WO2018168258A1 - 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、及び電子デバイスの製造方法 - Google Patents
感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、及び電子デバイスの製造方法 Download PDFInfo
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
Definitions
- the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and an electronic device manufacturing method.
- an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption.
- the photoacid generator in the exposed portion is decomposed by exposure to excimer laser, electron beam, extreme ultraviolet light, etc. to generate an acid, and a post-exposure baking (PEB) : Post Exposure Bake) using an acid generated as a reaction catalyst to change an alkali-insoluble group to an alkali-soluble group and removing an exposed portion with an alkali developer.
- PEB post-exposure baking
- Patent Document 1 describes a positive resist composition containing a resin having a p-hydroxystyrene-based repeating unit.
- the three-dimensional memory layer is mainly used to increase the capacity. It is becoming.
- the resist film is required to be increased from a conventional nano size to a micron size.
- the present inventors made a thick resist film (1 ⁇ m or more) using a resin having a p-hydroxystyrene repeating unit described in Patent Document 1, and examined the performance of the pattern after exposure and development. As a result, it was clarified that the resolution is not always sufficient and there is room for further improvement.
- this invention makes it a subject to provide the actinic-ray-sensitive or radiation-sensitive resin composition which can give the pattern excellent in resolution.
- Another object of the present invention is to provide a resist film, a pattern forming method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.
- the present inventors have made the present invention by setting the content of impurities having absorption at a wavelength of 248 nm in the actinic ray-sensitive or radiation-sensitive resin composition to a predetermined amount or less. As a result, the present invention has been completed. That is, it has been found that the above object can be achieved by the following configuration.
- An actinic ray-sensitive or radiation-sensitive resin composition used for forming a pattern having a thickness of 1 ⁇ m or more, Containing resin The actinic ray-sensitive or radiation-sensitive resin composition, wherein the content of impurities having absorption at a wavelength of 248 nm is 1.00% by mass or less based on the resin.
- the resin contains a repeating unit represented by the following general formula (I), The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the impurity is a compound represented by the following general formula (X).
- the resin is a resin synthesized in the presence of a basic compound, The actinic ray-sensitive or radiation-sensitive resin composition according to [5], wherein the content of basic impurities derived from the basic compound is 0.10% by mass or less based on the resin.
- the actinic-ray-sensitive or radiation-sensitive resin composition which can give the pattern excellent in resolution can be provided.
- the resist film using the said actinic-ray-sensitive or radiation-sensitive resin composition, the pattern formation method, and the manufacturing method of an electronic device can be provided.
- the description which has not described substitution and non-substitution includes the group which has a substituent with the group which 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 light represented by an excimer laser, extreme ultraviolet light (EUV light: Extreme Ultraviolet), X-ray, and electron beam (EB). : Electron Beam) or the like.
- light means actinic rays or radiation.
- exposure in the present specification includes not only exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), and X-rays, but also electron beams, And drawing with particle beams such as ion 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.
- the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by Tosoh Corporation) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ L, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: differential refractive index It is defined as a polystyrene-converted value by a detector (Refractive Index Detector).
- the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter simply referred to as “the composition of the present invention”) is used for the formation of a pattern having a film thickness of 1 ⁇ m or more.
- a resin composition comprising: Containing resin, The content of impurities having absorption at a wavelength of 248 nm is 1.00% by mass or less based on the resin.
- the composition of the present invention is a so-called resist composition, which may be a positive resist composition or a negative resist composition. Further, it may be a resist composition for alkali development or a resist composition for organic solvent development.
- the composition of the present invention is typically a chemically amplified resist composition.
- composition of the present invention is excellent in resolution when a pattern is formed by adopting the above configuration.
- the present inventors have an influence of impurities that have not been a problem in the lithography process of a conventional nano-sized resist film. Has been found to occur significantly. Specifically, during exposure, light is absorbed by impurities contained in the thick resist film, and the phenomenon that the light does not reach the deep part of the thick film becomes significant. As a result, it has been confirmed that the resolution of the formed pattern deteriorates and a desired shape cannot be obtained.
- the inventors of the present invention have further studied the above-described impurities.
- the impurities are formed by setting the content of impurities having absorption at a wavelength of 248 nm in the resist film to 1.00% by mass or less based on the resin. It was clarified that the resolution of the pattern is excellent.
