Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
  • C07C233/90—Carboxylic acid amides having nitrogen atoms of carboxamide groups further acylated
  • C07C233/92—Carboxylic acid amides having nitrogen atoms of carboxamide groups further acylated with at least one carbon atom of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/24—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of a carbon skeleton containing six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/39—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing halogen atoms bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
  • C07C311/51—Y being a hydrogen or a carbon atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
  • C07C63/68—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings containing halogen
  • C07C63/70—Monocarboxylic acids
• • 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
  • G03F7/038—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

Definitions

• the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, a method of manufacturing an electronic device, and a compound.
• Patent Document 1 discloses a resist composition containing a compound represented by the following formula.
• the actinic ray-sensitive or radiation-sensitive resin composition using the compound disclosed in Patent Document 1 has shelf stability. It has been found that may not always be sufficient. We also found that there is room for improvement in the LWR (line width roughness) performance of the obtained pattern.
• An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin having a repeating unit having a group which is decomposed by the action of an acid to increase the polarity and a compound Q represented by the general formula (I).
• A represents a single bond.
• any one of R 1 , R 5 , R 6 and R 10 is a group represented by General Formula (II), described in [1] or [2] Actinic ray-sensitive or radiation-sensitive resin composition of [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], further comprising a photoacid generator other than the compound Q. [5] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4].
• [6] A process of forming a resist film on a support using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], a process of exposing the resist film, and the exposure And b. Developing the resist film with a developer solution.
• the manufacturing method of an electronic device including the pattern formation method as described in [6].
• [8] Compounds represented by General Formula (I-2).
• [9] The compound as described in [8], wherein A represents a single bond in general formula (I-2).
• any one of R 1 , R 5 , R 6 and R 10 is a group represented by general formula (II), [8] or [9] The compound as described in.
• an actinic ray-sensitive or radiation-sensitive resin composition which is excellent in storage stability and can obtain a pattern excellent in LWR performance.
• Another object of the present invention is to provide a resist film, a method of forming a pattern, a method of manufacturing an electronic device, and a compound relating to the actinic ray-sensitive or radiation-sensitive resin composition.
• the present invention will be described in detail. Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments.
• the notation not describing substitution and non-substitution also 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).
• organic group in the present specification means a group containing at least one carbon atom.
• actinic ray refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV light), X-rays, and electron beams (EB). Means Electron Beam) and the like.
• light herein is meant actinic radiation or radiation.
• exposure in the present specification includes not only exposure by the bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X rays, EUV light, etc., but also electron beams and Also includes drawing by particle beam such as ion beam.
• “to” is used in the meaning including the numerical values described before and after it as the lower limit value and the upper limit value.
• (meth) acrylate represents acrylate and methacrylate.
• the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (also referred to as molecular weight distribution) (Mw / Mn) of a resin are GPC (Gel Permeation Chromatography) devices (HLC- manufactured by Tosoh Corporation) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ L, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: differential refraction It is defined as a polystyrene conversion value by a refractive index detector (Refractive Index Detector).
• pKa acid dissociation constant pKa
• Chemical Handbook (II) (revised 4th edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.) Defined in).
• the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25 ° C. using an infinite dilution aqueous solution.
• values based on Hammett's substituent constant and a database of known literature values can also be obtained by calculation. All the pKa values described in the present specification indicate values calculated by using this software package.
• halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be mentioned.
• composition Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition
• the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also simply referred to as “composition” or “composition of the present invention”) of the present invention will be described.
• the composition of the present invention is a so-called resist composition, and may be a positive resist composition or a negative resist composition. Further, it may be a resist composition for alkali development or a resist composition for organic solvent development.
• the composition of the present invention is typically a chemically amplified resist composition.
• the characteristic point of the composition of the present invention is that it contains a resin having a repeating unit having a group which is decomposed by the action of an acid to increase the polarity, and a compound Q represented by the general formula (I) described later.
• a resin having a repeating unit having a group which is decomposed by the action of an acid to increase the polarity and a compound Q represented by the general formula (I) described later.
• the compound Q is a betaine compound, and its ionicity is reduced because the charge is neutralized in the molecule.
• the compatibility with the resin is improved, and the resin can be dispersed uniformly in the film to improve the LWR performance.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin having a repeating unit having a group which is decomposed by the action of an acid to increase the polarity (hereinafter, also referred to as "acid-degradable group”) Acid degradable resin "or" resin A ").
• acid-degradable group acid degradable resin "or” resin A
• the resin A preferably has a repeating unit having an acid decomposable group.
• the acid-degradable group preferably has a structure in which the polar group is protected by a group (leaving group) which is decomposed and eliminated by the action of acid.
• a polar group a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonyl imide group, (alkylsulfonyl) (alkyl carbonyl) methylene group, (alkyl sulfonyl) (alkyl carbonyl) imide group , Bis (alkyl carbonyl) methylene group, bis (alkyl carbonyl) imide group, bis (alkyl sulfonyl) methylene group, bis (alkyl sulfonyl) imide group, tris (alkyl carbonyl) methylene group, and tris (alkyl sulfonyl) methylene group
• the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and is a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, and an electron attracting group such as a fluorine atom at the ⁇ position as a hydroxyl group
• an electron attracting group such as a fluorine atom at the ⁇ position as a hydroxyl group
• aliphatic alcohols substituted with sex groups eg, hexafluoroisopropanol group etc.
• the alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 to 20.
• the polar group is preferably a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.
• a preferred group as the acid-degradable group is a group obtained by substituting a hydrogen atom of these groups with a group (leaving group) which is released by the action of an acid.
• Examples of the group capable of leaving by the action of an acid (leaving group) include, for example, —C (R 36 ) (R 37 ) (R 38 ), —C (R 36 ) (R 37 ) (OR 39 ), and And -C (R 01 ) (R 02 ) (OR 39 ) and the like.
• each of R 36 to R 39 independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
• R 36 and R 37 may combine with each other to form a ring.
• Each of R 01 and R 02 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
• the cycloalkyl group of R 36 to R 39 , R 01 and R 02 may be monocyclic or polycyclic.
• a cycloalkyl group having a carbon number of 3 to 8 is preferable, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
• the polycyclic ring is preferably a cycloalkyl group having a carbon number of 6 to 20, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an ⁇ -pinel group, a tricyclodecanyl group and a tetracyclododecyl group. And androstanyl groups and the like.
• one or more carbon atoms in the cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.
• the aryl group of R 36 to R 39 , R 01 and R 02 is preferably an aryl group having a carbon number of 6 to 10, and examples thereof include a phenyl group, a naphthyl group and an anthryl group.
• the aralkyl group of R 36 to R 39 , R 01 and R 02 is preferably an aralkyl group having a carbon number of 7 to 12, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
• the alkenyl group of R 36 to R 39 , R 01 and R 02 is preferably an alkenyl group having a carbon number of 2 to 8, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group. .
• the ring formed by bonding R 36 and R 37 to each other is preferably a cycloalkyl group (monocyclic or polycyclic).
• a monocyclic cycloalkyl group a cyclopentyl group or a cyclohexyl group is preferable, and as a polycyclic cycloalkyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group or the like is preferable. preferable.
