Classifications

• • 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
  • G03F7/20—Exposure; Apparatus therefor

Definitions

• the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and an electronic device manufacturing method.
• a pattern formation method using chemical amplification has been used to compensate for the sensitivity reduction due to light absorption.
• a photoacid generator contained in an exposed portion is decomposed by light irradiation to generate an acid.
• PEB Post Exposure Bake
• the alkali-insoluble group contained in the photosensitive composition is changed to an alkali-soluble group by the catalytic action of the generated acid.
• development is performed using, for example, an alkaline solution.
• an exposed part is removed and a desired pattern is obtained.
• various alkali developers have been proposed.
• this alkaline developer a 2.38 mass% TMAH (tetramethylammonium hydroxide aqueous solution) aqueous alkaline developer is generally used.
• the exposure light source has become shorter and the projection lens has a higher numerical aperture (high NA).
• high NA numerical aperture
• an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed.
• a method of filling a liquid having a high refractive index (hereinafter also referred to as “immersion liquid”) between the projection lens and the sample has been proposed.
• Patent Document 1 discloses a resist composition that generates an acid upon exposure and changes its solubility in a developer due to the action of an acid, and includes a base material component whose solubility in a developer changes due to the action of an acid.
• a resist composition containing a nitrogen-containing compound having a boiling point of 50 to 200 ° C. and a pKa of a conjugate acid of 0 to 7 and a photobase deactivator is described.
• Patent Document 2 discloses a polymer compound having a repeating unit in which a hydroxy group is substituted with an acid labile group and an acid generator, or a repeating unit in which a hydroxy group is substituted with an acid labile group and a repeating unit that generates an acid upon exposure.
• a resist composition containing a polymer compound having a unit, a sulfonium salt or an iodonium salt of fluoroalkylsulfonamide, and an organic solvent is applied on a substrate, and after the heat treatment, the resist film is exposed with a high energy ray, and the heat treatment is performed.
• a pattern forming method for obtaining a negative pattern in which an unexposed portion is dissolved by using a developer with an organic solvent later and the exposed portion is not dissolved is described.
• the problem to be solved by the present invention is excellent in the LWR performance and the rectangular shape of the cross-sectional shape of the pattern, and at the time of forming a blank pattern (for example, an isolated hole pattern) and a remaining pattern (for example, an isolated dot pattern).
• a blank pattern for example, an isolated hole pattern
• a remaining pattern for example, an isolated dot pattern.
• the present inventors have intensively studied and found that the above problem can be solved by using an onium salt having an amide structure (onium salt (C)) in a counter cation having a specific structure.
• the onium salt (C) used in the present invention has an amide structure and has a weaker basicity than a basic compound (typically amines) usually used in a resist composition.
• the portion hardly inhibits the action of the acid generated from the photoacid generator, and the unexposed portion functions sufficiently as an acid quencher (trap agent). Thereby, it is considered that the LWR performance can be improved.
• the onium salt (C) used in the present invention has a low volatility by having a salt structure, and can suppress volatilization from the film surface that occurs when an actinic ray-sensitive or radiation-sensitive film is formed.
• the presence of the onium salt (C) as a quencher at the upper part of the pattern can obtain a desired pattern shape, so that the rectangularity of the cross-sectional shape of the pattern and the LWR performance can be improved. it is conceivable that.
• the onium salt (C) was able to improve the common DOF performance because it has an appropriate diffusivity in addition to the above-described characteristics.
• the present inventors have found that the above problem can be solved by the following configuration.
• An actinic ray-sensitive or radiation-sensitive resin composition containing The onium salt (C) is represented by the following general formula (1), The actinic ray-sensitive or radiation-sensitive resin composition, wherein the content of the onium salt (C) in the actinic ray-sensitive or radiation-sensitive resin composition is less than the content of the compound (B) in terms of mole.
• X 1 represents a sulfur atom, an iodine atom, or a nitrogen atom
• Q 1 represents a group having an amide structure
• Q 2 represents an alkyl group, a cycloalkyl group, or an aryl group.
• at least one of Q 1 and k Q 2 represents an alkyl group or a cycloalkyl group.
• X 1 represents a sulfur atom
• k 2
• X 1 represents an iodine atom
• Y 1 represents an organic counter anion.
• Q 1 and at least one of k Q 2 may be bonded to each other to form a ring structure.
• Q 3 and Q 4 each independently represents an alkyl group or a cycloalkyl group
• L 1 represents an alkylene group or a cycloalkylene group
• Q 5 and Q 6 each independently represent a hydrogen atom
• an alkyl group Represents a group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, or a heteroaryl group.
• At least two of Q 3 to Q 6 and L 1 may be bonded to each other to form a ring structure.
• Y 2 is an organic counter anion.
• the actinic ray-sensitive or radiation-sensitive resin composition according to item 1. [8] The actinic ray according to any one of [1] to [7], further comprising (D) a hydrophobic resin having at least one of a fluorine atom and a silicon atom, which is different from the resin (A). Or radiation sensitive resin composition. [9] The actinic ray-sensitive or radiation-sensitive resin composition according to [8], wherein the hydrophobic resin (D) is a fluorine-containing (meth) acrylate resin. [10] The content of the hydrophobic resin (D) in the actinic ray-sensitive or radiation-sensitive resin composition is 1 to 10% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition.
• the actinic ray-sensitive or radiation-sensitive resin composition according to [8] or [9].
• the LWR performance and the rectangular shape of the cross-sectional shape of the pattern are excellent, and a large common DOF is felt when forming a blank pattern (for example, an isolated hole pattern) and a remaining pattern (for example, an isolated dot pattern).
• An actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film using the same, a pattern formation method, and an electronic device manufacturing method can be provided.
• the description of group (atomic group) in this specification the description which has not described substitution and non-substitution includes what has a substituent with what does not have a 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” refers to a group containing at least one carbon atom.
• active light refers to, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV), X-rays, and electron beams (EB: Electron Beam) or the like.
• light means actinic rays or radiation.
• exposure in the present specification is not only exposure by the emission line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, EUV, etc., but also electron beams and ions. This includes drawing with particle beams such as beams.
• “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
• (meth) acrylate represents acrylate and methacrylate
• (meth) acryl represents acryl and methacryl
• the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of the resin are GPC (Gel Permeation Chromatography) apparatus (HLC-produced by Tosoh Corporation).
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) will be described.
• the composition of the present invention comprises (A) a resin whose polarity is increased by the action of an acid to change its solubility in a developer, (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and (C) a counter cation. It contains an onium salt having an amide structure.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably a 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 resist composition of the present invention is typically a chemically amplified resist composition.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is also referred to as a resin ("acid-decomposable resin” or "resin (A)") whose polarity is increased by the action of an acid and its solubility in a developer is changed. ).
• the resin (A) preferably has a group (hereinafter also referred to as “acid-decomposable group”) that is decomposed by the action of an acid to increase the polarity.
• the resin (A) is a resin that increases in polarity by the action of an acid and increases in solubility in an alkaline developer, and is preferably a resin that decreases in solubility in an organic developer.
• a positive pattern is suitably formed, and when an organic developer is used as the developer, a negative pattern is formed.