- an impurity means a component other than a resin, a photoacid generator, an acid diffusion controller, a surfactant, a solvent, a hydrophobic resin, and a crosslinking agent that can be contained in the composition of the present invention.
- ingredients such as raw materials brought into the composition through the above components (for example, unreacted monomers brought from the resin, modified products of the unreacted monomers, and bases used in the deprotection reaction in the synthesis of the resin) Compound etc.).
- the content of impurities having absorption at a wavelength of 248 nm among impurities is 1.00% by mass or less based on the resin.
- the impurity having absorption at a wavelength of 248 nm is not particularly limited as long as it has absorption at a wavelength of 248 nm. Among them, an impurity having an absorption peak at a wavelength of 220 to 280 nm is preferable.
- the impurity when the impurity is an aromatic compound (for example, a compound having a benzene ring), it has high absorption derived from the aromatic ring in the vicinity of a wavelength of 248 nm, and therefore it is desirable to remove it by purification.
- Impurities having absorption at a wavelength of 248 nm include, for example, a resin (for example, a repeating unit having a group that increases in polarity by the action of an acid (particularly, a phenolic hydroxyl group is decomposed and eliminated by the action of an acid).
- the unreacted monomer and the modified product of the unreacted monomer are brought into the composition through the resin. Therefore, when using the above-mentioned resin, it is necessary to reduce unreacted monomers and modified products of unreacted monomers by purification treatment.
- Examples of the impurity having absorption at the wavelength of 248 nm include compounds represented by the general formula (X).
- the resin contains a repeating unit having a phenolic hydroxyl group (particularly, a repeating unit represented by the general formula (I)), the compound represented by the general formula (X) is easily brought in as an impurity.
- R a is a group represented by formula (Y1), or a group represented by the general formula (Y2).
- R 41, R 42 and R 43 are the same as defined for each group in the general formula (I) to be described later.
- R 44 represents an alkyl group.
- the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1.
- R b represents a hydrogen atom or a protecting group. Examples of the protecting group include an alkyl group and —CO—R c .
- R c represents an alkyl group.
- the carbon number of the alkyl group represented by R b and the alkyl group represented by R c is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1. * Represents a bonding position.
- the content of impurities having absorption at a wavelength of 248 nm is 1.00% by mass or less with respect to the resin (total resin mass), and is 0.95 in that the pattern resolution is excellent.
- % By mass or less is preferable, 0.80% by mass or less is more preferable, 0.60% by mass or less is further preferable, and 0% by mass is particularly preferable. That is, the compound having absorption at a wavelength of 248 nm is not contained in the composition of the present invention, or when contained (the content of the compound having absorption at a wavelength of 248 nm is more than 0% by mass with respect to the resin). If present) is 1.00% by mass or less.
- the content of impurities having absorption at a wavelength of 248 nm in the composition of the present invention can be identified by liquid chromatography.
- the content of basic impurities among the impurities is preferably reduced with respect to the resin. This is because when the composition of the present invention contains basic impurities, the acid generated from the photoacid generator is deactivated by irradiation with radiation and actinic rays.
- the basic impurity means a basic compound such as an amine compound and a metal hydroxide (for example, an alkali metal ion as a metal).
- the basic impurity corresponds to the “impurity having absorption at a wavelength of 248 nm” and is not included in the “basic impurity”.
- the basic impurity contains a resin having a repeating unit having a phenolic hydroxyl group (particularly, a repeating unit represented by the general formula (I)) in the composition of the present invention, Often brought in.
- a resin having a repeating unit having a phenolic hydroxyl group for example, a resin having a repeating unit derived from hydroxystyrene is generally synthesized using acetoxystyrene as a raw material. For this reason, it is necessary to undergo a deprotection reaction in which the acetoxy group is deprotected to a phenolic hydroxyl group in the presence of a basic compound either during the synthesis of the monomer or after the synthesis of the resin.
- the composition of the present invention contains a resin synthesized in the presence of a basic compound, the content of basic impurities derived from the basic compound is 0.10% by mass with respect to the resin. The following is preferable. When the content of the basic impurity derived from the basic compound is 0.10% by mass or less based on the resin, the pattern resolution is excellent.