• the acid-degradable group preferably has a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or an acetal ester group, and more preferably has an acetal group or a tertiary alkyl ester group. preferable.
• the resin A preferably has a repeating unit represented by the following general formula (AI) as a repeating unit having an acid decomposable group.
• T represents a single bond or a divalent linking group.
• the divalent linking group for T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-.
• Rt represents an alkylene group, a cycloalkylene group or an arylene group.
• T is preferably a single bond or -COO-Rt-.
• Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, and more preferably -CH 2 -,-(CH 2 ) 2- or-(CH 2 ) 3- . More preferably, T is a single bond.
• Xa 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
• Xa 1 is preferably a hydrogen atom or an alkyl group.
• the alkyl group of Xa 1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
• the alkyl group of Xa 1 preferably has 1 to 4 carbon atoms, and examples include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group.
• the alkyl group of Xa 1 is preferably a methyl group.
• Rx 1 to Rx 3 each independently represent an alkyl group or a cycloalkyl group. Any two of Rx 1 to Rx 3 may be combined to form a ring structure or may not be formed.
• the alkyl group of Rx 1 , Rx 2 and Rx 3 may be linear or branched and may be methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group Preferred is a group, an isobutyl group, and a t-butyl group.
• the carbon number of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
• a part of carbon-carbon bonds may be a double bond.
• the cycloalkyl group of Rx 1 , Rx 2 and Rx 3 may be monocyclic or polycyclic. Examples of monocyclic cycloalkyl groups include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic cycloalkyl group include norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group.
• the ring formed by combining two of Rx 1 , Rx 2 and Rx 3 may be monocyclic or polycyclic.
• single rings include monocyclic rings such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, and cyclooctane ring.
• polycyclic rings include polycyclic cycloalkyl rings such as norbornane ring, tetracyclodecane ring, tetracyclododecane ring, and adamantane ring. Among them, a cyclopentyl ring, a cyclohexyl ring or an adamantane ring is preferable.
• the rings shown below are also preferable.
• the resin A have a repeating unit described in paragraphs ⁇ 0336> to ⁇ 0369> of US Patent Application Publication No. 2016/0070167 A1 as a repeating unit having an acid decomposable group.
• resin A is decomposed by the action of the acid described in paragraphs ⁇ 0363> to ⁇ 0364> of US Patent Application Publication No. 2016/0070167 A1 as a repeating unit having an acid decomposable group, to thereby obtain an alcoholic hydroxyl group. You may have a repeating unit containing the group which arises.
• the resin A may have a single type of repeating unit having an acid-degradable group, or may have two or more types.
• the content of the repeating units having an acid decomposable group contained in the resin A (the total of the repeating units having an acid degradable group, in the case where a plurality of repeating units having an acid degradable group are present) % Is preferable, 20 to 80 mol% is more preferable, and 30 to 70 mol% is more preferable.
• the resin A preferably has a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.
• the lactone structure or sultone structure may have a lactone ring or a sultone ring, and a lactone structure having a 5- to 7-membered lactone ring or a sultone structure having a 5- to 7-membered sultone ring is preferable.
• a lactone structure in which another ring is fused to a 5- to 7-membered lactone ring in the form of forming a bicyclo structure or a spiro structure is also preferred.
• a sultone structure in which another ring is fused to a 5- to 7-membered sultone ring to form a bicyclo structure or a spiro structure is also preferred.
• the resin A has a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-22), or any one of the following formulas (SL1-1) to (SL1-3) It is preferable to have a repeating unit having a sultone structure represented. Also, a lactone structure or a sultone structure may be directly bonded to the main chain. Among them, general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), general formula (LC1-21), Alternatively, the lactone structure represented by the general formula (LC1-22) or the sultone structure represented by the general formula (SL1-1) is preferable.
• the lactone structure or sultone structure may or may not have a substituent (Rb 2 ).
• a substituent (Rb 2 ) an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxy group, A halogen atom, a hydroxyl group, a cyano group, or an acid-degradable group is preferable, and an alkyl group having 1 to 4 carbon atoms, a cyano group or an acid-degradable group is more preferable.
• n 2 represents an integer of 0 to 4; When n 2 is 2 or more, a plurality of substituents (Rb 2 ) may be the same or different. Moreover, two or more substituents (Rb 2 ) may be combined to form a ring.
• a repeating unit having a lactone structure or a sultone structure As a repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (III) is preferable.
• A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-).
• n is the number of repetition of the structure represented by -R 0 -Z- and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0.
• n is 0, (-R 0 -Z-) n is a single bond.
• R 0 represents an alkylene group, a cycloalkylene group, or a combination thereof. When a plurality of R 0 are present, the plurality of R 0 may be the same or different.
• the alkylene group or cycloalkylene group of R 0 may have a substituent.
• Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
• the plurality of Z may be the same or different.
• Z is preferably an ether bond or an ester bond, more preferably an ester bond.
• R 8 represents a monovalent organic group having a lactone structure or a sultone structure.
• carbon atoms constituting a lactone structure or a sultone structure in any of the structures represented by formulas (LC1-1) to (LC1-22) and formulas (SL1-1) to (SL1-3) It is preferable that it is a group formed by removing one hydrogen atom from one.
• the carbon atom from which one hydrogen atom is removed is preferably not a carbon atom constituting the substituent (Rb 2 ).
• R 7 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
• a repeating unit having a lactone structure or a sultone structure As a repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (III-2) is also preferable.
• RIII independently represents a hydrogen atom or a substituent.
• substituent include a halogen atom and a monovalent organic group (preferably a methyl group).
• RIII is preferably a hydrogen atom.
• cyc represents a group having a lactone structure or a sultone structure.
• lactone structure or sultone structure It is preferable that it is a group which remove
• the carbon atom removed two said hydrogen atom is preferably not a carbon atom constituting a substituent (Rb 2).
• the resin A may have a repeating unit having a carbonate structure.
• a carbonate structure a cyclic carbonate structure is preferable.
• a repeating unit having a cyclic carbonate structure a repeating unit represented by the following general formula (A-1) is preferable.
• R A 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
• n represents an integer of 0 or more.
• R A 2 represents a substituent. When n is 2 or more, a plurality of R A 2 may be the same or different.
• A represents a single bond or a divalent linking group.
• Z represents an atomic group forming a single ring structure or a multiple ring structure with a group represented by -O-CO-O- in the formula.
• Resin A is a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure as described in paragraphs ⁇ 0370> to ⁇ 0414> of US Patent Application Publication No. 2016/0070167 A1. It is also preferred to have the described repeat units.
• the resin A may have a single repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, and may have two or more types. Good.
• monomers corresponding to repeating units having at least one selected from the group consisting of lactone structure, sultone structure, and carbonate structure are exemplified.
• a methyl group bonded to a vinyl group may be replaced by a hydrogen atom, a halogen atom, or a monovalent organic group.
• the resin A has a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure
• the lactone structure, a sultone structure, and a carbonate structure contained in the resin A The content of repeating units having at least one selected (total of repeating units having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, if any), the resin
• the amount is preferably 5 to 70 mol%, more preferably 10 to 65 mol%, still more preferably 20 to 60 mol%, based on all repeating units in A.
