarboxylic acid, etc.), and the like. Examples thereof include carbonylsulfonylimide acid, bis (alkylsulfonyl) imide acid, and tris (alkylsulfonyl) methidoic acid.
  • Photoacid generator (C) include, for example, a compound represented by the following general formula (ZI), a compound represented by the following general formula (ZII), and a compound represented by the following general formula (ZIII). Examples include compounds.
  • R 201 , R 202 and R 203 each independently represent an organic group.
  • the number of carbon atoms of the organic group as R 201 , R 202 and R 203 is generally 1 to 30, preferably 1 to 20.
  • 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 two of the group formed by bonding of the R 201 ⁇ R 203, an alkylene group (e.g., butylene, pentylene) and -CH 2 -CH 2 -O-CH 2 -CH 2 - and the like can.
  • Z - represents an anion.
  • the photoacid generator (C) 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), and at least one of R 201 ⁇ R 203 of another compound represented by formula (ZI), a single bond Alternatively, it may be a compound having a structure bonded via a linking group.
  • the compound (ZI-1) is an aryl sulfonium compound in which at least one of R 201 to R 203 of the above general formula (ZI) is an aryl group, that is, a compound having an aryl sulfonium as a cation.
  • R 201 to R 203 may be an aryl group, or a part of R 201 to R 203 may be an aryl group and the rest may be an alkyl group or a cycloalkyl group.
  • aryl sulfonium compound examples include a triaryl sulfonium compound, a diallyl alkyl sulfonium compound, an aryl dialkyl sulfonium compound, a diallyl cycloalkyl sulfonium compound, and an aryl dicycloalkyl sulfonium compound.
  • aryl group of the aryl sulfonium compound a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
  • the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues and the like.
  • the aryl sulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
  • the alkyl group or cycloalkyl group contained in the arylsulfonium compound as required is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms.
  • the group is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.
  • the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 are independently an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), and an aryl group (for example, carbon number of carbon atoms). 6 to 14), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be used as a substituent.
  • the compound (ZI-2) is a compound in which R 201 to R 203 in the general formula (ZI) each independently represent an organic group having no aromatic ring.
  • the aromatic ring also includes an aromatic ring containing a hetero atom.
  • the organic group having no aromatic ring as R 201 to R 203 generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
  • Each of R 201 to R 203 is independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and more preferably a linear or branched 2-oxoalkyl group or 2-oxocycloalkyl group.
  • it is an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.
  • the alkyl group and cycloalkyl group of R 201 to R 203 are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.). Butyl group and pentyl group), and cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group) can be mentioned.
  • R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
  • the compound (ZI-3) is represented by the following general formula (ZI-3) and has a phenacylsulfonium salt structure.
  • R 1c to R 5c are independently hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cyclo.
  • R 6c and R 7c independently represent 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 represent 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 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y are combined to form a ring structure, respectively.
  • this ring structure may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
  • the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings in which two or more of these rings are combined.
  • the ring structure include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.
  • Examples of the group formed by combining any two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y include a butylene group and a pentylene group.
  • the group formed by bonding R 5c and R 6c , and R 5c and R x is preferably a single bond or an alkylene group.
  • Examples of the alkylene group include a methylene group and an ethylene group.
  • Zc - represents an anion.
  • l represents an integer of 0 to 2
  • r represents an integer of 0 to 8
  • R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, and the like.
  • it represents a group having an alkoxycarbonyl group
  • R 14 represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, or a cycloalkylsulfonyl group.
  • each of the R 15s independently represents an alkyl group, a cycloalkyl group or a naphthyl group, and the two R 15s may be bonded to each other to form a ring.
  • the ring skeleton may contain a hetero atom such as an oxygen atom, or a nitrogen atom.
  • two R 15 is an alkylene group, it is preferable to form a ring structure.
  • Z - represents an anion.
  • the alkyl groups of R 13 , R 14 and R 15 are linear or branched, preferably those having 1 to 10 carbon atoms, and are methyl group, ethyl group and n-.
  • a butyl group, a t-butyl group, or the like is more preferable.
  • R 204 to R 207 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
  • a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
  • the aryl group of R 204 to R 207 may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like.
  • Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
  • the alkyl group and cycloalkyl group of R 204 to R 207 are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.). Butyl group and pentyl group), cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group) can be mentioned.
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may each have an independent substituent.
  • substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have include an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 to 15 carbon atoms). 15), aryl groups (for example, 6 to 15 carbon atoms), alkoxy groups (for example, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like can be mentioned.
  • Z - represents an anion.
  • pf represents an integer of 0 to 10
  • qf represents an integer of 0 to 10
  • rf represents an integer of 1 to 3
  • Xf independently represents a fluorine atom or at least one. Representing an alkyl group substituted with one fluorine atom, when rf is an integer of 2 or more, a plurality of -C (Xf) 2 -may be the same or different, and R 4f and R 5f are independent of each other.
  • Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
  • Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More preferably, Xf is a fluorine atom or CF 3. In particular, it is preferable that both Xfs are fluorine atoms.
  • R 4f and R 5f each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are a plurality of R 4f and R 5f , they may be the same or different from each other.
  • the alkyl group as R 4f and R 5f may have a substituent and preferably has 1 to 4 carbon atoms.
  • R 4f and R 5f are preferably hydrogen atoms.
  • Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in Formula An-1.
  • L f represents a divalent linking group, and when there are a plurality of L f , the L f may be the same or different.
  • Examples include a divalent linking group.
  • -COO -, - OCO -, - CONH -, - NHCO -, - CO -, - O -, - SO 2 -, - COO- alkylene group -, - OCO- alkylene group -, - CONH- alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.
  • W represents an organic group containing a cyclic structure.
  • a cyclic organic group is preferable.
  • the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
  • the alicyclic group may be a monocyclic type or a polycyclic type.
  • Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • polycyclic alicyclic group examples include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • alicyclic groups having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferable.
  • the aryl group may be monocyclic or polycyclic.
  • Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group and an anthryl group.
  • the heterocyclic group may be monocyclic or polycyclic.
  • the polycyclic type can suppress the diffusion of acid more.
  • the heterocyclic group may or may not have aromaticity.
  • Examples of the aromatic heterocycle include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
  • non-aromatic heterocycle examples include a tetrahydropyran ring, a lactone ring, a sultone ring and a decahydroisoquinoline ring.
  • lactone ring and the sultone ring examples include the lactone structure and the sultone structure exemplified in the above-mentioned resin.
  • the heterocycle in the heterocyclic group a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.
  • the cyclic organic group may have a substituent.
  • the substituent may be, for example, an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms) and a cycloalkyl group (which may be monocyclic, polycyclic or spirocyclic). Often, 3 to 20 carbon atoms are preferable), an aryl group (preferably 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid. Examples include ester groups.
  • the carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be a carbonyl carbon.
  • Examples of the anion represented by the formula An-1, SO 3 - -CF 2 -CH 2 -OCO- (L f) q -W, SO 3 - -CF 2 -CHF-CH 2 -OCO- (L f ) q -W, SO 3 - -CF 2 -COO- (L f) q -W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 - (L f) qf -W, SO 3 - - CF 2 -CH (CF 3) -OCO- (L f) q -W may be mentioned as preferred.
  • L f , qf and W are the same as in the formula An-1. q represents an integer from 0 to 10.
  • X B1 and X B2 each independently represent a monovalent organic group having no hydrogen atom or fluorine atom. It is preferable that X B1 and X B2 are hydrogen atoms. X B3 and X B4 each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of X B3 and X B4 is a fluorine atom or a monovalent organic group having a fluorine atom, and both X B3 and X B4 are monovalent organic groups having a fluorine atom or a fluorine atom. Is more preferable.
  • both X B3 and X B4 are fluorine-substituted alkyl groups.
  • L, q and W are synonymous with L f , qf and W in the general formula An-1, respectively, and the specific examples and preferable ranges are also the same.
  • the represented anion is also preferred.
  • Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • Xb independently represents an organic group having no hydrogen atom or fluorine atom.
  • the definitions and preferred embodiments of o, p, q, R 4 , R 5 , L, and W are similar to rf, pf, qf, R 4f , R 5f , L f , and W in the general formula An-1, respectively. Is.
  • Z in the general formula (ZI) -, Z in the general formula (ZII) -, Zc in formula (ZI-3) -, and Z in the general formula (ZI-4) - may be a benzenesulfonic acid anion Often, it is preferably a benzenesulfonic acid anion substituted with a branched alkyl group or a cycloalkyl group.
  • Ar represents an aryl group and may further have a substituent other than the sulfonic acid anion and the ⁇ (DB) group. Further, examples of the substituent which may be possessed include a fluorine atom and a hydroxyl group.
  • N represents an integer of 0 or more.
  • n is preferably 1 to 4, more preferably 2 to 3, and most preferably 3.
  • D represents a single bond or a divalent linking group.
  • the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonic acid ester group, an ester group, and a group composed of a combination of two or more of these. ..
  • B represents a hydrocarbon group
  • D is a single bond and B is an aliphatic hydrocarbon structure.
  • B is more preferably an isopropyl group or a cyclohexyl group.
  • the photoacid generator (C) is an ionic compound containing a cation and an anion, and the anion is the general formula (An-1), the following general formula (An-2) and the following general formula (An-3). ) Is preferably included.