- the content of the basic impurities derived from the basic compound is more preferably 0.05% by mass or less, still more preferably 0.01% by mass or less, and particularly preferably 0% by mass with respect to the resin. That is, the basic impurity is not contained in the composition of the present invention or when it is contained (when the content of the basic impurity is more than 0% by mass with respect to the resin), it is 0.10. It is preferable that it is below mass%.
- Examples of the amine compound include triethylamine, N, N-dimethyl-4-aminopyridine, and diazabicycloundecene.
- Examples of the metal hydroxide include sodium hydroxide and potassium hydroxide.
- the content of the basic impurities in the composition of the present invention can be identified / quantified by gas chromatography, capillary electrophoresis, neutralization titration, and the like.
- the composition of the present invention contains a resin.
- the resin is a resin (hereinafter, also referred to as “acid-decomposable group” or “resin (A)”) having a group (hereinafter also referred to as “acid-decomposable group”) that is decomposed by the action of an acid to increase polarity. It is preferable to contain.
- acid-decomposable group typically, when an alkaline developer is employed as the developer, a positive pattern is suitably formed, and when an organic developer is employed as the developer.
- the negative pattern is preferably 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 by a group (leaving group) that decomposes and leaves by the action of an acid.
- 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
- 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 a functional group (for example, a hexafluoroisopropanol group).
- 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 — C (R 01 ) (R 02 ) (OR 39 ) and the like can be mentioned.
- 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 cycloalkyl group 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.
- an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an ⁇ -pinel group, a tricyclodecanyl group, A tetracyclododecyl group, an androstanyl group, etc. are mentioned.
- at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
- the aryl group of R 36 to R 39 , R 01 and R 02 is preferably an aryl group having 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 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 may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, An isobutyl group or a t-butyl group is preferred.
- 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.
- cycloalkyl group of Rx 1 , Rx 2 and Rx 3 a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group
- a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group
- a polycyclic cycloalkyl group such as
- 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 tetra
- a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, a norbornane ring, a tetra
- a polycyclic cycloalkyl ring such as a cyclodecane 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.
- the lactone structure or sultone structure only needs to have a lactone structure or sultone structure, and a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable.
- Those having other ring structures condensed to the sultone structure are more preferable.
- the resin (A) is a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21), or any one of the following general formulas (SL1-1) to (SL1-3) It is more preferable to have a repeating unit having a sultone structure. A lactone structure or a sultone structure may be directly bonded to the main chain.
- 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.
- An alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-decomposable group is preferable.
- 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.
- repeating unit having a lactone structure or a sultone structure a repeating unit represented by the following general formula (III) is preferable.
- A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
- n is the number of 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. When n is 0, —R 0 —Z— does not exist and becomes a single bond.
- R 0 represents an alkylene group, a cycloalkylene group, or a combination thereof. If R 0 is plural, R 0 each independently represents a 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 Z 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 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. When n is 2 or more, each R A 2 independently represents a substituent.
- 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 have 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, and may have two or more in combination. It may be.
- the following monomers are also suitably used as the raw material for the resin (A).
- the total number of repeating units having at least one kind is preferably 5 to 70 mol%, more preferably 10 to 65 mol%, more preferably 20 to 60 mol% is more preferable.
- 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 have the repeating unit which has a polar group individually by 1 type, and may have 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) may 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.
- the resin (A) may have one type of repeating unit that has neither an acid-decomposable group nor a polar group, or may have two or more types in combination.
- 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) is, other than the above repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or further, general required characteristics of resist, resolving power, heat resistance, sensitivity, etc.
- Various repeating structural units may be included for the purpose of adjusting the above. Examples of such a repeating structural unit include, but are not limited to, a repeating structural unit corresponding to a predetermined monomer.
- the predetermined monomer has one addition polymerizable unsaturated bond selected from, for example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Compounds and the like.
- addition polymerizable unsaturated compounds that can be copolymerized with monomers corresponding to the above various repeating structural units may be used.
- 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 is preferably 5 mol% or less, more preferably 3 mol% or less with respect to all repeating units in the resin (A). 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 (a) having an aromatic hydrocarbon group.
- the repeating unit (a) having an aromatic hydrocarbon group is preferably a repeating unit (a1) having a phenolic hydroxyl group.
- the phenolic hydroxyl group is a group formed by substituting a hydrogen atom of an aromatic hydrocarbon group with a hydroxyl group.
- the aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.