• the resin A may have a repeating unit having a polar group separately from the group described above.
• a polar group a hydroxyl group, a cyano group, a carboxy group, and a fluorinated alcohol group etc. are mentioned.
• the repeating unit having a polar group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group.
• the repeating unit which has a polar group does not have an acid degradable group.
• an alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted by the polar group an adamantyl group or a norbornane group is preferable.
• the resin A may have one type of repeating unit having a polar group alone, or may have two or more types.
• the content of the repeating unit having a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, based on all the repeating units in the resin A.
• 10 to 25 mol% is more preferable.
• the resin A may further have a repeating unit having neither an acid-degradable group nor a polar group, apart from the above-mentioned groups. It is preferable that the repeating unit which does not have any of an acid-degradable group and a polar group has an alicyclic hydrocarbon structure. Examples of the repeating unit having neither an acid degradable group nor a polar group include the repeating units described in paragraphs ⁇ 0236> to ⁇ 0237> of US Patent Application Publication No. 2016 / 0026083A1. Preferred examples of the monomer corresponding to the repeating unit having neither an acid-degradable group nor a polar group are shown below.
• the resin A may have a single type of repeating unit having neither an acid-degradable group nor a polar group, and may have two or more types.
• the content of the repeating unit having neither an acid degradable group nor a polar group is the total repeating unit in the resin A.
• 5 to 40 mol% is preferable, 5 to 30 mol% is more preferable, and 5 to 25 mol% is more preferable.
• Resin A controls dry etching resistance, standard developer suitability, substrate adhesion, resist profile or, in addition to the above-mentioned repeating structural units, resolution, heat resistance, sensitivity, etc. which are generally necessary characteristics of resists. You may have various repeating structural units in order to do. Such repeating structural units include, but are not limited to, repeating structural units corresponding to predetermined monomers.
• the predetermined monomer for example, one addition polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like The compound etc. which it has are mentioned.
• addition polymerizable unsaturated compounds copolymerizable with the monomers corresponding to the above-mentioned various repeating structural units may be used.
• the content molar ratio of each repeating structural unit is appropriately set to adjust various performances.
• the resin A substantially does not have an aromatic group from the viewpoint of ArF light transmittance. More specifically, the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, with respect to all the repeating units in the resin A, and ideally It is further preferred that it has 0 mol%, that is, it does not have a repeating unit having an aromatic group. Further, the resin A preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
• all the repeating units may be composed of (meth) acrylate repeating units.
• all of the repeating units may be methacrylate repeating units, or all of the repeating units may be acrylate repeating units, and all of the repeating units are combinations of methacrylate repeating units and acrylate repeating units. It may be Among them, the content of the acrylate-based repeating unit is preferably 50 mol% or less based on all the repeating units of the resin A.
• paragraphs ⁇ 0055> to ⁇ 0191> of US Patent Application Publication 2016 / 0274458A1, paragraphs ⁇ 0035> to ⁇ 0085> of US Patent Application Publication 2015/0004544 A1, and US Patent Application Publication 2016 / Known resins disclosed in paragraphs ⁇ 0045> to ⁇ 0090> of the specification of 0147150 Al can be suitably used as the resin A.
• resin A When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, resin A preferably has a repeating unit having an aromatic hydrocarbon group, and resin A has a repeating group containing a phenolic hydroxyl group. It is more preferred to have a unit. As a repeating unit containing a phenolic hydroxyl group, a hydroxystyrene repeating unit and a hydroxystyrene (meth) acrylate repeating unit can be mentioned. When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, resin A is a group (leaving group) from which hydrogen atoms of phenolic hydroxyl groups are decomposed and released by the action of acid.
• the content of the repeating unit having an aromatic hydrocarbon group contained in the resin A is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, with respect to all the repeating units in the resin A. 50 to 100 mol% is more preferable.
• the weight average molecular weight of the resin A is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3,000 to 15,000, and particularly preferably 3,000 to 12,000. .
• the dispersion degree (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and still more preferably 1.1 to 2.0. preferable.
• the resin A may be used alone or in combination of two or more.
• the content of the resin A in the composition is generally 20% by mass or more in many cases, preferably 40% by mass or more, and more preferably 60% by mass or more, based on the total solid content in the composition. % Or more is more preferable. Although the upper limit in particular is not restrict
• the component except the solvent in a composition is intended.
• composition of the present invention comprises compound Q.
• the compound Q is a compound represented by the general formula (I).
• Each of R 1 to R 10 independently represents a hydrogen atom or a substituent.
• any one of R 1 to R 10 is a group represented by general formula (II).
• one of the groups represented by general formula (II) exists among R 1 to R 10 , and the remaining nine groups are a substituent other than the group represented by general formula (II) or hydrogen It is an atom.
• A represents a single bond or a divalent linking group.
• the divalent linking group is not particularly limited.
• R F represents a hydrogen atom or an alkyl group
• the divalent linking group is preferably an alkylene group (preferably having a carbon number of 1 to 3) which may have a substituent, an ester group, or a group consisting of a combination thereof.
• a substituent which the said alkylene group may have a halogen atom is preferable and a fluorine atom is still more preferable.
• A is preferably a single bond.
• X - is, -SO 3 -, - (SO 2) -N - - (SO 2) R 11, - (SO 2) -N - -COR 12, -CO-N - - (SO 2) R 13, Or -CO-N -- COR 14 is represented.
• R 11 to R 14 independently represents an organic group.
• the organic group is preferably an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent.
• the alkyl group may be linear or branched.
• the carbon number is preferably 1 to 6.
• the alkyl group methyl group, ethyl group, propyl group, isopropyl group, t-butyl group or n-butyl group is preferable.
• the cycloalkyl group may be monocyclic or polycyclic. The carbon number is preferably 5 to 10.
• a substituent which the said alkyl group and the cycloalkyl group may have a halogen atom is preferable and a fluorine atom is more preferable.
• a halogen atom preferably a fluorine atom
• the alkyl group is a fluoroalkyl group (including a perfluoroalkyl group, preferably having 1 to 6 carbon atoms).
• a group R 3 or R 8 is represented by formula (II), and, - (SO 2) -N - - (SO 2)
• R 11 is other than a trifluoromethyl group It is preferred to represent an organic group.
• any one of R 1 , R 5 , R 6 , and R 10 is a point of obtaining a pattern that the storage stability of the composition is more excellent and the LWR performance is more excellent.
• the group represented by formula (II) is preferable.
• one other than the group represented by general formula (II) is a substituent other than a hydrogen atom or a group represented by general formula (II) .
• a substituent other than the group represented by General Formula (II) a group other than an anionic group is preferable.
• the substituent other than the group represented by General Formula (II) is, for example, an alkyl group which may be substituted by a halogen atom (preferably a fluorine atom) Can be mentioned.
• the alkyl group may be linear or branched and may have a cyclic structure.
• the carbon atom which comprises an alkyl group may be substituted by one or more groups selected from the group which consists of an ether group, a carbonyl group, and an ester group (for example, the carbon atom of the root in an alkyl group) Are substituted with an ether group, and the alkyl group may be in the form of an alkoxy group).