  • Rfa independently represents a monovalent organic group having a fluorine atom, and a plurality of Rfas may be bonded to each other to form a ring.
  • Rfa is preferably an alkyl group substituted with at least one fluorine atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Further, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Further, it is preferable that the plurality of Rfas are bonded to each other to form a ring.
  • photoacid generator (C) compounds C-1 to C-16 used in Examples are also preferably mentioned, but are not limited thereto.
  • the volume of the acid generated by the photoacid generator (C) is not particularly limited, but 240 ⁇ 3 or more is preferable from the viewpoint of suppressing the diffusion of the acid generated by exposure to the unexposed portion and improving the resolution. , 305 ⁇ 3 or more is more preferable, 350 ⁇ 3 or more is further preferable, and 400 ⁇ 3 or more is particularly preferable.
  • the volume of the acid generated from the photoacid generator (C) is preferably 1500 ⁇ 3 or less, 1000 ⁇ 3, more preferably less, 700 ⁇ 3 or less is more preferable.
  • the above volume value is obtained using "WinMOPAC" manufactured by Fujitsu Limited.
  • the volume value In calculating the volume value, first, the chemical structure of the acid is input, and then the most stable conformation of each acid is calculated by molecular mechanics using the MM (Molecular Mechanics) 3 method with this structure as the initial structure. The conformation is determined, and then the "accessible volume" of each acid can be calculated by performing molecular orbital calculation using the PM (Parameterized Model number) 3 method for these most stable conformations.
  • MM Molecular Mechanics
  • the structure of the acid generated by the photoacid generator (C) is not particularly limited, but the acid and resin generated by the photoacid generator (C) in terms of suppressing the diffusion of the acid and improving the resolution (C) It is preferable that the interaction with A) is strong.
  • the acid generated by the photoacid generator (C) is an organic acid
  • an organic acid group for example, a sulfonic acid group, a carboxylic acid group, a carbonylsulfonylimide acid group, a bissulfonylimide acid group, a trissulfonyl
  • Examples of the polar group include an ether group, an ester group, an amide group, an acyl group, a sulfo group, a sulfonyloxy group, a sulfonamide group, a thioether group, a thioester group, a urea group, a carbonate group, a carbamate group, a hydroxyl group and a mercapto.
  • the group etc. can be mentioned.
  • the number of polar groups contained in the acid generated by the photoacid generator (C) is not particularly limited, and is preferably 1 or more, and more preferably 2 or more. However, from the viewpoint of suppressing excessive development, the number of polar groups is preferably less than 6, more preferably less than 5, and even more preferably less than 4.
  • the photoacid generator (C) is preferably a photoacid generator composed of an anion portion and a cation portion.
  • Examples of the photoacid generator (C) include the photoacid generator described in paragraphs 0144 to 0173 of JP-A-2019-045864.
  • the actinic light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is a composition for KrF exposure
  • the content of the photoacid generator (C) (the total if a plurality of types exist). Is preferably 0.1 to 20% by mass, more preferably 2 to 10% by mass, and 2 to 5% by mass with respect to the total solid content of the actinic light-sensitive or radiation-sensitive resin composition. It is more preferably%.
  • the actinic light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is a composition for ArF exposure, EUV exposure, or EB exposure
  • the content of the photoacid generator (C) (plurality).
  • the total (if any species are present) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, based on the total solid content of the actinic cheilitis or radiation-sensitive resin composition. It is preferably 10 to 35% by mass, more preferably 10 to 35% by mass. Therefore, the light to be put into the container in the step (1) so that the content of the photoacid generator (C) in the actinic cheilitis or radiation-sensitive resin composition produced by the production method of the present invention is within the above range. It is preferable to adjust the amount of the acid generator (C).
  • the photoacid generator (C) may be used alone or in combination of two or more. When two or more photoacid generators (C) are used in combination, the total amount thereof is preferably within the above range.
  • Acid diffusion control agent also referred to as “acid diffusion control agent (D)” will be described.
  • the acid diffusion control agent (D) traps the acid generated from the photoacid generator (C) or the like at the time of exposure, and causes the reaction of the resin (A) (acid-degradable resin) in the unexposed portion by the excess generated acid. It acts as a suppressive quencher.
  • the acid diffusion control agent (D) include a basic compound (DA), a basic compound (DB) whose basicity is reduced or eliminated by irradiation with active light or radiation, and a photoacid generator (C).
  • Onium salt (DC) which is a relatively weak acid
  • low molecular weight compound (DD) which has a nitrogen atom and has a group which is eliminated by the action of acid
  • onium salt compound (DE) which has a nitrogen atom in the cation part.
  • DD low molecular weight compound
  • DE onium salt compound
  • a known acid diffusion control agent can be appropriately used.
  • the acid diffusion control agent (D) is used as the acid diffusion control agent (D).
  • the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention preferably contains a nitrogen-containing compound as the acid diffusion control agent (D) from the viewpoint of the stability of the pattern over time. It is more preferable to contain a nitrogen basic compound.
  • Base compound (DA) As the basic compound (DA), preferably, a compound having a structure represented by the following formulas (A) to (E) can be mentioned.
  • R 200 , R 201 and R 202 may be the same or different, respectively, independently of a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl. Represents a group (6 to 20 carbon atoms).
  • R 201 and R 202 may be combined with each other to form a ring.
  • R 203 , R 204 , R 205 and R 206 may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl groups in the formulas (A) and (E) may have a substituent or may be unsubstituted.
  • the alkyl group having a substituent 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 is preferable. It is more preferable that the alkyl groups in the formulas (A) and (E) are unsubstituted.
  • guanidine As the basic compound (DA), guanidine, aminopyrrolidin, pyrazole, pyrazoline, piperazin, aminomorpholine, aminoalkylmorpholin, piperidine and the like are preferable, and imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, etc.
  • a compound having a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, and the like are more preferable.
  • a basic compound (DB) whose basicity is reduced or eliminated by irradiation with active light or radiation (hereinafter, also referred to as “compound (DB)”) has a proton acceptor functional group and is active light or It is a compound that is decomposed by irradiation with radiation to reduce or disappear its proton accepting property, or to change from proton accepting property to acidic.
  • a proton-accepting functional group is a functional group having a group or an electron capable of electrostatically interacting with a proton, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a ⁇ -conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute.
  • the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.
  • Preferred partial structures of the proton acceptor functional group include, for example, crown ether, aza-crown ether, primary to tertiary amines, pyridine, imidazole, and pyrazine structure.
  • the compound (DB) is decomposed by irradiation with active light or radiation to reduce or eliminate the proton acceptor property, or generate a compound in which the proton acceptor property is changed to acidic.
  • the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to the acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group, and is specific.
  • the acid dissociation constant pKa of the compound generated by decomposing the compound (DB) by irradiation with active light or radiation preferably satisfies pKa ⁇ -1, more preferably -13 ⁇ pKa ⁇ -1, and -13 ⁇ pKa. ⁇ -3 is more preferable.
  • the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined in, for example, Chemical Handbook (II) (Revised 4th Edition, 1993, edited by Japan Chemical Society, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the higher the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution. Alternatively, the following software package 1 can be used to calculate Hammett's substituent constants and values based on a database of publicly known literature values. All the values of pKa described in the present specification indicate the values obtained by calculation using the following software package 1.
  • An onium salt (DC), which is a weak acid relative to the photoacid generator can be used as the acid diffusion control agent (D).
  • the photoacid generator is activated by active light or by irradiation with radiation.
  • the weak acid is released by salt exchange to form an onium salt having a strong acid anion. In this process, the strong acid is exchanged for the weak acid having a lower catalytic ability, so that the acid is apparently inactivated and the acid diffusion can be controlled.
  • the acid diffusion control agent preferably contains at least one compound selected from the group consisting of the compounds represented by the formulas d1-1 to d1-3 from the viewpoint of the tolerance of the depth of focus and the pattern linearity. ..
  • R 51 represents a hydrocarbon group which may have a substituent
  • Z 2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. It is assumed that no fluorine atom is bonded to the carbon atom adjacent to the S atom
  • R 52 represents an organic group
  • Y 3 represents a linear, branched or cyclic alkylene group or arylene group
  • Rf represents a hydrocarbon group containing a fluorine atom
  • M + independently represents an ammonium cation, a sulfonium cation or an iodonium cation.
  • Preferred examples of the sulfonium cation or iodonium cation represented by M + include the sulfonium cation exemplified by the formula (ZI) and the iodonium cation exemplified by the formula (ZII).
  • the compound (DCA) is preferably a compound represented by any of the following formulas C-1 to C-3.
  • R 1, R 2, and R 3 each independently represent one or more substituents carbon atoms.
  • L 1 represents a divalent linking group or a single bond that links the cation site and the anion site.
  • -X - is, -COO -
  • -SO 3 - represents an anion portion selected from -R 4 -, -SO 2 -, and -N.
  • R 1 , R 2 , R 3 , R 4 , and L 1 may be combined with each other to form a ring structure. Further, in the formula C-3, two of R 1 to R 3 are combined to represent one divalent substituent, which may be bonded to an N atom by a double bond.