- repeating unit (a1) having a phenolic hydroxyl group examples include a repeating unit represented by the following general formula (I).
- R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- R 42 may form a ring with Ar 4, R 42 in this case represents a single bond or an alkylene group.
- X 4 represents a single bond, —COO—, or —CONR 64 —, and R 64 represents a hydrogen atom or an alkyl group.
- L 4 represents a single bond or a divalent linking group.
- Ar 4 represents an (n + 1) -valent aromatic hydrocarbon group, and when bonded to R 42 to form a ring, represents an (n + 2) -valent aromatic hydrocarbon group.
- n represents an integer of 1 to 5.
- n is an integer of 2 or more, or X 4 is —COO— or —CONR 64 —.
- Examples of the alkyl group represented by R 41 , R 42 and R 43 in the general formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, which may have a substituent,
- An alkyl group having 20 or less carbon atoms such as sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group is preferable, an alkyl group having 8 or less carbon atoms is more preferable, and an alkyl group having 3 or less carbon atoms is preferable. Further preferred.
- the cycloalkyl group represented by R 41 , R 42 and R 43 in the general formula (I) may be monocyclic or polycyclic.
- Examples of the halogen atom represented by R 41 , R 42 and R 43 in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
- the alkyl group contained in the alkoxycarbonyl group represented by R 41 , R 42 and R 43 in the general formula (I) the same alkyl groups as those described above for R 41 , R 42 and R 43 are preferable.
- Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls.
- Ar 4 represents an (n + 1) -valent aromatic hydrocarbon group.
- the divalent aromatic hydrocarbon group in the case where n is 1 may have a substituent, for example, an arylene having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group.
- An aromatic hydrocarbon group containing a heterocyclic group such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole is preferable.
- Specific examples of the (n + 1) -valent aromatic hydrocarbon group in the case where n is an integer of 2 or more include (n-1) arbitrary numbers of the above-described specific examples of the divalent aromatic hydrocarbon group.
- a group formed by removing a hydrogen atom can be preferably exemplified.
- the (n + 1) -valent aromatic hydrocarbon group may further have a substituent.
- Examples of the substituent that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n + 1) -valent aromatic hydrocarbon group may have include R 41 , R 42 , and R 43 in the general formula (I).
- R 64 represents a hydrogen atom or an alkyl group
- An alkyl group having 20 or less carbon atoms such as isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group is preferable, and an alkyl group having 8 or less carbon atoms is more preferable.
- X 4 is preferably a single bond, —COO— or —
- the divalent linking group as L 4 is preferably an alkylene group, and as the alkylene group, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, which may have a substituent, And an alkylene group having 1 to 8 carbon atoms, such as an octylene group.
- Ar 4 an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms is preferable, and a benzene ring group, a naphthalene ring group, or a biphenylene ring group is more preferable.
- the repeating unit represented by general formula (I) is a repeating unit derived from hydroxystyrene. That is, Ar 4 is preferably a benzene ring group.
- repeating unit (a1) which has a phenolic hydroxyl group
- this invention is not limited to this.
- a represents 1 or 2.
- Resin (A) may have one type of repeating unit (a1) having a phenolic hydroxyl group, or two or more types in combination.
- the content of the repeating unit (a1) having a phenolic hydroxyl group is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, and more preferably 30 to 85 mol% with respect to all the repeating units of the resin (A). Further preferred.
- repeating unit (a) having an aromatic hydrocarbon group a repeating unit (a2) having a structure (acid-decomposable group) protected with a leaving group that decomposes and leaves a phenolic hydroxyl group by the action of an acid Can be preferably mentioned.
- Repeating unit (a2) having a structure (acid-decomposable group) protected by a leaving group that decomposes and leaves by the action of an acid of a phenolic hydroxyl group
- Examples of the leaving group that decomposes and leaves by the action of an acid include groups represented by formulas (Y1) to (Y4).
- Formula (Y1) —C (Rx 1 ) (Rx 2 ) (Rx 3 )
- Formula (Y2) —C ( ⁇ O) OC (Rx 1 ) (Rx 2 ) (Rx 3 )
- Formula (Y3) —C (R 36 ) (R 37 ) (OR 38 )
- Rx 1 to Rx 3 each independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups. Among these, Rx 1 to Rx 3 are more preferably each independently a repeating unit representing a linear or branched alkyl group, and Rx 1 to Rx 3 are each independently a linear group. More preferably, it is a repeating unit representing an alkyl group. Two of Rx 1 to Rx 3 may combine to form a monocycle or polycycle.