• the alkyl group methyl group, ethyl group, propyl group, isopropyl group, t-butyl group or n-butyl group is preferable. It is also preferable that some or all of the hydrogen atoms of these groups be substituted with a halogen atom (preferably a fluorine atom).
• the alkyl group is a fluoroalkyl group (including a perfluoroalkyl group, preferably having 1 to 6 carbon atoms).
• R 1 to R 10 other than the group represented by formula (II) 0 to 3 preferably represent a substituent, and more preferably 0 to 1 represent a substituent.
• the compound Q is preferably a compound represented by the general formula (I-2).
• R 1 to R 10 independently represents a hydrogen atom or a substituent. However, any one of R 1 to R 10 is a group represented by general formula (II).
• A represents a single bond or a divalent linking group.
• X - is, -SO 3 -, - (SO 2) -N - - (SO 2) R 11, - (SO 2) -N - -COR 12, -CO-N - - (SO 2) R 13, Or -CO-N -- COR 14 is represented.
• Each of R 11 to R 14 independently represents an organic group.
• each symbol in the general formula (I-2) has the same meaning as the corresponding group in the general formula (I), and the preferred range is also the same.
• a group R 3 or R 8 is represented by formula (II), and, - (SO 2) -N - - For (SO 2) R 11, R 11 represents an organic group other than a trifluoromethyl group.
• the compound Q is a molecule having both positive charge and negative charge in the molecule, and is a so-called zwitterion.
• the compound Q is preferably a compound capable of generating an acid upon irradiation with an actinic ray or radiation.
• the compound Q preferably exhibits basicity in the unexposed state to act as a so-called acid diffusion control agent.
• the acid diffusion control agent traps the acid generated from the photoacid generator and the like by exposure to light, and suppresses the reaction progress of the acid decomposable group of the resin A in the unexposed area by the extra generated acid.
• the compounds Q may be used alone or in combination of two or more. 0.5 mass% or more is preferable, as for content of the compound Q in the total solid of the composition of this invention, 1.0 mass% or more is more preferable, and 2.5 mass% or more is still more preferable.
• the upper limit is not particularly limited, but is preferably 15.0% by mass or less, more preferably 7.0% by mass or less, and still more preferably 5.0% by mass or less.
• the composition of the present invention preferably contains a photoacid generator which is a compound other than compound Q.
• the photoacid generator is a compound which generates an acid upon irradiation with an actinic ray or radiation, and is a compound other than the compound Q.
• a compound capable of generating an organic acid upon irradiation with an actinic ray or radiation is preferable.
• sulfonium salt compounds for example, sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imidosulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzyl sulfonate compounds.
• the photoacid generator may be a zwitterion but can not be a compound Q.
• photoacid generator known compounds which generate an acid upon irradiation with an actinic ray or radiation can be appropriately selected and used alone or as a mixture thereof.
• the known compounds disclosed in paragraphs ⁇ 0323> to ⁇ 0402> of the specification can be suitably used as a photoacid generator.
• the compound represented by the following general formula (ZI), general formula (ZII), or general formula (ZIII) is preferable, for example.
• Each of R 201 , R 202 and R 203 independently represents an organic group.
• the carbon number 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 combined to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
• Examples of the group formed by bonding of two of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group), and —CH 2 —CH 2 —O—CH 2 —CH 2 — Be Z - represents an anion.
• Preferred embodiments of the cation in the general formula (ZI) include the compounds (ZI-1), the compound (ZI-2), the compound (ZI-3) and the corresponding groups in the compound (ZI-4) described later. It can be mentioned.
• the photoacid generator may be a compound having a plurality of structures represented by general formula (ZI). For example, at least one of R 201 ⁇ R 203 of the compound represented by formula (ZI), at least one of R 201 ⁇ R 203 of another compound represented by formula (ZI) is a single bond Alternatively, it may be a compound having a structure bonded via a linking group.
• the compound (ZI-1) is an arylsulfonium compound in which at least one of R 201 to R 203 in the general formula (ZI) is an aryl group, that is, a compound having an arylsulfonium as a cation.
• the arylsulfonium compound all of R 201 to R 203 may be aryl groups, or a part of R 201 to R 203 may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group.
• arylsulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.
• the aryl group contained in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom or the like. Examples of the heterocyclic structure include pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue, and benzothiophene residue.
• the two or more aryl groups may be the same or different.
• the alkyl group or cycloalkyl group which the arylsulfonium compound optionally has is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms.
• the cycloalkyl group of 15 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 R201 to R203 are each independently an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, carbon atoms) 6 to 14), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group or a phenylthio group may be included as a substituent.
• the compound (ZI-2) is a compound in which each of R 201 to R 203 in formula (ZI) independently represents 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 R201 to R203 independently is 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-oxo It is a cycloalkyl group or 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 (eg, methyl group, ethyl group, And a propyl group, a butyl group and a pentyl group), and a cycloalkyl group having a carbon number of 3 to 10 (eg, a cyclopentyl group, a cyclohexyl group and a norbornyl group).
• R 201 to R 203 may be further substituted by 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 a compound represented by the following general formula (ZI-3) and having a phenacylsulfonium salt structure.
• R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom or a hydroxyl group , A nitro group, an alkylthio group or an arylthio group.
• R 6c and R 7c each 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 independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.
• R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y respectively combine to form a ring structure.
• Each of the ring structures may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond or an amide bond.
• Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic fused ring in which two or more of these rings are combined.
• the ring structure includes 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 bonding 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 combining 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.
• the compound (ZI-4) is represented by the following general formula (ZI-4).
• 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, a cycloalkylsulfonyl group, or a cycloalkyl group. These groups may have a substituent. When there are a plurality of R 14 's , they each independently represent the above-mentioned group such as a hydroxyl group. Each R 15 independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent.
• Two R 15 s may be bonded to each other to form a ring.
• the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom.
• Z - represents an anion.
• the alkyl group of R 13 , R 14 and R 15 is linear or branched.
• the carbon number of the alkyl group is preferably 1 to 10.
• the alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group or a t-butyl group.
• each of R 204 to R 207 independently represents an aryl group, an alkyl group or a cycloalkyl group.
• the aryl group of R 204 to R 207 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• 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 include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, A butyl group and a pentyl group) or a cycloalkyl group having a carbon number of 3 to 10 (eg, a cyclopentyl group, a cyclohexyl group and a norbornyl group) is preferable.
• the aryl group, alkyl group and cycloalkyl group of R 204 to R 207 may each independently have a substituent.
• substituents which the aryl group, alkyl group and cycloalkyl group of R 204 to R 207 may have include, for example, alkyl group (for example, 1 to 15 carbon atoms) and cycloalkyl group (for example, 3 carbon atoms) And an aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
• Z - represents an anion.
• o represents an integer of 1 to 3
• p represents an integer of 0 to 10.
• q represents an integer of 0 to 10;
• Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
• the carbon number of this alkyl group is preferably 1 to 10, and more preferably 1 to 4.
• a perfluoroalkyl group is preferable.
• Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF 3 . Among them, it is more preferable that both Xf be a fluorine atom.