  • Substituents having 1 or more carbon atoms in R 1 to R 3 include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino. Examples thereof include a carbonyl group and an arylaminocarbonyl group. It is preferably an alkyl group, a cycloalkyl group, or an aryl group.
  • L 1 as a divalent linking group includes a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and two kinds thereof. Examples thereof include groups formed by combining the above.
  • L 1 is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.
  • a small molecule compound (DD) having a nitrogen atom and having a group desorbed by the action of an acid has a group desorbed by the action of an acid on the nitrogen atom. It is preferably an amine derivative having.
  • an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminoal ether group is preferable, and a carbamate group or a hemiaminol ether group is more preferable. ..
  • the molecular weight of compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.
  • Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom.
  • the protecting group constituting the carbamate group can be represented by the following formula d-1.
  • R b is independently a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), and an aralkyl group (preferably 3 to 30 carbon atoms). It preferably represents 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). R b may be connected to each other to form a ring.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are independently hydroxy groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups and other functional groups, alkoxy groups, etc. Alternatively, it may be substituted with a halogen atom. The same applies to the alkoxyalkyl group indicated by R b.
  • R b a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable.
  • the ring formed by connecting the two R bs to each other include an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocyclic hydrocarbon and a derivative thereof.
  • Specific structures of the group represented by the formula d-1 include, but are not limited to, the structure disclosed in paragraph 0466 of US Patent Application Publication No. 2012/0135348.
  • the compound (DD) preferably has a structure represented by the following formula 6.
  • l represents an integer of 0 to 2
  • m represents an integer of 1 to 3
  • Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • the two Ras may be the same or different, and the two Ras may be interconnected to form a heterocycle with the nitrogen atom in the equation. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
  • R b has the same meaning as R b in the formula d-1, and preferred examples are also the same.
  • the alkyl group as R a, a cycloalkyl group, an aryl group, and aralkyl group each independently an alkyl group as R b, cycloalkyl group, aryl group and aralkyl group, may be substituted
  • the group may be substituted with a group similar to the group described above.
  • alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra are the same groups as those described above for R b.
  • Specific structures of a particularly preferred compound (DD) in the present invention include, but are not limited to, the compound disclosed in paragraph 0475 of U.S. Patent Application Publication No. 2012/0135348. No.
  • the onium salt compound (DE) having a nitrogen atom in the cation portion is preferably a compound having a basic moiety containing a nitrogen atom in the cation portion.
  • the basic moiety is preferably an amino group, more preferably an aliphatic amino group. It is more preferable that all the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Further, from the viewpoint of improving basicity, it is preferable that an electron-attracting functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly bonded to the nitrogen atom.
  • Preferred specific structures of compound (DE) include, but are not limited to, the compound disclosed in paragraph 0203 of US Patent Application Publication No. 2015/0309408.
  • the actinic cheilitis or radiation-sensitive resin composition produced by the production method of the present invention is a composition for KrF exposure
  • the content of the acid diffusion control agent (D) (the total of a plurality of types, if present). Is preferably 0.001 to 10.000% by mass, more preferably 0.001 to 1.000% by mass, based on the total solid content of the actinic light-sensitive or radiation-sensitive resin composition. preferable.
  • the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is a composition for ArF exposure, EUV exposure, or EB exposure
  • the content of the acid diffusion control agent (D) (plurality).
  • the total amount) is preferably 0.1 to 10.0% by mass, preferably 0.001 to 5.%, based on the total solid content of the sensitive light-sensitive or radiation-sensitive resin composition. More preferably, it is 0% by mass. Therefore, the acid to be put into the container in the step (1) so that the content of the acid diffusion control agent (D) in the actinic cheilitis or radiation-sensitive resin composition produced by the production method of the present invention is within the above range. It is preferable to adjust the amount of the diffusion control agent (D).
  • the acid diffusion control agent (D) may be used alone or in combination of two or more.
  • the solvent (S) includes (M1) propylene glycol monoalkyl ether carboxylate, and (M2) propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and. It preferably contains at least one selected from the group consisting of alkylene carbonates.
  • the solvent in this case may further contain components other than the components (M1) and (M2).
  • the solvent containing the component (M1) or (M2) is used in combination with the above-mentioned resin (A), the coatability of the actinic cheilitis or radiation-sensitive resin composition is improved, and the number of development defects is small. This is preferable because a pattern can be formed.
  • the solvent (S) includes, for example, an alkylene glycol monoalkyl ether carboxylate, an alkylene glycol monoalkyl ether, a lactate alkyl ester, an alkyl alkoxypropionate, a cyclic lactone (preferably having 4 to 10 carbon atoms), and a ring.
  • organic solvents such as a monoketone compound (preferably having 4 to 10 carbon atoms), an alkylene carbonate, an alkyl alkoxyacetate, and an alkyl pyruvate.
  • the content of the solvent (S) is such that the solid content concentration of the sensitive light-sensitive or radiation-sensitive resin composition is 0.5 to 0.5. It is preferable to adjust the content to 40% by mass.
  • the solid content concentration of the actinic cheilitis or radiation-sensitive resin composition is preferably 10% by mass or more in that the effect of the present invention is more excellent. Therefore, the amount of the solvent (S) to be put into the container in the step (1) is adjusted so that the solid content concentration of the actinic cheilitis or radiation-sensitive resin composition produced by the production method of the present invention is within the above range. Is preferable.
  • the solid content concentration of the actinic cheilitis or radiation-sensitive resin composition refers to other components (actinic cheilitis or radiation-sensitive) other than the solvent with respect to the total mass of the actinic cheilitis or radiation-sensitive resin composition. It means the mass percentage of the mass of (components that can constitute a sex film).
  • the step (1) in addition to the resin (A), the photoacid generator (C), the acid diffusion control agent (D), and the solvent (S), other components other than these are added. You may put it in a container.
  • Other components include, for example, surfactants, hydrophobic resins, cross-linking agents, alkali-soluble resins, dissolution-inhibiting compounds, dyes, plasticizers, photosensitizers, light absorbers, compounds that promote solubility in developers. And so on.
  • the acidic compound added in the step (2) is substantially excluded from the other components that may be put in the container in the step (1).
  • Substantially excluding is the case where the acidic compound added in the step (2) is completely excluded from the other components which may be put in the container in the step (1), and the case where the amount is small as long as the effect of the present invention is not impaired.
  • the content of the acidic compound in the container before the step (2) is preferably 0.03% by mass or less with respect to the total solid content of the container. , 0.01% by mass or less, and most preferably 0% by mass. Therefore, when the acidic compound is put into the container in the step (1), it is stored in the container before the step (2). It is preferable to adjust the content of the acidic compound in the product so as to be within the above range.
  • the other components may be added into the container in the step (1), or may be added in a step other than the step (1) instead of the step (1).
  • the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention may contain a surfactant (also referred to as "surfactant (E)").
  • a surfactant also referred to as "surfactant (E)"
  • E surfactant
  • fluorine-based and / or silicon-based surfactant is preferable. Examples of fluorine-based and / or silicon-based surfactants include the surfactants described in paragraph 0276 of US Patent Application Publication No. 2008/0248425.
  • Ftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafuck F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Co., Ltd.); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troysol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); K
  • the surfactant (E) is a fluorocarbon produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method) in addition to the known surfactants as shown above. It may be synthesized using an aliphatic compound. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as the surfactant (H). This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-090991.
  • the polymer having a fluoroaliphatic group a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable, and the polymer is irregularly distributed. It may be a block copolymerized product.
  • the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, and a poly (oxybutylene) group, and poly (oxyethylene, oxypropylene, and oxyethylene).
  • a unit having alkylenes having different chain lengths within the same chain length such as poly (block conjugate of oxyethylene and oxypropylene), may be used.
  • the copolymer of the monomer having a fluoroaliphatic group and the (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer, but also a monomer having two or more different fluoroaliphatic groups.
  • a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates) or the like may be used.
  • acrylates having a C 6 F 13 group ( or methacrylate) and (poly (oxyalkylene)) acrylate (copolymer of or methacrylate), acrylate having a C 3 F 7 group (or methacrylate) (poly (oxyethylene) and) acrylate (or methacrylate) (poly (Oxypropylene)) Copolymer with acrylate (or methacrylate) can be mentioned.
  • surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph [0280] of US Patent Application Publication No. 2008/0248425 may be used.
  • surfactants (E) may be used alone or in combination of two or more.
  • the content of the surfactant (E) is the total solid content of the above composition. On the other hand, it is preferably 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass. Therefore, when the surfactant (E) is put into the container in the step (1), the content of the surfactant (E) in the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is high. It is preferable to adjust the amount of the surfactant (E) to be put into the container in the step (1) so as to be within the above range.
  • the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention may contain a hydrophobic resin (also referred to as “hydrophobic resin (F)”).
  • the hydrophobic resin (F) is a hydrophobic resin different from the above resin (A).
  • the hydrophobic resin (F) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and is a polar substance and a non-polar substance. Does not have to contribute to the uniform mixing of.
  • the effects of adding the hydrophobic resin (F) include controlling the static and dynamic contact angles of the resist film surface with respect to water, suppressing outgas, and the like.