• a mold pattern is suitably formed.
• Resin (A) preferably has a repeating unit having an acid-decomposable group.
• the acid-decomposable group preferably has a structure in which a polar group is protected with a group capable of decomposing and leaving by the action of an acid (leaving group).
• polar groups carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Acid groups (groups dissociating in an aqueous 2.38 mass
• the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group). Excludes aliphatic alcohols substituted with sexual groups (for example, hexafluoroisopropanol groups).
• the alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.
• Preferred polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.
• a preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving by the action of an acid (leaving group).
• Examples of the group (leaving group) leaving by the action of an acid include —C (R 36 ) (R 37 ) (R 38 ), —C (R 36 ) (R 37 ) (OR 39 ), and — And C (R 01 ) (R 02 ) (OR 39 ).
• R 36 to R 39 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
• R 36 and R 37 may be bonded to each other to form a ring.
• R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
• the alkyl group of R 36 to R 39 , R 01 and R 02 is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl Group, and octyl group.
• the cycloalkyl group of R 36 to R 39 , R 01 and R 02 may be monocyclic or polycyclic.
• the monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
• a cycloalkyl group having 6 to 20 carbon atoms is preferable.
• the aryl group of R 36 to R 39 , R 01 and R 02 is preferably an aryl group having 6 to 10 carbon atoms, 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 7 to 12 carbon atoms, 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 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
• the ring formed by combining R 36 and R 37 with each other is preferably a cycloalkyl group (monocyclic or polycyclic).
• cycloalkyl group a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferable. .
• a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group is preferable, and an acetal ester group or a tertiary alkyl ester group is more 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.
• Xa 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
• T represents a single bond or a divalent linking group.
• Rx 1 to Rx 3 each independently represents an alkyl group or a cycloalkyl group. Any two of Rx 1 to Rx 3 may be bonded to form a ring structure, or may not be formed.
• Examples of the divalent linking group for T include an alkylene group, an arylene group, —COO—Rt—, —O—Rt—, and the like.
• 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, more preferably —CH 2 —, — (CH 2 ) 2 —, or — (CH 2 ) 3 —. More preferably, T is a single bond.
• 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 thereof 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.
• the alkyl group of Rx 1 , Rx 2 and Rx 3 may be linear or branched, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl. Group, t-butyl group and the like are preferable.
• the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
• a part of the carbon-carbon bond may be a double bond.
• Examples of the cycloalkyl group represented by Rx 1 , Rx 2 and 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, an adamantyl group, and the like.
• the polycyclic cycloalkyl group is preferable.
• the ring structure formed by combining two of Rx 1 , Rx 2 and Rx 3 includes a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, a norbornane ring, a tetracyclo ring, or the like.
• a polycyclic cycloalkyl ring such as a decane ring, a tetracyclododecane ring and an adamantane ring is preferred.
• a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferable.
• the ring structure formed by combining two of Rx 1 , Rx 2 and Rx 3 the structures shown below are also preferable.
• the resin (A) preferably has a repeating unit described in paragraphs ⁇ 0336> to ⁇ 0369> of US Patent Application Publication No. 2016 / 0070167A1 as a repeating unit having an acid-decomposable group.
• Resin (A) is decomposed by the action of an acid described in paragraphs ⁇ 0363> to ⁇ 0364> of US Patent Application Publication No. 2016 / 0070167A1 as a repeating unit having an acid-decomposable group. You may have a repeating unit containing the group which produces
• Resin (A) may contain one type of repeating unit having an acid-decomposable group, or two or more types in combination.
• the content of the repeating unit having an acid-decomposable group contained in the resin (A) (when there are a plurality of repeating units having an acid-decomposable group, the total) is based on the total repeating units of the resin (A), 10 to 90 mol% is preferable, 20 to 80 mol% is more preferable, and 30 to 70 mol% is still more preferable.
• 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.
• Any lactone structure or sultone structure can be used as long as it has a lactone structure or sultone structure, but a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable.
• lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3) More preferably, it has a repeating unit.
• a lactone structure or a sultone structure may be directly bonded to the main chain. Preferred structures are (LC1-1), (LC1-4), (LC1-5), (LC1-8), (LC1-16), (LC1-21) and (SL1-1).
• the lactone structure portion or the sultone structure portion may or may not have a substituent (Rb 2 ).
• Preferred substituents (Rb 2 ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, and carboxyl groups.
• n 2 represents an integer of 0 to 4. When n 2 is 2 or more, the plurality of substituents (Rb 2 ) may be the same or different. A plurality of substituents (Rb 2 ) may be bonded to form a ring.
• the repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following general formula (III).
• A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
• n is the number of repetitions of the structure represented by —R 0 —Z—, and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0.
• R 0 represents an alkylene group, a cycloalkylene group, or a combination thereof.
• each R 0 independently represents an alkylene group, a cycloalkylene group, or a combination thereof.
• Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
• each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
• R 8 represents a monovalent organic group having a lactone structure or a sultone structure.
• R 7 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).
• the alkylene group or cycloalkylene group of R 0 may have a substituent.
• Z is preferably an ether bond or an ester bond, and more preferably an ester bond.
• the following monomers are also suitably used as the raw material for the resin (A).
• the resin (A) may have a repeating unit having a carbonate structure.
• the carbonate structure is preferably a cyclic carbonate structure.
• the repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).
• 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.
• R A 2 each independently represents a substituent when n is 2 or more.
• A represents a single bond or a divalent linking group.
• Z represents an atomic group that forms a monocyclic structure or a polycyclic structure together with a group represented by —O—C ( ⁇ O) —O— in the formula.
• the 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, and paragraphs ⁇ 0370> to ⁇ 0414> of US Patent Application Publication No. 2016 / 0070167A1. It is also preferable to have the repeating unit described in 1.
• Resin (A) may contain one or more repeating units having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, or may contain two or more kinds in combination.
• the total (when there are a plurality of repeating units having at least one kind) is preferably 5 to 70 mol%, and preferably 10 to 65 mol%, based on all the repeating units of the resin (A). More preferably, it is more preferably 20 to 60 mol%.
• the resin (A) preferably has a repeating unit having a polar group.
• the polar group include a hydroxyl group, a cyano group, a carboxyl group, and a fluorinated alcohol group.
• 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-decomposable group.
• the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group or a norbornane group.
• Resin (A) may contain the repeating unit which has a polar group individually by 1 type, and may contain 2 or more types together.
• the content of the repeating unit having a polar group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (A).
• Resin (A) can further have a repeating unit having neither an acid-decomposable 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-decomposable 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-decomposable group nor a polar group are shown below.
• Resin (A) may contain the repeating unit which has neither an acid-decomposable group nor a polar group individually by 1 type, and may contain 2 or more types together.
• the content of the repeating unit having neither an acid-decomposable group nor a polar group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, based on all repeating units in the resin (A). 5 to 25 mol% is more preferable.
• Resin (A) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general required properties of resist, in addition to the above repeating structural units.
• various repeating structural units can be included. Examples of such a repeating structural unit include, but are not limited to, a repeating structural unit corresponding to a monomer.