• R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R 4 and R 5 are present, the plurality of R 4 and the plurality of R 5 may be the same or different.
• the alkyl group represented by R 4 and R 5 may have a substituent, and preferably has 1 to 4 carbon atoms.
• R 4 and R 5 are preferably hydrogen atoms. Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as specific examples and preferred embodiments of Xf in the general formula (3).
• L represents a divalent linking group.
• the plurality of L may be the same or different.
• a divalent linking group for example, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO 2- , an alkylene group ( Preferable examples include C1-6), cycloalkylene groups (preferably C3-15), alkenylene groups (preferably C2-6), and a divalent linking group combining a plurality of these, and the like.
• -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 preferred .
• W represents an organic group containing a cyclic structure.
• a cyclic organic group is preferable.
• an alicyclic group an alicyclic group, an aryl group, and a heterocyclic group are mentioned, for example.
• the alicyclic group may be monocyclic or polycyclic.
• monocyclic alicyclic group monocyclic cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, are mentioned, for example.
• polycyclic alicyclic group examples include polycyclic cycloalkyl groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group.
• polycyclic cycloalkyl groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group.
• an alicyclic group having a bulky structure having 7 or more carbon atoms is preferable, and examples thereof include norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group.
• the aryl group may be monocyclic or polycyclic. Examples of this aryl group include phenyl group, naphthyl group, phenanthryl group, and anthryl group.
• the heterocyclic group may be monocyclic or polycyclic. The polycycle can suppress the diffusion of acid more.
• the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the hetero ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
• hetero ring having no aromaticity examples include tetrahydropyran ring, lactone ring, sultone ring, and decahydroisoquinoline ring.
• lactone ring and sultone ring examples include lactone structure and sultone structure exemplified in the above-mentioned resin.
• the heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring.
• the cyclic organic group may have a substituent.
• substituents include, for example, an alkyl group (which may be linear or branched and preferably has 1 to 12 carbon atoms), a cycloalkyl group (including a single ring, multiple rings (spiro ring, etc.) And C 3-20 are preferable), aryl groups (preferably having 6-14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, A sulfonamide group and a sulfonate ester group can be mentioned.
• the carbon constituting the cyclic organic group may be carbonyl carbon.
• SO 3 -- CF 2 -CH 2 -OCO- (L) q'-W SO 3 -- CF 2 -CHF-CH 2 -OCO- (L) q'-W, SO 3 - -CF 2 -COO- (L) q'-W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 - (L) q-W, or, SO 3 - -CF 2 -CH (CF 3 ) -OCO- (L) q'-W is preferred.
• L, q, and W are the same as in the general formula (3).
• the anion represented by formula (4) is also preferred.
• Each of X B1 and X B2 independently represents a hydrogen atom or a monovalent organic group having no fluorine atom.
• X B1 and X B2 are preferably hydrogen atoms.
• Each of X B3 and X B4 independently represents a hydrogen atom or a monovalent organic group.
• At least one of X B3 and X B4 is preferably a fluorine atom or a monovalent organic group having a fluorine atom, and both of X B3 and X B4 are a fluorine atom or a monovalent organic group having a fluorine atom Is more preferred. More preferably, both X B3 and X B4 are a fluorine-substituted alkyl group.
• L, q and W are the same as in the general formula (3).
• the anion represented by is also preferable.
• Xa each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
• Each Xb independently represents a hydrogen atom or an organic group having no fluorine atom.
• 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) - is a benzenesulfonate anion And is preferably a benzenesulfonic acid anion substituted by a branched alkyl group or a cycloalkyl group.
• Ar represents an aryl group, and may further have a substituent other than a sulfonate anion and a-(D-B) group.
• substituent which may further have include a fluorine atom and a hydroxyl group.
• N represents an integer of 0 or more. As n, 1 to 4 is preferable, 2 to 3 is more preferable, and 3 is more preferable.
• 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 sulfonic acid 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 isopropyl or cyclohexyl.
• Trisulfonic carbanion, for example, C - is an anion represented by (SO 2 -R p) 3.
• R p represents an alkyl group which may have a substituent, a fluoroalkyl group is preferable, a perfluoroalkyl group is more preferable, and a trifluoromethyl group is still more preferable.
• the disulfonamide anion is, for example, an anion represented by N ⁇ (SO 2 -R q ) 2 .
• R q represents an alkyl group which may have a substituent, a fluoroalkyl group is preferable, and a perfluoroalkyl group is more preferable.
• Two R q may combine with each other to form a ring.
• the group formed by bonding two R q to each other is preferably an alkylene group which may have a substituent, a fluoroalkylene group is preferable, and a perfluoroalkylene group is more preferable.
• the carbon number of the above-mentioned alkylene group (preferably a fluoroalkylene group, more preferably a perfluoroalkylene group) is preferably 2 to 4.
• the photoacid generator may be in the form of a low molecular weight compound, or may be in the form of being incorporated into a part of a polymer. Also, the form of the low molecular weight compound and the form incorporated into a part of the polymer may be used in combination.
• the photoacid generator is preferably in the form of a low molecular weight compound.
• the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less.
• the lower limit is not particularly limited, but is usually 50 or more.
• the photoacid generator When the photoacid generator is incorporated into a part of the polymer, it may be incorporated into a part of the resin A described above, or may be incorporated into a resin different from the resin A.
• the photoacid generator may be used alone or in combination of two or more.
• the content of the photoacid generator in the composition (the total amount of the multiple types, if any) is preferably 0.1 to 35% by mass, based on the total solid content of the composition, 0.5 to 25% by mass Is more preferable, and 3 to 20% by mass is more preferable.
• the composition of the present invention may contain a hydrophobic resin.
• the hydrophobic resin is preferably a resin different from the resin A.
• the composition of the present invention can control the static and / or dynamic contact angle on the surface of the actinic ray-sensitive or radiation-sensitive film by including a hydrophobic resin. This makes it possible to improve development characteristics, suppress outgassing, improve immersion liquid followability in immersion exposure, and reduce immersion defects.
• the hydrophobic resin is preferably designed to be localized on the surface of the resist film, but unlike the surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and it is possible to uniformly use polar substances and nonpolar substances. It does not have to contribute to mixing.
• the hydrophobic resin is at least one selected from the group consisting of "fluorine atom”, “silicon atom”, and "CH 3 partial structure contained in the side chain portion of the resin” from the viewpoint of localization to the film surface. It is preferable that it is resin which has a repeating unit which has a seed
• the hydrophobic resin contains a fluorine atom and / or a silicon atom
• the fluorine atom and / or the silicon atom in the hydrophobic resin may be contained in the main chain of the resin and is contained in the side chain. May be
• the hydrophobic resin contains a fluorine atom
• the resin has a fluorine atom-containing alkyl group, a fluorine atom-containing cycloalkyl group, or a fluorine atom-containing aryl group as a partial structure having a fluorine atom.
• the hydrophobic resin preferably has at least one group selected from the following groups (x) to (z).