  • Hydrophobic resin (F) from the viewpoint of uneven distribution in the film surface layer, "fluorine atom", “silicon atom”, and, any one of “includes the CH 3 moiety to the side chain portion of the resin” It is preferable to have the above, and it is more preferable to have two or more kinds. Further, the hydrophobic resin (F) preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin or may be substituted in the side chain.
  • the fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin, and may be contained in the side chain. It may be included.
  • the partial structure having a fluorine atom is preferably an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. ..
  • the alkyl group having a fluorine atom (preferably 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. Further, it may have a substituent other than a fluorine atom.
  • 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 a substituent other than the fluorine atom.
  • the aryl group having a fluorine atom include a phenyl group and a group in which at least one hydrogen atom of an aryl group such as a naphthyl group is substituted with a fluorine atom, and further has a substituent other than the fluorine atom. May be good.
  • Examples of repeating units having a fluorine atom or a silicon atom include those exemplified in paragraph 0519 of US2012 / 0251948.
  • the hydrophobic resin (F) has a CH 3-part structure in the side chain portion.
  • CH 3 partial structure contained in the side chain portion in the hydrophobic resin comprises ethyl group, and a CH 3 partial structure having a propyl group.
  • the methyl group directly bonded to the main chain of the hydrophobic resin (F) (for example, the ⁇ -methyl group of a repeating unit having a methacrylic acid structure) is on the surface of the hydrophobic resin (F) due to the influence of the main chain. for contribution to uneven distribution is small, it shall not be included in the CH 3 partial structures in the present invention.
  • hydrophobic resin (F) the resins described in JP-A-2011-248019, JP-A-2010-175859, and JP-A-2012-032544 can also be preferably used.
  • the content of the hydrophobic resin (F) is the total solid content of the composition. On the other hand, it is preferably 0.01 to 20% by mass, and more preferably 0.1 to 15% by mass. Therefore, when the hydrophobic resin (F) is put into the container in the step (1), the content of the hydrophobic resin (F) in the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is high. It is preferable to adjust the amount of the surfactant (E) to be put into the container in the step (1) so as to be within the above range.
  • the time when the step (1) is completed (the end of the step (1)) is the essential component to be put in the container in the step (1) (a resin having a group which is decomposed by the action of an acid to generate a polar group, active light or radiation. This is when the compound that generates acid by irradiation, the acid diffusion control agent, and the solvent) have been put into the container.
  • step (1-2) in addition to the acid-degradable resin, photoacid generator, acid diffusion control agent, and solvent contained in the container in step (1), other components may be further mixed. .. Other components are as described above.
  • the mixing method in the step (1-2) is not particularly limited, but for example, it is preferable to stir and mix with the above-mentioned stirring blade.
  • Step (1-2) starts after step (1) is completed.
  • the step (1-2) may be continuously performed with the above-mentioned step (1) (the step (1-2) may be started at the same time as the step (1) is completed), and the step (1) After that, the step (1-2) may be started after a while, but from the viewpoint of productivity, it is preferable to start the step (1) continuously.
  • step (1) when the acid-degradable resin, the photoacid generator, the acid diffusion control agent, and the solvent are put into the container in the step (1), the stirring blade in the container is operated and all the above components are put into the container.
  • step (1-2) may be started (that is, the inside of the container is continuously stirred from the start of step (1) to the end of step (1-2). May be good).
  • the mixing time in the step (1-2) (that is, the time for performing the step (1-2)) is not particularly limited, but is preferably 30 minutes or more, more preferably 1 hour or more, and 2 hours or more. It is more preferably 4 hours or more, particularly preferably 6 hours or more, and most preferably 8 hours or more.
  • the upper limit of the mixing time is not particularly limited, but from the viewpoint of productivity, it is preferably 48 hours or less, more preferably 24 hours or less, and further preferably 16 hours or less.
  • the temperature at the time of mixing (the temperature of the contents in the container) is not particularly limited, but is preferably 15 to 32 ° C, more preferably 20 to 24 ° C. Further, when mixing, the temperature of the contents in the container is preferably kept constant, preferably within ⁇ 10 ° C., more preferably within ⁇ 5 ° C., and even more preferably within ⁇ 1 ° C. from the set temperature. ..
  • the rotation speed of the stirring blade is not particularly limited, but 20 to 500 rpm (rotation speed per minute) is preferable, 40 to 350 rpm is more preferable, and 50 to 300 rpm is further preferable.
  • ultrasonic waves may be applied to the contents in the container. When stopping the mixing, it is preferable to confirm that each component is dissolved or uniformly dispersed in the solvent.
  • Step (2) is a resin having a group that decomposes by the action of an acid to generate a polar group, a compound that generates an acid by irradiation with active light or radiation, an acid diffusion control agent, and a solvent (and other components if necessary). )
  • the container in the step (2) the same container as that described in the step (1) can be used.
  • the container in the step (2) may be the same as the container in the step (1) or may be different.
  • the step (2) is performed after the step (1) is completed, but it is preferable to perform the step (2) 30 minutes or more after the step (1) is completed. Between step (1) and step (2), it is preferable to leave 30 minutes or more, more preferably 1 hour or more, further preferably 2 hours or more, further preferably 4 hours or more, and 6 hours. It is particularly preferable to leave at least 8 hours, and most preferably at least 8 hours.
  • the upper limit of the time between the steps (1) and the step (2) is not particularly limited, but is preferably 48 hours or less, more preferably 24 hours or less, and 16 hours or less from the viewpoint of productivity. Is even more preferable.
  • the step (1-2) is performed after the step (1), and then the step (2) is performed.
  • the step (2) may be carried out continuously with the above-mentioned step (1-2), or may be carried out after a time after the step (1-2), but from the viewpoint of productivity, it may be carried out. It is preferable to carry out the step (1-2) continuously.
  • the step (1-2) and the step (2) are continuously performed, the step (1-2) is completed when the step (2) is started (that is, when the addition of the acidic compound is started). And.
  • the step (2) while the step (2) is being performed, the mixing of the contents in the container may be continued following the step (1-2).
  • the addition of the acidic compound in the step (2) may be carried out to the container contained in the container used in the step (1), or may be transferred from the container used in the step (1) to another container. You may go to the container.
  • step (2) when the acidic compound is added, the contents in the container may or may not be agitated. Further, in the production method of the present invention, the inside of the container may be continuously stirred from the start of the step (1) to the end of the step (2).
  • the time when the step (2) ends (the end of the step (2)) is when the acidic compound has been put into the container in the step (2). It is preferable that the component added in the step (2) is only an acidic compound.
  • the acidic compound added in the step (2) will be described.
  • the acidic compound added in the step (2) is also referred to as "acidic compound (AE)".
  • the acidic compound (AE) may be a low molecular weight compound or a high molecular weight compound, but the influence of basic components in the atmosphere is effectively suppressed by appropriately diffusing the acidic compound (AE) in the coating film.
  • a low molecular weight compound (for example, a compound having a molecular weight of 1500 or less) is preferable because it can be produced.
  • the acidic compound (AE) is not an ethylene-based polymerizable compound.
  • the molecular weight of the acidic compound (AE) is preferably 40 or more and 1000 or less, more preferably 40 or more and 500 or less, and further preferably 80 or more and 300 or less.
  • the acidic compound (AE) is not particularly limited, and examples thereof include organic carboxylic acid, organic sulfonic acid, organic sulfinic acid, phosphorus oxo acid, phenols, enol, thiol, acidimide, oxime, and sulfonamide.
  • organic carboxylic acid examples include Formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, oleic acid, acrylic acid, methacrylic acid, trans-2,3-dimethyl Acrylic acid, stearic acid, linoleic acid, linolenic acid, arachidonic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, 2-naphthoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, galvanic acid Monocarboxylic acids such as acids and shikimic acid; Dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, o
  • organic sulfonic acid examples include benzenesulfonic acid and p-toluenesulfonic acid.
  • organic sulfinic acid examples include benzenesulfinic acid, p-toluenesulfinic acid and the like.
  • Examples of the phosphorus oxo acid include inorganic acids such as phosphoric acid, phosphorous acid, hypophosphorous acid, peroxomonophosphoric acid, and pyrophosphoric acid, as well as diethylphosphinic acid, methylphenylphosphinic acid, diphenylphosphinic acid, and the like.
  • examples thereof include organic phosphonic acids such as organic phosphinic acid, methylphosphonic acid, ethylphosphonic acid, t-butylphosphonic acid, cyclohexylphosphonic acid and phenylphosphonic acid.
  • phenols examples include monovalent phenols such as phenol, cresol, 2,6-xylenol, and naphthol; Divalent phenols such as catechol, resorcinol, hydroquinone, 1,2-naphthalenediol; Examples thereof include phenols having a valence of trivalent or higher such as pyrogallol and 2,3,6-naphthalene triol.
  • Examples of the enol include 2-hydroxy-3-methyl-2-butene and 3-hydroxy-4-methyl-3-hexene.
  • thiol examples include mercaptoethanol, mercaptopropanol and the like.
  • the acid imide examples include, for example.
  • Carboxylic acid imides such as maleimide and succinimide;
  • sulfonic acid imides such as di (trifluoromethanesulfonic acid) imide and di (pentafluoroethanesulfonic acid) imide.
  • Examples of the above oxime include, for example. Aldoximes such as benzaldoxime and salicylaldoxime; Examples thereof include ketoxims such as diethyl ketoxim, methyl ethyl ketoxim, and cyclohexanone oxime.