- the alkyl group of Rx 1 to Rx 3 is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. .
- Examples of the cycloalkyl group represented by Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Are preferred.
- Examples of the cycloalkyl group formed by combining two of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group. And a polycyclic cycloalkyl group such as an adamantyl group are preferred. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
- the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. It may be replaced.
- Rx 1 is a methyl group or an ethyl group
- Rx 2 and Rx 3 are bonded to form the above cycloalkyl group. preferable.
- R 36 to R 38 each independently represents a hydrogen atom or a monovalent organic group.
- R 37 and R 38 may be bonded to each other to form a ring.
- the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
- R 36 is preferably a hydrogen atom.
- Ar represents an aromatic hydrocarbon group.
- Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
- Rn and Ar may be bonded to each other to form a non-aromatic ring.
- Ar is more preferably an aryl group.
- repeating unit (a2) those having a structure in which a hydrogen atom in a phenolic hydroxyl group is protected by a group represented by formulas (Y1) to (Y4) are preferable.
- the repeating unit (a2) is preferably a repeating unit represented by the following general formula (AII).
- R 61 , R 62 and R 63 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- R 62 may be bonded to Ar 6 to form a ring, and R 62 in this case represents a single bond or an alkylene group.
- X 6 represents a single bond, —COO—, or —CONR 64 —.
- R 64 represents a hydrogen atom or an alkyl group.
- L 6 represents a single bond or an alkylene group.
- Ar 6 represents an (n + 1) -valent aromatic hydrocarbon group, and when bonded to R 62 to form a ring, represents an (n + 2) -valent aromatic hydrocarbon group.
- Y 2 independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ⁇ 2. However, at least one of Y 2 represents a group capable of leaving by the action of an acid.
- the group capable of leaving by the action of an acid as Y 2 is preferably represented by formulas (Y1) to (Y4).
- n represents an integer of 1 to 4.
- Each of the above groups may have a substituent.
- substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and Examples thereof include alkoxycarbonyl groups (having 2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferred.
- a2 repeating unit
- Resin (A) may have the repeating unit (a2) alone or in combination of two or more.
- the content of the repeating unit (a2) in the resin (A) is preferably 5 to 80 mol% with respect to all the repeating units in the resin (A), and preferably 5 to 75 mol. % Is more preferable, and 10 to 65 mol% is still more preferable.
- the repeating unit having an acid-decomposable group and an aromatic hydrocarbon group corresponds to both a repeating unit having an acid-decomposable group and a repeating unit having an aromatic hydrocarbon group.
- the composition of the present invention contains a crosslinking agent (G) described later
- the composition of the present invention contains an alkali-soluble resin (B) having a phenolic hydroxyl group (hereinafter also referred to as “resin (B)”). It is preferable.
- the resin (B) preferably has a repeating unit having a phenolic hydroxyl group. In this case, typically, a negative pattern is suitably formed.
- the crosslinking agent (G) may be supported on the resin (B).
- the resin (B) may have the acid-decomposable group described above.
- the repeating unit having a phenolic hydroxyl group contained in the resin (B) is preferably a repeating unit represented by the following general formula (II).
- R 2 represents a hydrogen atom, an alkyl group (preferably a methyl group), or a halogen atom (preferably a fluorine atom).
- B ′ represents a single bond or a divalent linking group.
- Ar ′ represents an aromatic ring group.
- m represents an integer of 1 or more.
- Resin (B) may be used individually by 1 type, and may use 2 or more types together. Preferred examples of the resin (B) include the resins disclosed in paragraphs ⁇ 0142> to ⁇ 0347> of US Patent Application Publication No. 2016 / 0282720A1.
- composition of the present invention may contain both a resin (A) and a resin (B).
- the method for polymerizing the resin is not particularly limited, and a known method can be used. However, in the production of the resin, it is necessary to sufficiently carry out a purification treatment in order to further reduce impurities taken into the composition from the resin (for example, impurities having absorption at a wavelength of 248 nm and basic impurities). .
- the purification method for reducing the impurities include a method (precipitation purification) in which a resin-containing solution dissolved in a good solvent is brought into contact with a poor solvent to precipitate a solid. It is preferable to repeat the precipitation purification a plurality of times.