• Examples of the acid group (x) include phenolic hydroxyl group, carboxy group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) ) Imido group, bis (alkyl carbonyl) methylene group, bis (alkyl carbonyl) imide group, bis (alkyl sulfonyl) methylene group, bis (alkyl sulfonyl) imide group, tris (alkyl carbonyl) methylene group, and tris (alkyl sulfonyl) And the like) and the like.
• a fluorinated alcohol group preferably hexafluoroisopropanol
• a sulfoneimide group or a bis (alkylcarbonyl)
• Examples of the group (y) which is decomposed by the action of the alkali developer to increase the solubility in the alkali developer include, for example, lactone group, carboxy ester group (-COO-), acid anhydride group (-CO-O-CO- ), Acid imide group (-NHCONH-), carboxy thioester group (-COS-), carbonate group (-O-CO-O-), sulfate group (-OSO 2 O-), and sulfonate group (-SO 2 O-) etc. are mentioned, and a lactone group or a carboxy ester group (-COO-) is preferable.
• repeating unit containing these groups it is a repeating unit which these groups are directly couple
• these groups may be bonded to the main chain of the resin via a linking group.
• this repeating unit may be introduced at the end of the resin by using a polymerization initiator or chain transfer agent having these groups at the time of polymerization.
• a repeating unit which has a lactone group the thing similar to the repeating unit which has the lactone structure previously demonstrated by the term of the resin A is mentioned, for example.
• the content of the repeating unit having a group (y) which is decomposed by the action of the alkali developer to increase the solubility in the alkali developer is preferably 1 to 100 mol% with respect to all the repeating units in the hydrophobic resin, 3 to 98 mol% is more preferable, and 5 to 95 mol% is more preferable.
• the repeating unit having a group (z) capable of decomposing by the action of an acid in the hydrophobic resin may be the same as the repeating unit having an acid decomposable group mentioned in the resin A.
• the repeating unit having a group (z) capable of decomposing under the action of an acid may have at least one of a fluorine atom and a silicon atom.
• the content of the repeating unit having a group (z) decomposable by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, with respect to all the repeating units in the hydrophobic resin. 60 mol% is more preferred.
• the hydrophobic resin may further have another repeating unit other than the above-described repeating unit.
• the repeating unit containing a fluorine atom is preferably 10 to 100% by mole, and more preferably 30 to 100% by mole, relative to all repeating units in the hydrophobic resin.
• the repeating unit containing a silicon atom is preferably 10 to 100% by mole, and more preferably 20 to 100% by mole, relative to all repeating units in the hydrophobic resin.
• the hydrophobic resin does not substantially contain a fluorine atom and a silicon atom, particularly when the hydrophobic resin contains a CH 3 partial structure in the side chain portion.
• the hydrophobic resin is preferably substantially constituted only by a repeating unit constituted only by an atom selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom.
• the weight average molecular weight of the hydrophobic resin in terms of standard polystyrene is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000.
• the total content of the remaining monomer and / or oligomer components contained in the hydrophobic resin is preferably 0.01 to 5% by mass, and more preferably 0.01 to 3% by mass.
• the degree of dispersion (Mw / Mn) is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0.
• known resins can be appropriately selected and used alone or as a mixture thereof.
• known resins disclosed in paragraphs ⁇ 0451> to ⁇ 0704> of US Patent Application Publication No. 2015/0168830 A1 and in paragraphs ⁇ 0340> to ⁇ 0356> of US Patent Application Publication No. 2016/0274458 A1. Can be suitably used as a hydrophobic resin.
• repeating units disclosed in paragraphs ⁇ 0177> to ⁇ 0258> of US Patent Application Publication No. 2016/0237190 A1 are also preferable as repeating units constituting the hydrophobic resin.
• the hydrophobic resin may be used alone or in combination of two or more. It is also preferable to use a mixture of two or more hydrophobic resins different in surface energy, from the viewpoint of achieving both the immersion liquid followability and the development characteristics in immersion exposure.
• the content of the hydrophobic resin in the composition is preferably 0.01 to 10% by mass, and more preferably 0.03 to 8% by mass, with respect to the total solid content in the composition of the present invention.
• the composition of the present invention may contain a surfactant.
• a fluorine-based and / or silicon-based surfactant specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom
• a fluorine-based and / or silicon-based surfactant specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom
• composition of the present invention contains a surfactant
• a surfactant when an exposure light source of 250 nm or less (especially 220 nm or less) is used, a pattern with less adhesion and development defects can be obtained with good sensitivity and resolution.
• the fluorine-based and / or silicon-based surfactant the surfactants described in paragraph ⁇ 0276> of US Patent Application Publication No. 2008/0248425 can be mentioned.
• other surfactants than the fluorine-based and / or silicon-based surfactants described in paragraph ⁇ 0280> of US Patent Application Publication No. 2008/0248425 can also be used.
• the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, with respect to the total solid content of the composition. preferable.
• the content of the surfactant is 10 mass ppm or more with respect to the total solid content of the composition, the surface uneven distribution of the hydrophobic resin is increased. As a result, the surface of the actinic ray-sensitive or radiation-sensitive film can be made more hydrophobic, and the water followability at the time of immersion exposure is improved.
• the composition of the present invention may contain a solvent.
• known resist solvents can be appropriately used.
• paragraphs ⁇ 0665> to ⁇ 0670> of U.S. Patent Application Publication 2016 / 0070167A1; paragraphs ⁇ 0210> to ⁇ 0235> of U.S. Patent Application Publication 2015 / 0004544A1, U.S. Patent Application Publication 2016 / 0237190A1 Known solvents disclosed in paragraphs ⁇ 0424> to ⁇ 0426> of the specification and paragraphs ⁇ 0357> to ⁇ 0366> of US Patent Application Publication 2016/0274458 A1 can be suitably used.
• solvents examples include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, alkyl alkoxypropionate, cyclic lactone (preferably having a carbon number of 4 to 10), Examples thereof include organic solvents such as monoketone compounds (preferably having a carbon number of 4 to 10) which may have a ring, alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.
• the mixed solvent which mixed the solvent which has a hydroxyl group in a structure may be used, and the solvent which does not have a hydroxyl group.
• the solvent having a hydroxyl group and the solvent having no hydroxyl group the above-mentioned exemplified compounds can be appropriately selected, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether or alkyl lactate is preferable, and propylene glycol monomethyl ether (PGME ), Propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred.
• PGME propylene glycol monomethyl ether
• PGEE Propylene glycol monoethyl ether
• 2-hydroxyisobutyrate or ethyl lactate
• alkylene glycol monoalkyl ether acetate alkyl alkoxy propionate
• a monoketone compound which may have a ring alkyl alkoxy propionate
• a monoketone compound which may have a ring alkyl alkoxy propionate
• a monoketone compound which may have a ring alkyl alkoxy propionate
• a monoketone compound which may have a ring alkyl acetate and the like are preferable.
• Propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, cyclopentanone or butyl acetate is more preferable, and propylene glycol monomethyl ether acetate, ⁇ -butyrolactone, ethyl ethoxy pro More preferred are propionate, cyclohexanone, cyclopentanone or 2-heptanone.
• Propylene carbonate is also preferred as the solvent having no hydroxyl group.
• the mixing ratio (mass ratio) of the solvent having a hydroxyl group to the solvent having no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. preferable.