• the monomer examples include compounds having one addition polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Can be mentioned. In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized. In the resin (A), the content molar ratio of each repeating structural unit is appropriately set in order to adjust various performances.
• the resin (A) preferably has substantially no aromatic group from the viewpoint of ArF light transmittance. More specifically, the repeating unit having an aromatic group in all the repeating units of the resin (A) is preferably 5 mol% or less, more preferably 3 mol% or less, ideally Is more preferably 0 mol%, that is, it does not have a repeating unit having an aromatic group.
• the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
• all of the repeating units are composed of (meth) acrylate-based repeating units.
• all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units.
• the acrylate-based repeating unit is 50 mol% or less with respect to all the repeating units of the resin (A).
• the resin (A) preferably contains a repeating unit having an aromatic hydrocarbon group. It is more preferable that the resin (A) contains a repeating unit containing a phenolic hydroxyl group. Examples of the repeating unit containing a phenolic hydroxyl group include a hydroxystyrene repeating unit and a hydroxystyrene (meth) acrylate repeating unit.
• the resin (A) is a group (leaving group) in which the hydrogen atom of the phenolic hydroxyl group is decomposed and eliminated by the action of an acid.
• the content of the repeating unit having an aromatic hydrocarbon group contained in the resin (A) is preferably from 30 to 100 mol%, more preferably from 40 to 100 mol%, based on all 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 more preferably 3,000 to 11,000. Particularly preferred.
• the degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and even more preferably 1.1 to 2.0. preferable.
• Resin (A) may be used individually by 1 type, and may use 2 or more types together.
• the content of the resin (A) in the total solid content of the composition of the present invention is generally 20% by mass or more. 40 mass% or more is preferable, 60 mass% or more is more preferable, and 80 mass% or more is still more preferable. Although an upper limit in particular is not restrict
• the total solid content in the composition represents all components other than the solvent in the composition.
• composition of the present invention contains a compound (also referred to as “compound (B)”, “photoacid generator”, or “acid generator”) that generates an acid upon irradiation with actinic rays or radiation.
• a photo-acid generator the compound which generate
• Examples thereof include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzyl sulfonate compounds.
• photoacid generator known compounds that generate an acid upon irradiation with actinic rays or radiation can be appropriately selected and used alone or as a mixture thereof.
• known compounds that generate an acid upon irradiation with actinic rays or radiation can be appropriately selected and used alone or as a mixture thereof.
• Paragraphs ⁇ 0125> to ⁇ 0319> of US Patent Application Publication No. 2016 / 0070167A1 Paragraphs ⁇ 0086> to ⁇ 0094> of US Patent Application Publication No. 2015 / 0004544A1
• US Patent Application Publication No. 2016 / 0237190A1 US Patent Application Publication No. 2016 / 0237190A1.
• Known compounds disclosed in paragraphs ⁇ 0323> to ⁇ 0402> of the specification can be suitably used as the photoacid generator.
• R 201 , R 202 and R 203 each independently represents an organic group.
• the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
• Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
• Examples of the group formed by combining two members out 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 —. it can.
• Z ⁇ represents an anion.
• the photoacid generator may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of R 201 ⁇ R 203 of the compound represented by formula (ZI), 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 through a linking group.
• Compound (ZI-1) is an arylsulfonium compound in which at least one of R 201 to R 203 in formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.
• R 201 to R 203 may be an aryl group
• a part of R 201 to R 203 may be an aryl group
• the rest may be an alkyl group or a cycloalkyl group.
• arylsulfonium compound examples include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.
• the aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and 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. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.
• the two or more aryl groups may be the same or different.
• the alkyl group or cycloalkyl group optionally contained in the arylsulfonium compound 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.
• a group is preferred, 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 each independently an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having a carbon number) 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 substituted.
• Compound (ZI-2) is a compound in which R 201 to R 203 in formula (ZI) each independently represents an organic group having no aromatic ring.
• the aromatic ring 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.
• R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, Or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.
• the alkyl group and cycloalkyl group represented by 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, Butyl group and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group).
• R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, having 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 represents 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 cyclo Represents an alkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group; R 6c and R 7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
• R x and R y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
• R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to form a ring structure.
• the ring structure may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
• Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic condensed rings formed by combining two or more of these rings.
• Examples of the ring structure include a 3- to 10-membered ring, a 4- to 8-membered ring is preferable, and a 5- or 6-membered ring is more preferable.
• 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 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).
• 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, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.
• 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.
• R 15 each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent.
• Two R 15 may be bonded to each other to form a ring.
• the ring skeleton may contain an oxygen atom or a heteroatom such as a nitrogen atom.
• Z ⁇ represents an anion.
• the alkyl groups of R 13 , R 14 and R 15 are linear or branched and preferably have 1 to 10 carbon atoms, and may be a methyl group, an ethyl group, n- A butyl group or a t-butyl group is more preferable.
• R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
• the aryl group for R 204 to R 207 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
• the aryl group represented by 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 represented by 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, Butyl group and pentyl group) and cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group).
• the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may each independently have a substituent.
• substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have include, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 3 carbon atoms). 15), aryl groups (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.
• Z ⁇ represents an anion.
• the anion represented is preferred.
• 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 each independently represents a fluorine atom or an alkyl group substituted with at least one 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, and when there are a plurality of R 4 and R 5 , R 4 and R 5 are the same But it can be different.
• L represents a divalent linking group, and when there are a plurality of L, Ls may be the same or different.
• W represents an organic group containing a cyclic structure.
• 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 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.
• Xf is more preferably a fluorine atom or CF 3 . In particular, it is preferable that both Xf are fluorine atoms.
• R 4 and R 5 each independently represents 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 4 and R 5 , they may be the same or different.
• the alkyl group as R 4 and R 5 may have a substituent, and preferably has 1 to 4 carbon atoms.
• R 4 and R 5 are preferably a hydrogen atom.
• 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 (3).
• L represents a divalent linking group, and when there are a plurality of L, Ls may be the same or different.
• the divalent linking group include —COO — (— C ( ⁇ O) —O—), —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, — SO—, —SO 2 —, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and combinations thereof And divalent linking groups.
• —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 monocyclic or polycyclic.
• the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
• polycyclic alicyclic group examples include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• 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 acid diffusion more.
• the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic 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.
• heterocyclic ring examples include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
• lactone ring and sultone ring examples include the lactone structure and sultone structure exemplified in the aforementioned resin.
• a heterocyclic ring 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.
• substituents include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), and a cycloalkyl group (monocyclic, polycyclic or spirocyclic).
• alkyl group which may be linear or branched, preferably 1 to 12 carbon atoms
• a cycloalkyl group monocyclic, polycyclic or spirocyclic.
• Well preferably having 3 to 20 carbon atoms
• aryl group preferably having 6 to 14 carbon atoms
• hydroxyl group alkoxy group
• ester group amide group, urethane group, ureido group, thioether group, sulfonamide group, and sulfonic acid
• An ester group is mentioned.
• the carbon constituting the cyclic organic group may be a carbonyl carbon.
• Formula (3) As the anion represented by, 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, SO 3 - -CF 2- CH (CF 3 ) —OCO— (L) q′—W is preferred.