  • Aldoximes such as benzaldoxime and salicylaldoxime
  • ketoxims such as diethyl ketoxim, methyl ethyl ketoxim, and cyclohexanone oxime.
  • sulfonamide examples include methyl sulfonamide, ethyl sulfonamide, benzene sulfonamide, toluene sulfonamide and the like.
  • the first acid dissociation constant pKa of the acidic compound (AE) at 25 ° C. is preferably 1.0 ⁇ pKa ⁇ 5.0.
  • the pKa of the acidic compound (AE) is more preferably 1.5 ⁇ pKa ⁇ 5.0, and even more preferably 2.5 ⁇ pKa ⁇ 5.0.
  • the primary acid dissociation constant pKa is the acid dissociation constant of the above acid when the acidic compound (AE) is a monovalent acid, and the acid for the dissociation of the first proton when it is a polyvalent acid. Represents the dissociation constant.
  • the first acid dissociation constant pKa represents pKa in an aqueous solution, and is described in, for example, Chemical Handbook (II) (Revised 4th Edition, 1993, edited by Japan Chemical Society, Maruzen Co., Ltd.). The lower the value, the higher the acid strength.
  • pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and Hammett's substituent using the following software package 1. Values based on a database of constants and known literature values can also be obtained by calculation. All the values of pKa in the present specification indicate the values calculated by using this software package.
  • Software Package 1 Advanced Chemistry Development (ACD / Labs) Software V8.00 for Solaris (1994-2004 ACD / Labs).
  • the acidic compound (AE) is preferably at least one selected from the group consisting of organic carboxylic acids, organic sulfonic acids, and phosphorus oxo acids, and more preferably organic carboxylic acids or phosphorus oxo acids.
  • Organic carboxylic acid is more preferable.
  • the amount of the acidic compound (AE) added in the step (2) is not particularly limited, but is preferably 0.01 to 5% by mass with respect to the total solid content of the contents in the container.
  • the amount of the acidic compound (AE) added is more preferably 0.01 to 3% by mass, still more preferably 0.01 to 1% by mass, based on the total solid content of the contents in the container.
  • W1 / W2 which is the ratio of the mass W1 of the acidic compound (AE) in the step (2) to the mass W2 of the acid diffusion control agent in the step (1), is preferably 1.0 to 20.
  • W1 / W2 is more preferably 1.0 to 15, and even more preferably 1.0 to 5.0.
  • the container contained in the container before the step (2) contains substantially no acidic compound.
  • the contents in the container before the step (2) are substantially free of acidic compounds (particularly preferably low molecular weight acidic compounds).
  • the term "substantially free of acidic compounds" includes cases where the contents in the container do not contain acidic compounds and cases where the contents are contained in a small amount as long as the effects of the present invention are not impaired.
  • the content of the acidic compound in the contents in the container before the step (2) is preferably 0.03% by mass or less, preferably 0.01% by mass, based on the total solid content of the contents in the container. It is more preferably 0% by mass or less, and most preferably 0% by mass.
  • step (3) The manufacturing method of the present invention After step (2) It is preferable to have a step (3) of mixing a resin having a group that decomposes by the action of an acid to generate a polar group, a compound that generates an acid by irradiation with active light or radiation, an acid diffusion control agent, a solvent, and an acidic compound. ..
  • the mixing method in the step (3) is not particularly limited, but for example, it is preferable to stir and mix with the above-mentioned stirring blade.
  • the step (3) is started after the step (2) is completed.
  • the step (3) may be continuously performed with the above-mentioned step (2) (the step (3) may be started at the same time as the step (2) is completed), and after the step (2), the time The step (3) may be started after a while, but from the viewpoint of productivity, it is preferable to start the step (3) continuously.
  • the stirring blade in the container is operated, and at the same time when all the acidic compounds are put into the container (at the same time when the step (2) is completed), the step (3).
  • May be started that is, the inside of the container may be continuously stirred from the start of the step (2) to the end of the step (3)).
  • the mixing time in the step (3) (that is, the time for performing the step (3)) is not particularly limited, but is preferably 30 minutes or more, more preferably 1 hour or more, and preferably 2 hours or more. More preferably, it is more preferably 4 hours or more, particularly preferably 6 hours or more, and most preferably 8 hours or more. It is considered that when the mixing time is 30 minutes or more, the acidic compound added in the step (2) is sufficiently mixed with other components to obtain a homogeneous actinic cheilitis or radiation-sensitive resin composition.
  • the upper limit of the mixing time is not particularly limited, but from the viewpoint of productivity, it is preferably 48 hours or less, more preferably 24 hours or less, and further preferably 16 hours or less.
  • the temperature at the time of mixing is not particularly limited, but is preferably 15 to 32 ° C, more preferably 20 to 24 ° C. Further, when mixing, the temperature of the contents in the container is preferably kept constant, preferably within ⁇ 10 ° C., more preferably within ⁇ 5 ° C., and even more preferably within ⁇ 1 ° C. from the set temperature. ..
  • the rotation speed of the stirring blade is not particularly limited, but 20 to 500 rpm (rotation speed per minute) is preferable, 40 to 350 rpm is more preferable, and 50 to 300 rpm is further preferable.
  • ultrasonic waves may be applied to the contents in the container. When stopping the mixing, it is preferable to confirm that each component is dissolved or uniformly dispersed in the solvent.
  • the production method of the present invention may have other steps in addition to the above-mentioned steps (1), steps (1-2), steps (2) and steps (3).
  • the actinic light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention described above can be used for pattern formation in, for example, a manufacturing process of a semiconductor device.
  • the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is typically a resist composition (preferably a chemically amplified resist composition), and is a positive resist composition. It may be a negative resist composition. Further, the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention may be a resist composition for alkaline development or a resist composition for organic solvent development.
  • the pattern forming method using the actinic light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is not particularly limited, but it is preferable to have the following steps.
  • Step a A step of forming a resist film on a substrate using the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention.
  • Step b The resist film is exposed and the exposed resist is exposed.
  • Step c A step of developing an exposed resist film using a developing solution to form a pattern
  • Step a is a step of forming a resist film on a substrate using the actinic cheilitis or radiation-sensitive resin composition produced by the production method of the present invention.
  • Examples of the method of forming a resist film on a substrate using the actinic light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention include a method of applying the above composition on the substrate. It is preferable to filter the composition as necessary before coating.
  • the pore size of the filter is preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less, still more preferably 0.3 ⁇ m or less in the case of a sensitive light-sensitive or radiation-sensitive resin composition for KrF exposure. Further, in the case of an actinic light-sensitive or radiation-sensitive resin composition for ArF exposure, EUV exposure or EB exposure, 0.1 ⁇ m or less is preferable, 0.05 ⁇ m or less is more preferable, and 0.03 ⁇ m or less is further preferable. ..
  • the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
  • the actinic light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention has a spinner, a coater, or the like on a substrate (eg, silicon, silicon dioxide coating) such as that used in the production of integrated circuit elements. It can be applied by an appropriate application method of. As a coating method, spin coating using a spinner is preferable. After applying the above composition, the substrate may be dried to form a resist film. If necessary, various undercoat films (inorganic film, organic film, or antireflection film) may be formed under the resist film.
  • drying method examples include a heating method (pre-baking: PB).
  • the heating can be performed by a means provided in a normal exposure machine and / or a developing machine, and may be performed by using a hot plate or the like.
  • the heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C.
  • the heating time is preferably 30 to 1000 seconds, more preferably 40 to 800 seconds.
  • the film thickness of the resist film is not particularly limited, but in the case of a resist film for KrF exposure, 0.2 to 12 ⁇ m is preferable, and 0.3 to 5 ⁇ m is more preferable. Further, in the case of a resist film for ArF exposure or EUV exposure, 30 to 700 nm is preferable, and 40 to 400 nm is more preferable.
  • a top coat may be formed on the upper layer of the resist film by using the top coat composition. It is preferable that the topcoat composition is not mixed with the resist film and can be uniformly applied to the upper layer of the resist film.
  • the film thickness of the top coat is preferably 10 to 200 nm, more preferably 20 to 100 nm.
  • the top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs 0072 to 0082 of JP-A-2014-059543.
  • Step b is a step of exposing the resist film to obtain the exposed resist film.
  • the exposure method include a method of irradiating the formed resist film with active light rays or radiation through a predetermined mask.
  • the active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, and EB (Electron Beam), preferably 250 nm or less, more preferably 220 nm or less.
  • the heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C.
  • the heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds.
  • the heating can be performed by a means provided in a normal exposure machine and / or a developing machine, and may be performed by using a hot plate or the like. This step is also referred to as post-exposure baking.
  • Step c is a step of developing the exposed resist film using a developing solution to form a pattern.
  • a developing method a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), and a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle method).
  • a method of spraying the developer on the surface of the substrate spray method
  • a method of continuing to eject the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic discharge method).
  • a step of stopping the development may be carried out while substituting with another solvent.
  • the developing time is not particularly limited as long as the resin in the unexposed portion is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
  • the temperature of the developing solution is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.
  • the developing solution examples include an alkaline developing solution and an organic solvent developing solution.