• a mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable in view of coating uniformity.
• the solvent preferably comprises propylene glycol monomethyl ether acetate.
• the solvent may be propylene glycol monomethyl ether acetate alone or a mixed solvent of two or more kinds including propylene glycol monomethyl ether acetate.
• the solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and still more preferably 2.0 to 5.3% by mass. That is, when the composition contains a solvent, the content of the solvent in the composition is preferably adjusted so as to satisfy the above-mentioned preferable range of the solid content concentration.
• solid content concentration is a mass percentage of the mass of the other resist component except a solvent with respect to the total mass of a composition.
• a resist film an actinic ray-sensitive or radiation-sensitive composition
• a resist film comprising the composition of the present invention by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property or the film forming property. Film thickness can be adjusted.
• composition according to the present invention may further comprise resins other than those described above, crosslinkers, acid multipliers, dyes, plasticizers, photosensitizers, light absorbers, alkali soluble resins, dissolution inhibitors, dissolution accelerators, etc. May be included.
• the composition of the present invention is preferably used by dissolving the above components in a predetermined organic solvent (preferably the above mixed solvent), filtering it, and then applying it on a predetermined support (substrate).
• a predetermined organic solvent preferably the above mixed solvent
• 0.05 micrometer or less is preferable, as for the pore size of the filter used for filter filtration, 0.05 micrometer or less is more preferable, and 0.03 micrometer or less is still more preferable.
• the filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. In filter filtration, as disclosed in, for example, Japanese Patent Application Publication No. 2002-62667 (Japanese Patent Application Laid-Open No.
• cyclic filtration may be performed, and a plurality of types of filters are connected in series or in parallel. May be connected to
• the composition may also be filtered multiple times. Furthermore, the composition may be subjected to degassing treatment and the like before and after filter filtration.
• the composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition which changes its property in response to irradiation with an actinic ray or radiation. More specifically, the composition of the present invention can be used in semiconductor manufacturing processes such as IC (Integrated Circuit), production of circuit substrates such as liquid crystals or thermal heads, production of imprint mold structures, other photofabrication processes, or The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used for the production of a lithographic printing plate or an acid-curable composition.
• the pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode formation process, a rewiring formation process, MEMS (Micro Electro Mechanical Systems), and the like.
• the present invention also relates to a method of forming a pattern using the actinic ray-sensitive or radiation-sensitive resin composition.
• the pattern formation method of the present invention will be described.
• the resist film (the actinic ray sensitive or radiation sensitive film) of the present invention will also be described.
• the pattern formation method of the present invention is (I) A step of forming a resist film (an actinic ray sensitive or radiation sensitive film) on a support using the actinic ray sensitive or radiation sensitive resin composition described above (a resist film forming step (film forming step) ), (Ii) exposing the resist film (irradiating with an actinic ray or radiation) (exposure step), and (Iii) developing the exposed resist film with a developer (developing step).
• the pattern forming method of the present invention is not particularly limited as long as it includes the above steps (i) to (iii), and may further include the following steps.
• the exposure method in the exposure step may be immersion exposure.
• the pattern formation method of the present invention preferably includes (iv) a preheating (PB: PreBake) step before (ii) the exposure step.
• the pattern forming method of the present invention preferably includes (v) a post exposure baking (PEB) step after (ii) the exposure step and (iii) before the development step.
• PEB post exposure baking
• the pattern formation method of the present invention may include (ii) multiple exposure steps.
• the pattern formation method of the present invention may include (iv) a preheating step a plurality of times.
• the pattern formation method of the present invention may include (v) a post-exposure heating step a plurality of times.
• the above-described (i) resist film formation step (film formation step), (ii) exposure step, and (iii) development step can be performed by a generally known method. .
• the thickness of the resist film is preferably 90 nm or less, more preferably 85 nm or less, from the viewpoint of improving resolution.
• a resist underlayer film for example, SOG (Spin On Glass), SOC (Spin On Carbon), and an antireflective film
• SOG Spin On Glass
• SOC Spin On Carbon
• an antireflective film may be formed between the resist film and the support.
• a material which comprises a resist underlayer film well-known organic type or inorganic type material can be used suitably.
• a protective film (top coat) may be formed on the upper layer of the resist film.
• a well-known material can be used suitably as a protective film.
• composition for protective film formation disclosed by US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016 / 157988A can be suitably used.
• a composition for protective film formation what contains the acid diffusion control agent mentioned above is preferable.
• a protective film may be formed on the upper layer of the resist film containing the hydrophobic resin described above.
• the support is not particularly limited, and is generally used in a process of manufacturing a semiconductor such as an IC or a process of manufacturing a circuit substrate such as a liquid crystal or a thermal head, and other lithography processes of photofabrication.
• Substrate can be used.
• Specific examples of the support include inorganic substrates such as silicon, SiO 2 , and SiN.
• the heating temperature is preferably 70 to 150 ° C. and more preferably 80 to 120 ° C. in any of the (iv) pre-heating step and the (v) post-exposure heating step.
• the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds in any of the (iv) pre-heating step and (v) post-exposure heating step.
• the heating can be performed by means provided in the exposure apparatus and the developing apparatus, and may be performed using a hot plate or the like.
• the light source wavelength used in the exposure step is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams.
• far ultraviolet light is preferable, and its wavelength is preferably 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm.
• KrF excimer laser (248 nm), ArF excimer laser (193 nm), F 2 excimer laser (157 nm), X-ray, EUV (13 nm), or, preferably electron beams, KrF excimer laser, ArF excimer laser , EUV or electron beam is more preferable.
• the developer may be either an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).
• alkali developing solution quaternary ammonium salts represented by tetramethyl ammonium hydroxide are used as the alkali developing solution, but besides this, alkaline aqueous solutions such as inorganic alkalis, primary to tertiary amines, alcohol amines and cyclic amines are used. Are also available.
• the alkali developer may contain an appropriate amount of an alcohol and / or a surfactant.
• the alkali concentration of the alkali developer is usually 0.1 to 20% by mass.
• the pH of the alkaline developer is usually 10-15.
• the time for developing using an alkaline developer is usually 10 to 300 seconds.
• the alkali concentration, pH, and development time of the alkali developer can be appropriately adjusted according to the pattern to be formed.
• the organic developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Is preferred.
• ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples thereof include cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate and the like.
• ester solvents for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl 3-ethoxy propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, butyl lactate, butane And butyl acid, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
• the solvents disclosed in paragraphs ⁇ 0715> to ⁇ 0718> of US Patent Application Publication No. 2016/0070167 A1 can be used.
• a plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water.
• the water content of the developer as a whole is preferably less than 50% by weight, more preferably less than 20% by weight, still more preferably less than 10% by weight, and particularly preferably substantially free of water.
• the content of the organic solvent to the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, with respect to the total amount of the developer. % Is particularly preferred.
• the developer may contain an appropriate amount of a known surfactant as needed.
• the content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, with respect to the total amount of the developer.
• the organic developer may contain an acid diffusion control agent.