• L, q, and W are the same as those in the general formula (3).
• q ′ represents an integer of 0 to 10.
• X B1 and X B2 each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom.
• X B1 and X B2 are preferably hydrogen atoms.
• X B3 and X B4 each independently represent a hydrogen atom or a monovalent organic group.
• at least one of X B3 and X B4 is a fluorine atom or a monovalent organic group having a fluorine atom
• both X B3 and X B4 are a monovalent organic group having a fluorine atom or a fluorine atom. Is more preferable.
• both X B3 and X B4 are alkyl groups substituted with fluorine.
• L, q and W are the same as those in the general formula (3).
• the anion represented is preferred.
• each Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
• Xb each independently represents an organic group having no hydrogen atom or 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) - may be a benzenesulfonic acid anion Often, a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group is preferred.
• Ar represents an aryl group, and may further have a substituent other than the sulfonate anion and the — (DB) group. Further, examples of the substituent that may be included 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 sulfonate ester group, an ester group, and a group composed of a combination of two or more thereof.
• 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.
• Any of the above cations and anions can be used in combination as a photoacid generator.
• the photoacid generator may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
• the photoacid generator is preferably in the form of a low molecular compound.
• the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.
• the photoacid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above or may be incorporated in a resin different from the resin (A). .
• a photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
• the content of the photoacid generator in the composition of the present invention (when there are a plurality of types) is preferably 0.1 to 35% by mass based on the total solid content of the composition of the present invention, and 0 It is more preferably 5 to 25% by mass, further preferably 3 to 20% by mass, and particularly preferably 3 to 15% by mass.
• the photoacid generator includes a compound represented by the above general formula (ZI-3) or (ZI-4)
• the content of the photoacid generator contained in the composition (if there are multiple types, The total) is preferably 5 to 35% by mass, more preferably 7 to 30% by mass, based on the total solid content of the composition.
• the composition of the present invention contains an onium salt (C) represented by the general formula (1) and having an amide structure in the counter cation (also referred to as “onium salt (C)”).
• the onium salt (C) can act as an acid diffusion control agent or a quencher in the actinic ray-sensitive or radiation-sensitive film formed from the composition of the present invention.
• X 1 represents a sulfur atom, an iodine atom, or a nitrogen atom
• Q 1 represents a group having an amide structure
• Q 2 represents an alkyl group, a cycloalkyl group, or an aryl group.
• at least one of Q 1 and k Q 2 represents an alkyl group or a cycloalkyl group.
• X 1 represents a sulfur atom
• k 2
• X 1 represents an iodine atom
• Y 1 represents an organic counter anion.
• Q 1 and at least one of k Q 2 may be bonded to each other to form a ring structure.
• k represents 2 or 3
• at least two Q 2 may be bonded to each other to form a ring structure.
• Q 1 represents a group having an amide structure.
• the amide structure represents a group represented by the following formula (am).
• * 1 to * 3 represent a bond.
• * 1 to * 3 each represent a bond to another atom, and examples of the other atom include, but are not limited to, a hydrogen atom and a carbon atom.
• the group having an amide structure of Q 1 is preferably an alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, aryl group, heteroaryl group, or these having an amide structure A group consisting of a combination.
• Q 1 is an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, a heteroaryl group, or a combination thereof having an amide structure
• the above formula ( an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, a heteroaryl group, wherein the group represented by am) is bonded by any of the bonds * 1 to * 3 Or a group consisting of a combination thereof.
• the alkyl group may be linear or branched, preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and still more preferably Is an alkyl group having 1 to 8 carbon atoms.
• the cycloalkyl group is preferably a cycloalkyl group having 3 to 30 carbon atoms, more preferably a cycloalkyl group having 3 to 12 carbon atoms, and further preferably a cycloalkyl group having 3 to 8 carbon atoms.
• Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a bornyl group.
• the alkenyl group may be linear or branched and is preferably an alkenyl group having 2 to 15 carbon atoms.
• the cycloalkenyl group is preferably a cycloalkenyl group having 3 to 15 carbon atoms. Specific examples include a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cyclohexylene group, and a norbornene group.
• an alkynyl group having 1 to 15 carbon atoms is preferable, and specifically, an acetylene group, propynyl, butynyl group, pentynyl group, hexynyl group, 3,3-dimethyl-1-butynyl group, heptynyl group, octynyl group , Nonyl group, decynyl group, undecynyl group, dodecynyl group, tridecynyl group, tetradecynyl group, pentadecynyl group, and the like.
• the aryl group is preferably an aryl group having 6 to 15 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a naphthyl group, and an anthryl group.
• the heteroaryl group include pyridyl group, pyrazyl group, pyranyl group, pyrazolyl group, thiazolyl group, indole group, imidazolyl group, benzimidazolyl group, thiazolyl group, benzthiazolyl group, benzoxazolyl group, chromanyl group, quinolyl group, Examples thereof include an isoquinolyl group, a pyrimidyl group, and a furanyl group.
• Q 1 is a group (for example, an aralkyl group) formed by combining two or more selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, and a heteroaryl group. And a group having an amide structure. Q 1 may further have a substituent.
• substituents examples include a hydroxyl group, an alkoxy group, a nitro group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a carboxy group, an amino group, and a cyano group.
• Q 2 represents an alkyl group, a cycloalkyl group, or an aryl group.
• the alkyl group, cycloalkyl group, or aryl group as Q 2 is the same as that described as the alkyl group, cycloalkyl group, or aryl group in Q 1 .
• the alkyl group, cycloalkyl group, or aryl group as Q 2 may further have a substituent.
• the alkyl group may have an aryl group as a substituent (that is, it may be an aralkyl group).
• It is preferable that at least one of k Q 2 is an alkyl group or a cycloalkyl group, and it is more preferable that all are an alkyl group or a cycloalkyl group.
• At least one of Q 1 and k Q 2 represents an alkyl group or a cycloalkyl group.
• Q 1 is an alkyl group or a cycloalkyl group, and thus representing a cycloalkyl group having an alkyl group or an amide structure having an amide structure.
• at least one of Q 1 and k Q 2 in the general formula (1) represents an alkyl group or a cycloalkyl group, whereby the transparency of the onium salt (C) is improved and further improved.
• Various pattern shapes can be formed.
• Q 1 and at least one of k Q 2 may be bonded to each other to form a ring structure.
• k represents 2 or 3
• at least two Q 2 may be bonded to each other to form a ring structure.
• the ring structure is not particularly limited, for example, an aliphatic ring or an aromatic ring containing a X 1 and the carbon atom as ring members.
• the ring may contain a hetero atom (for example, an oxygen atom, a sulfur atom, or a nitrogen atom) as a ring member.
• the said ring may have a substituent.
• the ring has preferably 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms.
• Y 1 represents an organic counter anion.
• Y 1 is not particularly limited, specific examples and preferred ranges are, Z in formula (ZI) as the aforementioned photoacid generator -, Z in the general formula (ZII) -, in formula (ZI-3) Zc ⁇ and Z in formula (ZI-4) are the same as those described above.
• the onium salt (C) preferably does not have a structure in which an aromatic group is directly connected to a nitrogen atom of an amide structure.