- the good solvent is not particularly limited as long as it is a solvent in which the resin, unreacted monomers and the like are dissolved.
- the poor solvent is not particularly limited as long as it is a solvent for precipitating the resin.
- the purification method for reducing the impurities include a method of washing the resin using a solution containing a weak acid such as dilute hydrochloric acid, a method of removing basic impurities by washing with water, and the like.
- the content of the resin (A) and / or the resin (B) is generally 30% by mass or more based on the total solid content. In many cases, 40 mass% or more is preferable, and 50 mass% or more is more preferable. An upper limit in particular is not restrict
- the composition of the present invention typically contains a photoacid generator (hereinafter also referred to as “photoacid generator (C)”).
- the photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation.
- a compound capable of generating an organic acid upon irradiation with actinic rays or radiation is preferable.
- Examples 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.
- 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 / Known compounds disclosed in paragraphs ⁇ 0323> to ⁇ 0402> of the specification of 0237190A1 can be suitably used as the photoacid generator (C).
- photoacid generator (C) for example, compounds represented by the following general formula (ZI), general formula (ZII) or general formula (ZIII) are preferable.
- 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 —.
- Z ⁇ represents an anion.
- the photoacid generator (C) may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of R 201 ⁇ R 203 of the compound represented by formula (ZI), and at least one of R 201 ⁇ R 203 of another compound represented by formula (ZI), a single bond Alternatively, it may be a compound having a structure bonded 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 contained in 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 that the arylsulfonium compound has as necessary is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms.
- the cycloalkyl group is preferably 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, or a cyclohexyl group.
- the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 are each independently an alkyl group (eg, having 1 to 15 carbon atoms), a cycloalkyl group (eg, having 3 to 15 carbon atoms), an aryl group (eg, carbon (Chem. 6-14), an alkoxy group (for example, C 1-15), 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-oxocyclo An alkyl 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, Propyl group, butyl group, and pentyl group) and cycloalkyl groups having 3 to 10 carbon atoms (eg, 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 are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group Represents 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 an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic fused ring 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 0-2.
- r represents an integer of 0 to 8.
- R 13 represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or 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. When a plurality of R 14 are present, they each independently represent the above group such as a hydroxyl group. 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.
- the alkyl group preferably has 1 to 10 carbon atoms.
- a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like 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.
- Examples of the alkyl group and cycloalkyl group represented by R 204 to R 207 include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, A butyl group and a pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a 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 an alkyl group (eg, having 1 to 15 carbon atoms) and a cycloalkyl group (eg, having 3 to 3 carbon atoms). 15), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
- 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 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, and more preferably a fluorine atom or CF 3 . In particular, it is more 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 a plurality of R 4 and R 5 are present, R 4 and R 5 may be the same as or different from each other.
- the alkyl group represented by R 4 and R 5 may have a substituent, and preferably has 1 to 4 carbon atoms.
- R 4 and R 5 are preferably 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.
- L 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), a cycloalkyl group (monocyclic, polycyclic and spirocyclic). Any of them, 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 Groups, and sulfonate groups.
- the carbon constituting the cyclic organic group may be a carbonyl carbon.
- Examples of the anion represented by the general formula (3) include 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 a fluorine atom.
- L, q and W are the same as those in the general formula (3).
- 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.
- substituents 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 still more preferably 3.
- D represents a single bond or a divalent linking group.
- the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonic acid ester group, an ester group, and a group composed of a combination of two or more 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 combination of the above cations and anions can be used 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 (when there are a plurality of types) is preferably 0.1 to 35% by mass, based on the total solid content of the composition, preferably 0.5 to More preferably, it is 25% by mass, more preferably 1 to 20% by mass, and particularly preferably 1 to 15% by mass.
- the photoacid generator contains a compound represented by the above general formula (ZI-3) or (ZI-4)
- the total is preferably 1 to 35% by mass, more preferably 1 to 30% by mass, based on the total solid content of the composition.
- the composition of the present invention preferably contains an acid diffusion controller (D).
- the acid diffusion controller (D) acts as a quencher that traps the acid generated from the photoacid generator and the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid.
- a low molecular weight compound (DD) having a group capable of leaving by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation moiety can be used as an acid diffusion controller.