  • the alkaline developer it is preferable to use an alkaline aqueous solution containing an alkali.
  • the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH).
  • TMAH tetramethylammonium hydroxide
  • An appropriate amount of alcohols, surfactants and the like may be added to the alkaline developer.
  • the alkali concentration of the alkaline developer is usually 0.1 to 20% by mass.
  • the pH of the alkaline developer is usually 10.0 to 15.0.
  • the organic solvent developer is a developer containing an organic solvent.
  • the organic solvent used in the organic solvent developing solution include known organic solvents, and examples thereof include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.
  • the pattern forming method preferably includes a step of washing with a rinsing liquid after the step c.
  • a rinsing liquid used in the rinsing step after the step of developing with an alkaline developer include pure water.
  • An appropriate amount of surfactant may be added to the rinse solution.
  • the rinse solution used in the rinse step after the development step using the organic developer is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used.
  • a rinsing solution a rinsing solution containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent is used. Is preferable.
  • the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in the step c may be used as a mask to process the substrate (or the underlayer film and the substrate) to form the pattern on the substrate.
  • the processing method of the substrate (or the underlayer film and the substrate) is not particularly limited, but the substrate (or the underlayer film and the substrate) is dry-etched using the pattern formed in step c as a mask to obtain the substrate.
  • the method of forming the pattern is preferable.
  • the dry etching may be one-step etching or multi-step etching. When the etching is an etching consisting of a plurality of stages, the etching of each stage may be the same process or different processes.
  • etching any known method can be used for etching, and various conditions and the like are appropriately determined according to the type and application of the substrate.
  • the Bulletin of the International Society of Optical Engineering (Proc. Of SPIE) Vol. Etching can be performed according to 6924, 692420 (2008), Japanese Patent Application Laid-Open No. 2009-267112, and the like. It is also possible to follow the method described in "Chapter 4 Etching" of "Semiconductor Process Textbook 4th Edition 2007 Published Publisher: SEMI Japan". Of these, oxygen plasma etching is preferable as the dry etching.
  • the various materials used in the present invention do not contain impurities such as metals.
  • the content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppt (parts per million) or less, and further preferably 100 mass ppt (parts per million) or less. 10 mass ppt or less is particularly preferable, and 1 mass ppt or less is most preferable.
  • metal impurities Na, K, Ca, Fe, Cu, Mn, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Mo, Zr, Pb, Examples thereof include Ti, V, W, and Zn.
  • Examples of the method for removing impurities such as metals from the various materials include filtration using a filter.
  • the filter pore diameter is preferably 0.20 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.01 ⁇ m or less.
  • fluororesins such as polytetrafluoroethylene (PTFE) and perfluoroalkoxy alkane (PFA), polyolefin resins such as polypropylene and polyethylene, and polyamide resins such as nylon 6 and nylon 66 are preferable.
  • the filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of or a plurality of types of filters may be connected in series or in parallel.
  • filters having different pore diameters and / or materials may be used in combination.
  • various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step.
  • the circulation filtration step for example, a method disclosed in JP-A-2002-62667 is preferable.
  • the filter preferably has a reduced amount of eluate as disclosed in Japanese Patent Application Laid-Open No. 2016-201426.
  • impurities may be removed by an adsorbent, and filter filtration and an adsorbent may be used in combination.
  • a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.
  • the metal adsorbent include those disclosed in JP-A-2016-206500.
  • a method for reducing impurities such as metals contained in the various materials a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials.
  • a method such as lining or coating the inside of the apparatus with a fluororesin or the like to perform distillation under conditions in which contamination is suppressed as much as possible can be mentioned.
  • the preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as the above-mentioned conditions.
  • the above-mentioned various materials are stored in the containers described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Laid-Open No. 2015-123351, Japanese Patent Application Laid-Open No. 2017-13804, etc. in order to prevent contamination with impurities. It is preferable to be done.
  • Various materials may be diluted with the solvent used in the composition and used.
  • the present invention also relates to a method for manufacturing an electronic device including the above-mentioned pattern forming method, and an electronic device manufactured by this manufacturing method.
  • the electronic device of the present invention is suitably mounted on an electrical and electronic device (home appliance, OA (Office Automation), media-related device, optical device, communication device, etc.).
  • ⁇ Acid compound (AE)> The structures of the compounds AE-1 to AE-10 used as the acidic compounds in Examples and Comparative Examples are shown in Table 1 below. Table 1 also shows the values of the first acid dissociation constant pKa at 25 ° C. of each compound. pKa is a value calculated by using software package 1.
  • the resins A-1 to A-15 exemplified below were used as the resin (A).
  • the resins A-1 to A-15 those synthesized based on known techniques were used.
  • the weight average molecular weight (Mw) and the dispersity (Mw / Mn) of the resins A-1 to A-15 are polystyrene-equivalent values measured by the above-mentioned GPC method (carrier: tetrahydrofuran (THF)).
  • the composition ratio (mol% ratio) of the repeating unit in the resin was measured by 13 C-NMR (nuclear magnetic resonance).
  • E-2 Mega Fvck R-41 (manufactured by DIC Corporation)
  • E-3 KF-53 (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • E-4 Mega Fvck F176 (manufactured by DIC Corporation)
  • E-5 Mega Fvck R08 (manufactured by DIC Corporation)
  • ⁇ Hydrophobic resin (F)> The structures of the resins F-1 to F-2 used as the hydrophobic resin (F) in Examples and Comparative Examples are shown below.
  • the weight average molecular weight (Mw) and the dispersity (Mw / Mn) of the resins F-1 to F-2 are polystyrene-equivalent values measured by the above-mentioned GPC method (carrier: tetrahydrofuran (THF)).
  • the composition ratio (mol% ratio) of the repeating unit in the resin was measured by 13 C-NMR (nuclear magnetic resonance).
  • S Propylene glycol monomethyl ether acetate
  • PGMEA Propylene glycol monomethyl ether acetate
  • EL Ethyl lactate
  • EEP Ethyl 3-ethoxypropionate
  • MAK 2-Heptanone
  • MMP Methyl 3-methoxypropionate
  • S-7 Butyl acetate
  • Example 1 Using the resist composition manufacturing apparatus as shown in FIG. 1, the resist composition was manufactured as follows.
  • FIG. 2 schematically shows the step (1), step (1-2), step (2) and step (3) of Example 1.
  • the horizontal axis is time
  • t1 is the time when the solvent is started to be added to the stirring tank (container)
  • t2 is the time when the solvent is added
  • t3 is the time when the acid-degradable resin is added
  • t4 is the acid.
  • the time when the degradable resin was added t5 was the time when the photoacid generator was added, t6 was the time when the photoacid generator was added, t7 was the time when the acid diffusion control agent was added, and t8 was the acid diffusion control.
  • FIG. 2 is only a schematic diagram, and the actual time for performing each of the above operations and the length of the actual time for performing the steps (1), step (1-2), step (2), and step (3). Does not necessarily correspond to the length of time shown in FIG.
  • Step (1) The resin (A), photoacid generator (C), acid diffusion control agent (D) and solvent (S) shown in Table 2 were placed in a stirring tank. At this time, the solvent (S), the resin (A), the photoacid generator (C) and the acid diffusion control agent (D) were added in this order.
  • the input amount of each component of the resin (A), the photoacid generator (C), and the acid diffusion control agent (D) in the step (1), and the input amount of the surfactant (E) in the step (1-2) are Table 2 shows the ratio (mass%) of the input amount of each component to the total input amount of the resin (A), the photoacid generator (C), the acid diffusion control agent (D), and the surfactant (E). Adjusted to the value shown.
  • the amount of the solvent (S) added in the step (1) was adjusted so that the solid content concentration of the obtained actinic cheilitis or radiation-sensitive resin composition (resist composition 1) was the value shown in Table 3. ..
  • Step (2) The acidic compound (AE) shown in Table 3 was added to the contents in the stirring tank.
  • the amount of the acidic compound (AE) added in the step (2) is such that the amount of the acidic compound (AE) added (mass%) is the value shown in Table 3 with respect to the total solid content of the contents in the stirring tank. Adjusted to.
  • Step (3) The contents in the stirring tank were stirred (mixed) for 8 hours.
  • the temperature at the time of stirring (the temperature of the contained material) was kept constant at 24 ° C., and the rotation speed of the stirring blade was 200 rpm.
  • Step (1), step (1-2), step (2) and step (3) were all carried out continuously. From the start of the step (1) to the end of the step (3), the inside of the container was continuously stirred by the stirring blade.
  • the solution (mixture) obtained through the step (3) was filtered through a polyethylene filter having a pore size of 3 ⁇ m to produce an actinic light-sensitive or radiation-sensitive resin composition (resist composition 1).
  • Examples 2 to 24 The type and amount of each component used, and the stirring time in steps (1-2) and (3) were changed to the contents shown in Tables 2 and 3, except that the sensitive light rays were the same as in Example 1. Sexual or radiation-sensitive resin compositions (resist compositions 2 to 24) were obtained.
  • Comparative Example 2 For each component shown in Table 4 in the stirring tank, the solvent (S), the acidic compound (AE), the resin (A), the photoacid generator (C), and the acid so that the solid content concentration is 33.0% by mass.