• X 1 represents a sulfur atom and two Q 2 each independently represents an alkyl group or a cycloalkyl group, and more preferably represents an alkyl group. preferable.
• Q 1 and at least one of the two Q 2 may be bonded to each other to form a ring structure.
• two Q 2 is may be bonded to form a ring structure.
• the onium salt (C) is preferably represented by the following general formula (2).
• Q 3 and Q 4 each independently represents an alkyl group or a cycloalkyl group
• L 1 represents an alkylene group or a cycloalkylene group
• Q 5 and Q 6 each independently represent a hydrogen atom
• an alkyl group Represents a group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, or a heteroaryl group.
• At least two of Q 3 to Q 6 and L 1 may be bonded to each other to form a ring structure.
• Y 2 is an organic counter anion.
• Q 3 and Q 4 each independently represent an alkyl group or a cycloalkyl group, and are the same as those described as the alkyl group or cycloalkyl group as Q 2 . It is particularly preferable that Q 3 and Q 4 each independently represent an alkyl group.
• Q 5 and Q 6 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, or a heteroaryl group.
• the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, aryl group or heteroaryl group as Q 5 and Q 6 is an alkyl group, a cycloalkyl group, an alkenyl group in Q 1 , The same as those described as the cycloalkenyl group, alkynyl group, cycloalkynyl group, aryl group, or heteroaryl group.
• Q 5 and Q 6 preferably each independently represent a hydrogen atom or an alkyl group.
• L 1 represents an alkylene group or a cycloalkylene group.
• the alkylene group as L 1 is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and specific examples include a methylene group, an ethylene group, and a propylene group.
• the cycloalkylene group as L 1 is preferably a cycloalkylene group having 3 to 12 carbon atoms, and more preferably a cycloalkylene group having 3 to 8 carbon atoms.
• the alkylene group or cycloalkylene group may have a substituent.
• At least two of Q 3 to Q 6 and L 1 may be bonded to each other to form a ring structure.
• Q 1 in the general formula (1) and at least one of k Q 2 are bonded to each other to form a ring structure, and at least two Q 2 are bonded to each other to form a ring structure. It is the same as that described as the ring structure when forming.
• Y 2 represents an organic counter anion and is the same as Y 1 in General Formula (1) described above.
• the molecular weight of the cation portion of the onium salt (C) is preferably from 100 to 500, and more preferably from 120 to 350.
• the cation portion of the onium salt (C) refers to a structure other than the organic counter anion represented by Y 1 in the general formula (1), for example.
• onium salt (C) Specific examples of the onium salt (C) are shown below, but are not limited thereto.
• the onium salt (C) can be synthesized using a known method (for example, the method described in JP-A-2003-307839).
• An onium salt (C) may be used individually by 1 type, and may use 2 or more types together.
• the content of the onium salt (C) in the composition of the present invention (when there are a plurality of types) is preferably 0.05 to 30% by mass based on the total solid content of the composition of the present invention, 0.1 to 20% by mass is more preferable, 0.2 to 15% by mass is further preferable, and 0.2 to 10% by mass is particularly preferable.
• the content of the onium salt (C) in the composition of the present invention is less than the content of the photoacid generator in terms of mole. This is because the onium salt (C) has a structure that acts as a quencher, so if the content is higher than that of the photoacid generator, the acid generated by exposure is quenched before it acts sufficiently. This is because pattern formation becomes insufficient.
• the content of the onium salt (C) in the composition of the present invention is preferably 50% or less of the content of the photoacid generator in terms of mole, more preferably 1 to 40%, particularly preferably 5 to 30%. preferable.
• the composition of the present invention may further contain (D) a hydrophobic resin (“hydrophobic resin (D)”) having at least one of a fluorine atom and a silicon atom, which is different from the resin (A). preferable.
• a hydrophobic resin (“hydrophobic resin (D)”) having at least one of a fluorine atom and a silicon atom, which is different from the resin (A).
• the composition of the present invention contains the hydrophobic resin (D)
• the static / dynamic contact angle on the surface of the actinic ray-sensitive or radiation-sensitive film can be controlled. This makes it possible to improve development characteristics, suppress outgassing, improve immersion liquid follow-up in immersion exposure, reduce immersion defects, and the like.
• the hydrophobic resin (D) is preferably designed to be unevenly distributed on the surface of the resist film.
• the hydrophobic resin (D) is not necessarily required to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.
• the hydrophobic resin (D) is 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 uneven distribution in the membrane surface layer. It is preferable that it is resin containing the repeating unit which has at least 1 type.
• the hydrophobic resin (D) contains a fluorine atom and / or a silicon atom
• the fluorine atom and / or silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin. It may be contained in the chain.
• the hydrophobic resin (D) contains a fluorine atom
• it may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
• the hydrophobic resin (D) is preferably a fluorine-containing (meth) acrylate resin.
• the hydrophobic resin (D) preferably has at least one group selected from the following groups (x) to (z).
• Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkylsulfonyl) ) And a methylene group.
• the acid group is preferably a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulf
• Examples of the group (y) which is decomposed by the action of the alkali developer and increases the solubility in the alkali developer include a lactone group, a carboxylic acid ester group (—COO—), and an acid anhydride group (—C (O) OC. (O)-), acid imide group (—NHCONH—), carboxylic acid thioester group (—COS—), carbonate ester group (—OC (O) O—), sulfate ester group (—OSO 2 O—), and Examples thereof include a sulfonic acid ester group (—SO 2 O—), and a lactone group or a carboxylic acid ester group (—COO—) is preferable.
• the repeating unit containing these groups is a repeating unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include a repeating unit of an acrylate ester and a methacrylate ester.
• these groups may be bonded to the main chain of the resin via a linking group.
• this repeating unit may be introduce
• Examples of the repeating unit having a lactone group include those similar to the repeating unit having a lactone structure described above in the section of the resin (A).
• the content of the repeating unit having a group (y) that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer is 1 to 100 mol% based on all repeating units in the hydrophobic resin (D). 3 to 98 mol% is more preferable, and 5 to 95 mol% is still more preferable.
• Examples of the repeating unit having a group (z) that is decomposed by the action of an acid in the hydrophobic resin (D) include the same repeating units as those having an acid-decomposable group described for the resin (A).
• the repeating unit having a group (z) that decomposes by 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) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all repeating units in the resin (D). More preferred is ⁇ 60 mol%.
• the hydrophobic resin (D) may further have a repeating unit different from the above-described repeating unit.
• the repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all repeating units contained in the hydrophobic resin (D).
• the repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, based on all repeating units contained in the hydrophobic resin (D).
• hydrophobic resin (D) contains a CH 3 partial structure in the side chain portion
• a mode in which the hydrophobic resin (D) does not substantially contain a fluorine atom and a silicon atom is also preferable.
• hydrophobic resin (D) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom.
• the weight average molecular weight in terms of standard polystyrene of the hydrophobic resin (D) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
• the total content of residual monomers and / or oligomer components contained in the hydrophobic resin (D) is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass.
• the dispersity (Mw / Mn) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3.
• hydrophobic resin (D) known resins can be used by being appropriately selected alone or as a mixture thereof.