• a developing method for example, a method of immersing the substrate in a bath filled with a developer for a certain time (dip method), a method of raising the developer on the substrate surface by surface tension and standing still for a certain time (paddle method) The method of spraying the developer on the surface (spray method), and the method of continuing to discharge the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic dispense method), etc. It can be mentioned.
• the step of developing using an alkaline aqueous solution (alkali developing step) and the step of developing using a developer containing an organic solvent (organic solvent developing step) may be combined.
• alkali developing step alkaline aqueous solution
• organic solvent developing step organic solvent developing step
• the rinse liquid used for the rinse process after the image development process using an alkaline developing solution can use a pure water, for example.
• the pure water may contain an appropriate amount of surfactant.
• a process of removing the developer or rinse solution adhering on the pattern with a supercritical fluid may be added.
• heat treatment may be performed to remove moisture remaining in the pattern after the rinse treatment or treatment with a supercritical fluid.
• the rinse solution used for the rinse process after the development process using the developing solution containing an organic solvent does not have a restriction
• the solution containing a common organic solvent can be used.
• a rinse solution containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. It is preferable to do.
• hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include the same ones as described in the developer containing an organic solvent.
• a rinse solution containing a monohydric alcohol is more preferable.
• Examples of the monohydric alcohol used in the rinsing step include linear, branched or cyclic monohydric alcohol. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1 Heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and methyl isobutyl carbinol.
• the monohydric alcohol preferably has 5 or more carbon atoms, and examples thereof include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol And methyl isobutyl carbinol and the like.
• a plurality of each component may be mixed, or may be mixed with an organic solvent other than the above. 10 mass% or less is preferable, as for the moisture content in the rinse liquid used for the rinse process after the image development process using the developing solution containing an organic solvent, 5 mass% or less is more preferable, and 3 mass% or less is still more preferable. By setting the water content to 10% by mass or less, good development characteristics can be obtained.
• the rinse solution after the development step using a developer containing an organic solvent may contain an appropriate amount of surfactant.
• the developed substrate is washed using a rinse solution.
• the method of the cleaning process is not particularly limited, for example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotation coating method), and immersing the substrate in a bath filled with the rinse liquid for a fixed time
• examples include a method (dip method) or a method of spraying a rinse liquid on the substrate surface (spray method).
• preferred is a method in which the cleaning treatment is performed by spin coating, and after cleaning, the substrate is rotated at a rotational speed of 2,000 to 4,000 rpm to remove the rinse solution from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step.
• the heating temperature is usually 40 to 160 ° C., preferably 70 to 95 ° C.
• the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, and various materials used in the pattern forming method of the present invention preferably does not contain impurities such as metal components, isomers and residual monomers.
• the content of these impurities contained in the above various materials is preferably 1 mass ppm or less, more preferably 100 mass ppt or less, still more preferably 10 mass ppt or less, and substantially not including (detection of measuring device Or less) is particularly preferred.
• the pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
• a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable.
• the filter may be one previously washed with an organic solvent.
• plural types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes and / or different materials may be used in combination.
• the various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step.
• the filter one having a reduced elution product as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Application Laid-Open No. 2016-201426) is preferable.
• an adsorbent may be used to remove impurities, or filter filtration and an adsorbent may be used in combination.
• known adsorbents can be used.
• inorganic adsorbents such as silica gel or zeolite, or organic adsorbents such as activated carbon can be used.
• the metal adsorbent examples include those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Laid-Open No. 2016-206500).
• filter filtration is carried out on the materials constituting the various materials, selecting the materials having a low metal content as the materials constituting the various materials Alternatively, there may be mentioned a method such as distilling under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark) or the like.
• Teflon registered trademark
• the preferable conditions in the filter filtration performed with respect to the raw material which comprises various materials are the same as the conditions mentioned above.
• a method of improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention.
• a method of improving the surface roughness of the pattern for example, a method of processing the pattern by plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/0104957 can be mentioned.
• Japanese Patent Application Publication No. 2004-235468 Japanese Patent Laid-Open No. 2004-2354608
• US Patent Application Publication No. 2010/0020297 and Proc. of SPIE Vol.
• a known method may be applied as described in 8328 83280 N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement”.
• the pattern formed by the above method is disclosed, for example, in Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Application Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/0209941. It can be used as core of spacer process.
• the present invention also relates to a method of manufacturing an electronic device, including the pattern forming method described above.
• the electronic device manufactured by the method of manufacturing an electronic device according to the present invention is preferably used for electric and electronic devices (for example, home appliances, office automation (OA) related devices, media related devices, optical devices, communication devices, etc.). Will be mounted.
• electric and electronic devices for example, home appliances, office automation (OA) related devices, media related devices, optical devices, communication devices, etc.
• the invention also includes the invention of compounds.
• the compound of the present invention is the same as the compound represented by the general formula (II-2), and preferred conditions are also the same.
• Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition [component]
• components included in the actinic ray-sensitive or radiation-sensitive resin composition hereinafter, also referred to as “composition”
• composition also referred to as “composition”
• Photoacid generator used for preparation of a composition is shown below.
• ⁇ Surfactant> The surfactants used to prepare the composition are shown below.
• ⁇ Solvent> The solvents used to prepare the composition are shown below.
• composition Each of the components was dissolved in a solvent according to the composition described in the table shown in the latter part, and a solution having a solid content concentration of 3.8% by mass was prepared for each. Then, the solution obtained was filtered through a polyethylene filter having a pore size of 0.1 ⁇ m to prepare an actinic ray-sensitive or radiation-sensitive resin composition (composition).
• the resist film thus obtained was formed into a line width of 44 nm using an ArF excimer laser liquid immersion scanner (manufactured by ASML; XT 1700 i, NA 1.20, C-Quad, outer sigma 0.730, inner sigma 0.630, XY deflection) Exposed through a 6% halftone mask with a 1: 1 line and space pattern. Ultrapure water was used as the immersion liquid. Thereafter, the film was heated at 120 ° C. for 60 seconds, developed with butyl acetate for 30 seconds, and spin-dried to obtain a pattern.
• the storage stability of the composition was evaluated by applying the particle increase number calculated by “(number of particles after aging) ⁇ (initial particle value)” to the following criteria. The less the number of particles increases, the better the storage stability.
• substances having a particle diameter of 0.25 ⁇ m or more contained in 1.0 ml of the composition were counted as particles. The results are described in the following table.
• composition of the composition and the results of the evaluation performed using those compositions are shown in the following table.
• 10 g, 0.05 g and 0.03 g of a resin, a hydrophobic resin and a surfactant were blended respectively.
• the mass (g) shown by parenthesis with each component name was mix
• the solvent was blended so that the internal ratio (mass ratio) of each solvent was the ratio shown in each column, and the solid content concentration of the composition was 3.8 mass%.
• the composition of the present invention is excellent in storage stability and that a pattern excellent in LWR performance can be obtained.
• the storage stability of the composition is more excellent, and LWR is more preferable. It was confirmed that a pattern with better performance could be obtained (comparison of Examples 1, 2 and 5).
• the composition further contains a photoacid generator which is a compound other than the compound Q, it was confirmed that a pattern with more excellent LWR performance can be obtained (comparison of Examples 9 and 19).

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