  • the resist composition r2 was produced in the same manner as in Comparative Example 1 except that the diffusion control agent (D) and the surfactant (E) were added in this order.
  • the content of each component in the resist composition r2 (the content ratio of each component to the total solid content of the resist composition r2) is shown in Table 4.
  • the solid content means all components other than the solvent.
  • ⁇ Pattern formation method (1) KrF exposure, alkaline aqueous solution development> An antireflection layer on an 8-inch Si substrate (advanced materials technology manufactured by Advanced Materials Technology) treated with hexamethyldisilazane using a spin coater "ACT-8" manufactured by Tokyo Electron.
  • the resist composition produced above resist composition described in the column of "resist composition name” in Tables 3 and 4) was dropped while the substrate was stationary. After dropping, the substrate is rotated, and the rotation speed is maintained at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, further at 500 rpm for 3 seconds, again at 100 rpm for 2 seconds, and then the film thickness setting rotation.
  • a KrF excimer laser scanner (ASML) is used on the resist film via a mask having a line-and-space pattern such that the space width of the pattern formed after reduced projection exposure and development is 4.5 ⁇ m and the pitch width is 25 ⁇ m.
  • TMAH tetramethylammonium hydroxide
  • the pattern exposure is an exposure via a mask having a line-and-space pattern such that the space width after the reduced projection exposure is 4.5 ⁇ m and the pitch width is 25 ⁇ m, and the measurement of the space width of the pattern is a scanning type.
  • An electron microscope SEM: Scanning Electron Microscope
  • 9380II manufactured by Hitachi High-Technologies Corporation
  • the exposed wafer is left (leaved) for 60 minutes without being baked, and then the pattern is formed in the same manner except that the baking process is performed, and the evaluation pattern wafer (evaluation pattern wafer). 1b) was obtained.
  • the space width of the obtained pattern was measured using SEM, and the difference (CD variation) from the space width of the evaluation pattern wafer (1a) that was not intentionally placed was evaluated according to the following criteria.
  • W1 / W2 in Table 3 is the ratio of the mass W1 of the acidic compound (AE) in the step (2) to the mass W2 of the acid diffusion control agent (D) in the step (1).
  • Example 25 Using the resist composition manufacturing apparatus as shown in FIG. 1, the resist composition was manufactured as follows.
  • Step (1) The resin (A), photoacid generator (C), acid diffusion control agent (D) and solvent (S) shown in Table 5 were placed in a stirring tank. At this time, the solvent (S), the resin (A), the photoacid generator (C) and the acid diffusion control agent (D) were added in this order.
  • the input amount of (F) is each component with respect to the total input amount of the resin (A), the photoacid generator (C), the acid diffusion control agent (D), the surfactant (E), and the hydrophobic resin (F).
  • the ratio (mass%) of the input amount of the above was adjusted so as to be the value shown in Table 5.
  • the amount of the solvent (S) added in the step (1) was adjusted so that the solid content concentration of the obtained actinic cheilitis or radiation-sensitive resin composition (resist composition 25) was the value shown in Table 6. ..
  • Step (2) The acidic compound (AE) shown in Table 6 was added to the contents in the stirring tank.
  • the amount of the acidic compound (AE) added in the step (2) is such that the amount of the acidic compound (AE) added (mass%) is the value shown in Table 6 with respect to the total solid content of the contents in the stirring tank. Adjusted to.
  • Step (3) The contents in the stirring tank were stirred (mixed) for 6 hours.
  • the temperature at the time of stirring (the temperature of the contained material) was kept constant at 24 ° C., and the rotation speed of the stirring blade was 200 rpm.
  • Step (1), step (1-2), step (2) and step (3) were all carried out continuously. From the start of the step (1) to the end of the step (3), the inside of the container was continuously stirred by the stirring blade.
  • the obtained solution (mixture) is filtered in the order of a polyethylene filter having a pore size of 50 nm, then a nylon filter having a pore diameter of 10 nm, and finally a polyethylene filter having a pore diameter of 5 nm.
  • a radiation-sensitive resin composition resist composition 25 was produced.
  • Example 26 to 34 The type and amount of each component used, and the stirring time in steps (1-2) and (3) were changed to the contents shown in Tables 5 and 6, except that the sensitive light rays were the same as in Example 25. Sexual or radiation-sensitive resin compositions (resist compositions 26 to 34) were obtained.
  • the obtained solution was first filtered through a polyethylene filter having a pore size of 50 nm, then a nylon filter having a pore size of 10 nm, and finally a polyethylene filter having a pore size of 5 nm to produce a resist composition r5.
  • the content of each component in the resist composition r5 (the content ratio of each component to the total solid content of the resist composition r5) is shown in Table 7.
  • ⁇ Pattern formation method (2) ArF immersion exposure, alkaline aqueous solution development (positive)> An organic antireflection film forming composition SOC9110D (manufactured by Brewer Science) and a Si-containing antireflection film forming composition HM9825 (manufactured by Brewer Science) were applied on a silicon wafer to form an antireflection film.
  • the resist composition produced above on the obtained antireflection film resist composition described in the column of "name of resist composition” in Tables 6 and 7. However, resist compositions 27 and 32 are excluded.
  • PB Prebakke
  • the obtained wafer was subjected to a 1: 1 line-and-space pattern with a line width of 100 nm using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA0.85, Annual, outer sigma 0.9, inner sigma 0.6).
  • ASML ArF excimer laser immersion scanner
  • XT1700i NA0.85, Annual, outer sigma 0.9, inner sigma 0.6
  • Ultrapure water was used as the immersion liquid.
  • it was baked at 90 ° C. for 60 seconds (PEB: Post Exposure Bake).
  • a 1: 1 line-and-space (LS) pattern having a line width of 100 nm was formed by paddling and developing with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) as a developing solution for 30 seconds and rinsing with pure water. Formed.
  • a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the line and space width of the pattern. In this way, an evaluation pattern wafer (2a) having a substrate and a pattern formed on the surface of the substrate was obtained.
  • ⁇ Pattern formation method (3) ArF immersion exposure, organic solvent development (negative)>
  • the organic antireflection film forming composition SOC9110D and the Si-containing antireflection film forming composition HM9825 were applied on a silicon wafer to form an antireflection film.
  • the resist compositions 27 and 32 described in Table 6 prepared above were applied onto the obtained antireflection film, respectively, and baked (PB: Prebake) was performed at 100 ° C. for 60 seconds to obtain a resist having a film thickness of 100 nm. A film was formed.
  • the obtained wafer was subjected to a 1: 1 line-and-space pattern with a line width of 100 nm using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA0.85, Annual, outer sigma 0.9, inner sigma 0.6). Was exposed through a 6% halftone mask. Ultrapure water was used as the immersion liquid. Then, it was baked at 90 ° C. for 60 seconds (PEB: Post Exposure Bake). Then, it was developed by paddling with butyl acetate as a developing solution for 30 seconds and rinsed with methylisobutylcarbinol (MIBC) to form a 1: 1 line-and-space (LS) pattern having a line width of 100 nm.
  • MIBC methylisobutylcarbinol
  • a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the line and space width of the pattern. In this way, an evaluation pattern wafer (3a) having a substrate and a pattern formed on the surface of the substrate was obtained.
  • W1 / W2 in Table 6 is the ratio of the mass W1 of the acidic compound (AE) in the step (2) to the mass W2 of the acid diffusion control agent (D) in the step (1).
  • Example 35 Using the resist composition manufacturing apparatus as shown in FIG. 1, the resist composition was manufactured as follows.
  • Step (1) The resin (A), photoacid generator (C), acid diffusion control agent (D) and solvent (S) shown in Table 8 were placed in a stirring tank. At this time, the solvent (S), the resin (A), the photoacid generator (C) and the acid diffusion control agent (D) were added in this order.
  • the temperature at the time of stirring (the temperature of the contained material) was kept constant at 24 ° C., and the rotation speed of the stirring blade was 200 rpm. Further, the surfactant (E) shown in Table 8 was put into the stirring tank.
  • the input amount of each component of the resin (A), the photoacid generator (C), and the acid diffusion control agent (D) in the step (1), and the input amount of the surfactant (E) in the step (1-2) are Table 8 shows the ratio (mass%) of the input amount of each component to the total input amount of the resin (A), the photoacid generator (C), the acid diffusion control agent (D), and the surfactant (E). Adjusted to the value shown.
  • the amount of the solvent (S) added in the step (1) was adjusted so that the solid content concentration of the obtained actinic cheilitis or radiation-sensitive resin composition (resist composition 35) was the value shown in Table 9. ..
  • Step (2) The acidic compound (AE) shown in Table 9 was added to the contents in the stirring tank.
  • the amount of the acidic compound (AE) added in the step (2) is such that the amount of the acidic compound (AE) added (mass%) is the value shown in Table 9 with respect to the total solid content of the contents in the stirring tank. Adjusted to.
  • Step (3) The contents in the stirring tank were stirred (mixed) for 8 hours.
  • the temperature at the time of stirring (the contents were stirred (mixed) for 8 hours.
  • the temperature at the time of stirring (the temperature of the mixture) was kept constant at 24 ° C., and the rotation speed of the stirring blade was 200 rpm.
  • Step (1), step (1-2), step (2) and step (3) were all carried out continuously. From the start of the step (1) to the end of the step (3), the inside of the container was continuously stirred by the stirring blade.