• known resins disclosed in paragraphs ⁇ 0451> to ⁇ 0704> of U.S. Patent Application Publication No. 2015 / 0168830A1 and paragraphs ⁇ 0340> to ⁇ 0356> of United States Patent Application Publication No. 2016 / 0274458A1 are hydrophobic.
• the repeating units disclosed in paragraphs ⁇ 0177> to ⁇ 0258> of US Patent Application Publication No. 2016 / 0237190A1 are also preferable as the repeating units constituting the hydrophobic resin (D).
• Hydrophobic resin (D) may be used individually by 1 type, and may use 2 or more types together. It is preferable to use a mixture of two or more kinds of hydrophobic resins (D) having different surface energies from the viewpoint of achieving both immersion liquid followability and development characteristics in immersion exposure.
• the content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 10% by mass with respect to the total solid content in the composition of the present invention. More preferred is 10% by mass.
• a content of the hydrophobic resin (D) in the composition of 0.01% by mass or more is preferable from the viewpoint of easy control of surface characteristics, and a content of 10% by mass or less is preferable from the viewpoint of lithography performance.
• composition of this invention contains onium salt (C), you may use an acid diffusion control agent together further.
• the acid diffusion controller acts as a quencher that traps the acid generated from the acid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid.
• a basic compound (DA), a basic compound (DB) whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, an onium salt (DC) that becomes a weak acid relative to an acid generator, a nitrogen atom And a low molecular compound (DD) having a group capable of leaving by the action of an acid, an onium salt compound (DE) having a nitrogen atom in the cation moiety, or the like can be used as an acid diffusion controller.
• a known acid diffusion controller can be used as appropriate.
• the basic compound (DA) is preferably a compound having a structure represented by the following formulas (A) to (E).
• R 200 , R 201 and R 202 may be the same or different and each independently represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), or a cycloalkyl group. (Preferably having 3 to 20 carbon atoms) or an aryl group (6 to 20 carbon atoms).
• R 201 and R 202 may combine 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 group in the general formulas (A) and (E) may have a substituent or may be unsubstituted.
• the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
• the alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.
• guanidine As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like are preferable, imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, 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, or the like is more preferable.
• a basic compound (DB) whose basicity decreases or disappears upon irradiation with actinic rays or radiation (hereinafter also referred to as “compound (DB)”) has a proton acceptor functional group, and has an actinic ray or It is a compound that decomposes upon irradiation with radiation and whose proton acceptor property is lowered, disappears, or changes from proton acceptor property to acidity.
• the proton acceptor functional group is a functional group having an electron or a group capable of electrostatically interacting with a proton, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a ⁇ conjugate. 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 represented by the following formula.
• Preferred partial structures of the proton acceptor functional group include, for example, crown ether, azacrown ether, primary to tertiary amine, pyridine, imidazole, and pyrazine structures.
• the compound (DB) is decomposed by irradiation with actinic rays or radiation to generate a compound in which the proton acceptor property is reduced or lost, or 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 acid property is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group.
• the acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) upon irradiation with actinic rays or radiation preferably satisfies pKa ⁇ 1, more preferably ⁇ 13 ⁇ pKa ⁇ 1, and ⁇ 13 ⁇ pKa. ⁇ -3 is more preferred.
• the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined in, for example, Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.). It shows that acid strength is so large that the value of acid dissociation constant pKa is low.
• the acid dissociation constant pKa in the aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution.
• the following software package 1 can be used to calculate a value based on a Hammett substituent constant and a database of known literature values.
• the values of pKa described in this specification all indicate values obtained by calculation using this software package.
• an onium salt (DC) that is a weak acid relative to the acid generator can be used as an acid diffusion controller.
• DC an onium salt
• an acid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the acid generator are mixed and used, it is generated from the acid generator by irradiation with actinic rays or radiation.
• an onium salt having an unreacted weak acid anion a weak acid is released by salt exchange to yield an onium salt having a strong acid anion.
• the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.
• the onium salt that is a weak acid relative to the acid generator is preferably a compound represented by the following general formulas (d1-1) to (d1-3).
• R 51 represents a hydrocarbon group which may have a substituent
• Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon adjacent to S).
• R 52 is an organic group
• Y 3 is a linear, branched or cyclic alkylene group or an arylene group
• Rf is a fluorine atom.
• Each of the M + is independently an ammonium cation, a sulfonium cation or an iodonium cation.
• sulfonium cation or iodonium cation represented by M + include a sulfonium cation exemplified by the general formula (ZI) and an iodonium cation exemplified by the general formula (ZII).
• the compound (DCA) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).
• R 1 , R 2 , and R 3 each independently represent a substituent having 1 or more carbon atoms.
• L 1 represents a divalent linking group or a single bond linking the cation moiety and the anion moiety.
• -X - it is, -COO -, -SO 3 - represents an anion portion selected from -R 4 -, -SO 2 -, and -N.
• R 4 has a carbonyl group (—C ( ⁇ O) —), a sulfonyl group (—S ( ⁇ O) 2 —), and a sulfinyl group (—S ( ⁇ O) — at the linking site with the adjacent N atom.
• R 1 , R 2 , R 3 , R 4 , and L 1 may be bonded to each other to form a ring structure.
• R 1 to R 3 may be combined to represent one divalent substituent and may be bonded to the N atom by a double bond.
• Examples of the substituent having 1 or more carbon atoms in R 1 to R 3 include alkyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylamino A carbonyl group, an arylaminocarbonyl group, etc. are mentioned.
• An alkyl group, a cycloalkyl group, or an aryl group is preferable.
• L 1 as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples 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 thereof.
• a low molecular compound (DD) having a nitrogen atom and a group capable of leaving by the action of an acid has a group leaving on the nitrogen atom by the action of an acid. It is preferable that it is an amine derivative having.
• the group capable of leaving by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and more preferably a carbamate group or a hemiaminal ether group.
• the molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and still 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 general formula (d-1).
• each R b independently represents 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 Represents an aralkyl group (preferably 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably 1 to 10 carbon atoms).
• Rb may be connected to each other to form a ring.
• the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R b are each independently a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, an alkoxy group, Alternatively, it may be substituted with a halogen atom.
• Rb The same applies to the alkoxyalkyl group represented by Rb .
• R b is preferably a linear or branched alkyl group, a cycloalkyl group, or an aryl group, more preferably a linear or branched alkyl group or a cycloalkyl group.
• Examples of the ring formed by connecting two R b to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
• Specific examples of the group represented by the general formula (d-1) include, but are not limited to, the structures disclosed in paragraph ⁇ 0466> of US Patent Publication US2012 / 0135348A1. .
• the compound (DD) preferably has a structure represented by the following general formula (6).
• R a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
• the alkyl group as R a, a cycloalkyl group, an aryl group and aralkyl group is each independently an alkyl group as R b, cycloalkyl group, aryl group and aralkyl group, is substituted
• the group which may be substituted may be the same as the group described above.
• R a alkyl group, cycloalkyl group, aryl group, and aralkyl group are the same groups as the specific examples described above for R b. Is mentioned.
• Specific examples of the particularly preferable compound (DD) in the present invention include compounds disclosed in paragraph ⁇ 0475> of US Patent Application Publication No. 2012 / 0135348A1, but are not limited thereto. is not.
• the onium salt compound (DE) having a nitrogen atom in the cation part is preferably a compound having a basic site containing a nitrogen atom in the cation part.
• the basic moiety is preferably an amino group, and more preferably an aliphatic amino group. More preferably, all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. From the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is not directly connected to the nitrogen atom.
• a preferred specific structure of the compound (DE) includes, but is not limited to, the compound disclosed in paragraph ⁇ 0203> of US Patent Application Publication No. 2015 / 03009408A1.
• the composition of the present invention may or may not contain an acid diffusion controller, but when it is included, it may be used alone or in combination of two or more.
• the content of the acid diffusion control agent in the composition (the total when there are multiple types) is 0. 0 based on the total solid content of the composition. 1 to 10% by mass is preferable, and 0.1 to 5% by mass is more preferable.
• the composition of the present invention usually contains a solvent.
• a known resist solvent can be appropriately used.
• paragraphs ⁇ 0665> to ⁇ 0670> of U.S. Patent Application Publication No. 2016 / 0070167A1 paragraphs ⁇ 0210> to ⁇ 0235> of U.S. Patent Application Publication No. 2015 / 0004544A1, and Patent Publication No. 2016 / 0237190A1.
• Known solvents disclosed in paragraphs ⁇ 0424> to ⁇ 0426> of the specification and paragraphs ⁇ 0357> to ⁇ 0366> of U.S. Patent Application Publication No. 2016 / 0274458A1 can be preferably used.
• Examples of the solvent that can be used in preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), Examples thereof include an organic solvent such as a monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.
• a monoketone compound preferably having 4 to 10 carbon atoms
• the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure may be used as an organic solvent, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group.
• the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group the above-mentioned exemplary compounds can be selected as appropriate, but the solvent containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether or alkyl lactate, and propylene glycol monomethyl ether. (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferable.
• alkylene glycol monoalkyl ether acetate alkyl alkoxypropionate
• a monoketone compound which may contain a ring alkyl alkoxypropionate
• a monoketone compound which may contain a ring alkyl acetate, etc.
• propylene glycol monomethyl Ether acetate PGMEA
• ethyl ethoxypropionate 2-heptanone
• ⁇ -butyrolactone cyclohexanone
• cyclopentanone or butyl acetate propylene glycol monomethyl ether acetate
• ⁇ -butyrolactone propylene glycol monomethyl ether acetate
• ethyl ethoxypropionate cyclohexanone
• More preferred is cyclopentanone or 2-heptanone.
• propylene carbonate is also preferable.
• the mixing ratio (mass ratio) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. preferable.
• a mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is preferable from the viewpoint of coating uniformity.
• the solvent preferably contains propylene glycol monomethyl ether acetate, may be a propylene glycol monomethyl ether acetate single solvent, or may be two or more mixed solvents containing propylene glycol monomethyl ether acetate.
• the composition of the present invention may or may not contain a surfactant.
• 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) ) Is preferred.
• composition of the present invention contains a surfactant
• a surfactant when an exposure light source of 250 nm or less, particularly 220 nm or less is used, it is possible to obtain a resist pattern with good sensitivity and resolution and less adhesion and development defects. it can.
• the fluorine-based and / or silicon-based surfactant include surfactants described in paragraph ⁇ 0276> of US Patent Application Publication No. 2008/0248425.
• surfactants other 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.
• surfactants may be used alone or in combination of two or more.
• the content of the surfactant is preferably 0.0001 to 2% by mass, and 0.0005 to 1% by mass with respect to the total solid content of the composition. More preferred.
• the surfactant content is 10 ppm (parts per million) or more with respect to the total solid content of the composition, the surface unevenness of the hydrophobic resin is increased. Thereby, the surface of the actinic ray-sensitive or radiation-sensitive film can be made more hydrophobic, and water followability at the time of immersion exposure is improved.
• composition of the present invention may further contain an acid proliferator, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, a dissolution accelerator, or the like.
• the film thickness of the actinic ray-sensitive film or radiation-sensitive film made of the composition of the present invention is preferably 90 nm or less, and more preferably 85 nm or less, from the viewpoint of improving resolution. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property or film forming property.
• the solid content concentration of the composition of the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0 to 5.3% by mass.
• the solid content concentration is a mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.
• the composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably the above mixed solvent, filtering the solution, and applying the solution on a predetermined support (substrate).
• the pore size of the filter used for filter filtration is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and further preferably 0.03 ⁇ m or less.
• This filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
• a cyclic filtration may be performed, and a plurality of types of filters are connected in series. Alternatively, filtration may be performed in parallel.
• the composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and after filter filtration.
• the composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition that changes its properties upon reaction with irradiation with actinic rays or radiation. More specifically, the composition of the present invention can be used in semiconductor manufacturing processes such as IC (Integrated Circuit), circuit boards such as liquid crystals or thermal heads, fabrication of imprint mold structures, other photofabrication processes, or The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used for producing a lithographic printing plate or an acid-curable composition.
• the resist pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode forming process, a rewiring forming process, a MEMS (Micro Electro Mechanical Systems), and the like.
• the present invention also relates to a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition.
• the pattern formation method of this invention is demonstrated.
• the actinic ray-sensitive or radiation-sensitive film (typically a resist film) of the present invention will also be described.
• the pattern forming method of the present invention comprises: (I) a step of forming an actinic ray-sensitive or radiation-sensitive film on the support with the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition (film formation step); (Ii) a step of exposing the actinic ray-sensitive or radiation-sensitive film to an actinic ray or radiation (exposure step); and (Iii) a step of developing the actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation with a developer (development step),
• the pattern forming method of the present invention is not particularly limited as long as it includes the steps (i) to (iii), and may further include the following steps.
• the exposure method in the exposure step may be immersion exposure.
• the pattern forming method of the present invention preferably includes (ii) a pre-heating (PB) step before the exposure step.
• the pattern forming method of the present invention preferably includes (v) a post-exposure bake (PEB) step after (ii) the exposure step and before (iii) the development step.
• the pattern forming method of the present invention may include (ii) an exposure step a plurality of times.
• the pattern forming method of the present invention may include (iv) a preheating step a plurality of times.
• the pattern forming method of the present invention may include (v) a post-exposure heating step a plurality of times.
• the above-described (i) film formation step, (ii) exposure step, and (iii) development step can be performed by a generally known method.
• a resist underlayer film for example, SOG (Spin On Glass), SOC (Spin On Carbon), antireflection film
• SOG Spin On Glass
• SOC Spin On Carbon
• antireflection film is formed between the actinic ray-sensitive or radiation-sensitive film and the support. May be.
• As the resist underlayer film a known organic or inorganic material can be appropriately used.
• a protective film (topcoat) may be formed on the actinic ray-sensitive or radiation-sensitive film.
• a known material can be appropriately used.
• composition for forming a protective film disclosed in 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 actinic ray-sensitive or radiation-sensitive film containing the hydrophobic resin described above.