  • the obtained solution (mixture) is filtered in the order of a polyethylene filter having a pore size of 50 nm, then a nylon filter having a pore diameter of 10 nm, and finally a polyethylene filter having a pore diameter of 5 nm.
  • a radiation-sensitive resin composition resist composition 35 was produced.
  • Examples 36 to 45 The type and amount of each component used, and the stirring time in steps (1-2) and (3) were changed to the contents shown in Tables 8 and 9, but in the same manner as in Example 35, the sensitive light beam. Sexual or radiation-sensitive resin compositions (resist compositions 36 to 45) were obtained.
  • Comparative Example 12 For each component shown in Table 10, a solvent (S), a resin (A), a photoacid generator (C), an acidic compound (AE), an acid diffusion control agent (D) and a surfactant (E) were added to the stirring tank.
  • the resist composition r12 was produced in the same manner as in Comparative Example 10 except that they were charged in this order.
  • the content of each component in the resist composition r12 (the content ratio of each component to the total solid content of the resist composition r12) is shown in Table 10.
  • ⁇ Pattern formation method (4) EUV exposure, alkaline development (positive)> AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an underlayer film having a film thickness of 30 nm.
  • the resist compositions 36 to 38 and 42 and the resist composition r9 produced above were applied thereto, respectively, and baked (PB) at 120 ° C. for 60 seconds to form a resist film having a film thickness of 30 nm.
  • the resist film was subjected to pattern irradiation using an EUV exposure apparatus (Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech).
  • the resist film after exposure was baked (PEB) at 120 ° C. for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (TMAH, 2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds.
  • TMAH tetramethylammonium hydroxide
  • a silicon wafer was rotated at a rotation speed of 4000 rpm for 30 seconds and further baked at 90 ° C. for 60 seconds to obtain a line-and-space pattern having a pitch of 80 nm and a line width of 40 nm (space width of 40 nm).
  • a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the line and space width of the pattern. In this way, an evaluation pattern wafer (4a) having a substrate and a pattern formed on the surface of the substrate was obtained.
  • ⁇ Pattern formation method (5) EUV exposure, organic solvent development (negative)> AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an underlayer film having a film thickness of 30 nm.
  • the resist compositions 35, 39 to 41, 43 to 45 and the resist compositions r10 to r12 produced above are applied thereto, and baked (PB) at 120 ° C. for 60 seconds to obtain a resist film having a film thickness of 30 nm.
  • PB baked
  • the resist film was subjected to pattern irradiation using an EUV exposure apparatus (Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech).
  • EUV exposure apparatus Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech.
  • the exposed resist film was baked (PEB) at 120 ° C. for 60 seconds and then developed with butyl acetate for 30 seconds.
  • a silicon wafer was rotated at a rotation speed of 4000 rpm for 30 seconds and further baked at 90 ° C. for 60 seconds to obtain a line-and-space pattern having a pitch of 80 nm and a line width of 40 nm (space width of 40 nm).
  • a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the line and space width of the pattern. In this way, an evaluation pattern wafer (5a) having a substrate and a pattern formed on the surface of the substrate was obtained.
  • Example 36 has a mass ratio of 50/50.
  • W1 / W2 in Table 9 is the ratio of the mass W1 of the acidic compound (AE) in the step (2) to the mass W2 of the acid diffusion control agent (D) in the step (1).
  • C-12 / C-13 in Comparative Example 9 has a mass ratio of 50/50.
  • Example 46 Using the resist composition manufacturing apparatus as shown in FIG. 1, the resist composition was manufactured as follows.
  • Step (1) The resin (A), photoacid generator (C), acid diffusion control agent (D) and solvent (S) shown in Table 11 were placed in a stirring tank. At this time, the solvent (S), the resin (A), the photoacid generator (C) and the acid diffusion control agent (D) were added in this order.
  • the input amount of each component of the resin (A), the photoacid generator (C), and the acid diffusion control agent (D) in the step (1), and the input amount of the surfactant (E) in the step (1-2) are Table 11 shows the ratio (mass%) of the input amount of each component to the total input amount of the resin (A), the photoacid generator (C), the acid diffusion control agent (D), and the surfactant (E). Adjusted to the value shown.
  • the amount of the solvent (S) added in the step (1) was adjusted so that the solid content concentration of the obtained actinic cheilitis or radiation-sensitive resin composition (resist composition 46) was the value shown in Table 12. ..
  • Step (2) The acidic compound (AE) shown in Table 12 was added to the contents in the stirring tank.
  • the amount of the acidic compound (AE) added in the step (2) was adjusted so that the amount of the acidic compound added (mass%) was the value shown in Table 12 with respect to the total solid content of the contents in the stirring tank. ..
  • Step (3) The contents in the stirring tank were stirred (mixed) for 8 hours.
  • the temperature at the time of stirring (the temperature of the contained material) was kept constant at 24 ° C., and the rotation speed of the stirring blade was 200 rpm.
  • Step (1), step (1-2), step (2) and step (3) were all carried out continuously. From the start of the step (1) to the end of the step (3), the inside of the container was continuously stirred by the stirring blade.
  • an actinic light-sensitive or radiation-sensitive resin composition (resist composition 46).
  • Example 47 to 55 The type and amount of each component used, and the stirring time in steps (1-2) and (3) were changed to the contents shown in Tables 11 and 12, except that the sensitive light rays were the same as in Example 46. Sexual or radiation-sensitive resin compositions (resist compositions 47 to 55) were produced. In Examples 49 and 52, the cross-linking agent (G) was added next to the resin (A) in the step (1).
  • the amount of the surfactant (E) added in 1-2) is that of the resin (A), the cross-linking agent (G), the photoacid generator (C), the acid diffusion control agent (D), and the surfactant (E).
  • the ratio (mass%) of the input amount of each component to the total input amount was adjusted to be the value shown in Table 11.
  • ⁇ Pattern forming method (6) EB exposure, alkaline development (positive)>
  • the resist compositions produced above using the spin coater Mark8 manufactured by Tokyo Electron Limited (resist compositions listed in the "Resist composition name” column of Tables 12 and 13) are placed on a 6-inch wafer, respectively.
  • the coating was applied and baked (PB) on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having a film thickness of 80 nm.
  • the resist film was subjected to pattern irradiation using an electron beam drawing apparatus (manufactured by Elionix Inc .; ELS-7500, acceleration voltage 50 keV).
  • SEM Scanning Electron Microscope
  • the exposed wafer is left (leaved) for 60 minutes without being baked, and then the pattern is formed in the same manner except that the baking process is performed, and the evaluation pattern wafer (evaluation pattern wafer). 6b) was obtained.
  • the space width of the obtained pattern was measured using SEM, and the difference (CD variation) from the space width of the evaluation pattern wafer (6a) that was not intentionally placed was evaluated according to the following criteria.
  • W1 / W2 in Table 12 is the ratio of the mass W1 of the acidic compound (AE) in the step (2) to the mass W2 of the acid diffusion control agent (D) in the step (1).
  • the resist compositions of Examples produced using the production method of the present invention are: The shape of the obtained pattern and the retention stability were improved. Further, from the resist composition produced by Comparative Examples 2 to 4, 6 to 8, 10 to 12, 14 to 16, which is a production method in which the timing of adding the acidic compound (AE) is not after mixing the other components. The shape of the obtained pattern and the retention stability were all the same evaluation results as in the comparative example containing no acidic compound (AE), and it was found that the effect of adding the acidic compound (AE) could not be sufficiently obtained. rice field.
  • a method for producing a sensitive light-sensitive or radiation-sensitive resin composition having a good shape of a formed pattern and excellent retention stability the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition. It is possible to provide a pattern forming method using a manufacturing method of an object and a manufacturing method of an electronic device.

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

Abstract

L'invention concerne un procédé de production d'une composition de résine sensible aux rayons actiniques ou sensible aux rayonnements capable de former un motif ayant une bonne forme et une excellente stabilité de rétention de forme, un procédé de formation d'un motif en utilisant le procédé de production, et un procédé de formation d'un dispositif électronique.　L'invention concerne un procédé de production d'une composition de résine sensible aux rayons actiniques ou sensible aux rayonnements, comprend, dans l'ordre suivant, une étape (1) consistant à mettre en place une résine ayant un groupe qui est décomposé par l'action d'un acide pour générer un groupe polaire, un composé qui génère un acide lorsqu'il est irradié avec un rayon actinique ou un rayonnement, un agent de régulation de diffusion d'acide et un solvant dans un contenant, et une étape (2) consistant à ajouter un composé acide dans le contenant qui contient la résine ayant un groupe qui est décomposé par l'action d'un acide pour générer un groupe polaire, le composé qui génère un acide lorsqu'il est irradié avec un rayon actinique ou un rayonnement, l'agent de régulation de diffusion d'acide et le solvant, un procédé de formation d'un motif en utilisant le procédé de production, et un procédé de formation d'un dispositif électronique.
PCT/JP2021/006202 2020-02-27 2021-02-18 Procédé de production de composition de résine sensible aux rayons actiniques ou sensible aux rayonnements, procédé de formation de motif et procédé de fabrication de dispositif électronique Ceased WO2021172173A1 (fr)

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