• the support is not particularly limited, and is generally used in a manufacturing process of a semiconductor such as an IC, or a manufacturing process of a circuit board such as a liquid crystal or a thermal head, and other photofabrication lithography processes.
• a 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 130 ° C., more preferably 80 to 120 ° C. in both (iv) the preheating step and (v) the post-exposure heating step.
• the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and further preferably 30 to 90 seconds in both (iv) the preheating step and (v) the 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 wavelength is preferably 250 nm or less, more preferably 220 nm or less, and further 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), electron beam, etc.
• KrF excimer laser, ArF excimer laser, EUV or electron beam is preferred.
• the alkaline developer a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used.
• an alkaline aqueous solution such as an inorganic alkali, a primary to tertiary amine, an alcohol amine, and a cyclic amine can also be used. It can be used.
• the alkaline developer may contain an appropriate amount of alcohol and / or surfactant.
• the alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
• the pH of the alkaline developer is usually 10-15.
• the development time using an alkali 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. Preferably there is.
• 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 include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
• ester solvents include 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.
• Examples include butyl, 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 / 0070167A1 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 mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably substantially free of moisture.
• the content of the organic solvent in the organic developer is preferably 50% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and more preferably 90% by mass to 100% by mass with respect to the total amount of the developer. The following is more preferable, and 95% by mass or more and 100% by mass or less is particularly preferable.
• the organic developer can contain an appropriate amount of a known surfactant as required.
• the surfactant content is usually from 0.001 to 5 mass%, preferably from 0.005 to 2 mass%, more preferably from 0.01 to 0.5 mass%, based on the total amount of the developer.
• the organic developer may contain the acid diffusion control agent described above.
• a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and left stationary for a certain time (paddle method), a substrate A method of spraying the developer on the surface (spray method) or a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic dispensing method) is applied.
• dip method a method in which a substrate is immersed in a tank filled with a developer for a certain period of time
• paddle method a method in which the developer is raised on the surface of the substrate by surface tension and left stationary for a certain time
• a substrate A method of spraying the developer on the surface spray method
• a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed dynamic dispensing method
• a step of developing using an alkaline aqueous solution (alkali developing step) and a 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
• pure water can be used as the rinsing solution used in the rinsing step after the developing step using the alkaline developer.
• Pure water may contain an appropriate amount of a surfactant.
• a process for removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid may be added.
• a heat treatment may be performed in order to remove moisture remaining in the pattern.
• the rinsing solution used in the rinsing step after the developing step using the developing solution containing an organic solvent 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 rinse liquid a rinse liquid 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. Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent, and ether solvent are the same as those described in the developer containing an organic solvent.
• a rinse liquid containing a monohydric alcohol is more preferable.
• Examples of the monohydric alcohol used in the rinsing step include linear, branched, or cyclic monohydric alcohols. 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.
• Examples of monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl isobutyl carbinol. .
• a plurality of each component may be mixed, or may be used by mixing with an organic solvent other than the above.
• the water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.
• the rinse solution may contain an appropriate amount of a surfactant.
• the substrate that has been developed using the organic developer is washed with a rinse containing an organic solvent.
• the method of the cleaning process is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), and immersing the substrate in a bath filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), or the like can be applied.
• 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 ppm or less, more preferably 100 ppt (parts per trillation) or less, still more preferably 10 ppt or less (substantially no detection limit). Is particularly preferred).
• Examples of a method for removing impurities such as metals from the various materials include filtration using a filter.
• 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.
• a filter that has been washed in advance with an organic solvent may be used.
• a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, 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 a plurality of times may be a circulating filtration step.
• the filter is preferably a filter with reduced eluate as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Laid-Open No. 2016-201426).
• impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used.
• the adsorbent a known adsorbent can be used.
• an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.
• Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Laid-Open No. 2016-206500).
• 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 of performing distillation under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark) or the like can be mentioned. It is also possible to apply glass lining to all processes of manufacturing equipment that synthesizes various resist component materials (binders, photoacid generators, etc.). The preferred conditions for filter filtration performed in the same manner are the same as those described above.
• a method for 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 for improving the surface roughness of the pattern for example, a method of treating a resist pattern by plasma of hydrogen-containing gas disclosed in US Patent Application Publication No. 2015/0104957 can be cited.
• Japanese Patent Application Publication No. 2004-235468 JP 2004-2354608
• US Patent Application Publication No. 2010/0020297 Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Known methods such as those described in “Enhancement” may be applied.
• the resist pattern formed by the above-described method is, for example, a spacer disclosed in Japanese Patent Application Publication No. 1991-270227 (JP-A-3-270227) and US Patent Application Publication No. 2013/0209941. It can be used as a process core.
• the present invention also relates to an electronic device manufacturing method including the pattern forming method described above.
• the electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric / electronic device (for example, home appliances, OA (Office Automation) -related devices, media-related devices, optical devices, communication devices, etc.). Is done.
• an electric / electronic device for example, home appliances, OA (Office Automation) -related devices, media-related devices, optical devices, communication devices, etc.
• the reaction solution was allowed to cool and then added dropwise to a mixture of 900 ml of methanol / 100 ml of water over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain 27.2 g of resin (RA-1).
• the weight average molecular weight (Mw) of the obtained resin was 8500 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.72.
• the photoacid generator used is as follows.
• the onium salt (C) used is as follows. The following (QX-1) to (QX-5) are not onium salts (C), but are listed in the column of “onium salts (C)” for convenience in Table 1 below.
• W-1 Megafac F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
• W-2 Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
• ⁇ solvent ⁇ S1 Propylene glycol monomethyl ether acetate (PGMEA)
• S2 2-Heptanone
• S3 cyclohexanone
• S4 ⁇ -butyrolactone
• S5 Propylene glycol monomethyl ether (PGME)
• ⁇ Preparation of resist composition> The components shown in Table 1 below are dissolved in the amount shown in Table 1 in the solvent shown in Table 1 to prepare a solution having a solid content concentration of 5% by mass, and this is filtered through a polyethylene filter having a pore size of 0.03 ⁇ m. Thus, positive resist compositions (solutions) for the examples and comparative examples were prepared. Further, Table 1 below shows the molar ratio of the content of the onium salt (C) to the content of the photoacid generator in each resist composition (the content of the onium salt (C) is a photoacid in terms of mol. % Of the content of the generator).
• the prepared positive resist composition was evaluated by the following method, and the results are shown in Table 2.
• An antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied on a silicon wafer (12 inches in diameter) and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm.
• the resist composition prepared thereon was applied and baked at 100 ° C. for 60 seconds to form a photosensitive film (resist film) having a thickness of 100 nm. One inch is 0.0254 m.
• the obtained wafer was used with an ArF excimer laser immersion scanner (XT1700i, NA1.20, Annular, outer sigma 0.700, inner sigma 0.400, XY deflection manufactured by ASML), and the opening was 100 nm, and Exposure was made through a 6% halftone mask with a hole-to-hole pitch of 800 nm. Ultra pure water was used as the immersion liquid. After heating at 100 ° C. for 60 seconds, developing with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsing with pure water, and spin drying, an isolated hole pattern with a diameter of 85 nm was obtained. .

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