- DD low molecular weight compound having a group capable of leaving by the action of an acid
- DE onium salt compound having a nitrogen atom in the cation moiety
- a known acid diffusion controller can be used as appropriate.
- 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 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or aryl. Represents a group (having 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 electrons or a group capable of electrostatically interacting with protons, 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 to.
- 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, a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.
- 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, More preferably, 13 ⁇ pKa ⁇ -3 is satisfied.
- 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 photoacid generator can be used as an acid diffusion controller.
- DC onium salt
- the photoacid generator is generated by irradiation with actinic rays or radiation.
- the acid generated from the acid collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to produce 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.
- onium salt that is a weak acid relative to the photoacid generator compounds represented by the following general formulas (d1-1) to (d1-3) are preferable.
- R 51 is an optionally substituted hydrocarbon group
- Z 2c is an optionally substituted hydrocarbon group having 1 to 30 carbon atoms (provided that the 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 the iodonium cation represented by M + include the sulfonium cation exemplified by the general formula (ZI) and the 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 these 2 Examples include groups formed by combining more than one species.
- L 1 is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a combination of two or more of these groups.
- 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 is represented by the following general formula (d-1).
- R b each 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 3 to 30 carbon atoms), an aralkyl group. (Preferably having 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms).
- R b may be connected to each other to form a ring.
- the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by 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, and more preferably a linear or branched alkyl group or a cycloalkyl group.
- the ring two R b is formed by interconnected, alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
- Specific examples of the structure represented by the general formula (d-1) include, but are not limited to, the structure 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.
- R b has the same meaning as R b in formula (d-1), and preferred examples are also the same.
- the alkyl group as R a, a cycloalkyl group, an aryl group and aralkyl group 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 preferred compound (DD) in the present invention include, but are not limited to, compounds disclosed in paragraph ⁇ 0475> of US Patent Application Publication No. 2012 / 0135348A1.
- 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.
- an electron-withdrawing functional group such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom
- the compound (DE) include, but are not limited to, compounds disclosed in paragraph ⁇ 0203> of US Patent Application Publication No. 2015 / 03009408
- the acid diffusion controller (D) may be used alone or in combination of two or more.
- the content of the acid diffusion controller (D) in the composition (when there are a plurality of types) is preferably 0.1 to 10% by mass, based on the total solid content of the composition, preferably 0.1 to 5 mass% is more preferable.
- the composition of the present invention preferably contains a hydrophobic resin (E).
- the hydrophobic resin (E) is preferably a resin different from the resin (A) and the resin (B).
- the composition of the present invention contains the hydrophobic resin (E)
- 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 (E) is preferably designed to be unevenly distributed on the surface of the resist film. However, unlike the surfactant, the hydrophobic resin (E) is not necessarily required to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.
- the hydrophobic resin (E) 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 the resin has a repeating unit having at least one kind.
- the hydrophobic resin (E) contains a fluorine atom and / or a silicon atom
- the fluorine atom and / or silicon atom in the hydrophobic resin (E) may be contained in the main chain of the resin, It may be contained in the chain.
- the hydrophobic resin (E) 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. preferable.
- the hydrophobic resin (E) 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, for example, 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
- 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% with respect to all the repeating units in the hydrophobic resin (E). 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 (E) are the same as the repeating unit having an acid-decomposable group mentioned in 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 hydrophobic resin (E). 20 to 60 mol% is more preferable.
- the hydrophobic resin (E) 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 in the hydrophobic resin (E).
- the repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, based on all repeating units in the hydrophobic resin (E).
- hydrophobic resin (E) contains a CH 3 partial structure in the side chain portion
- a mode in which the hydrophobic resin (E) does not substantially contain a fluorine atom and a silicon atom is also preferable.
- hydrophobic resin (E) 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 (E) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
- the total content of the residual monomer and / or oligomer component contained in the hydrophobic resin (E) 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 (E) publicly known resins can be appropriately selected and used alone or as a mixture thereof.
- 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 (E).
- Hydrophobic resin (E) 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 (E) having different surface energies from the viewpoint of compatibility between the immersion liquid followability and the development characteristics in the immersion exposure.
- the content of the hydrophobic resin (E) in the composition is preferably 0.01 to 10% by mass and more preferably 0.05 to 8% by mass with respect to the total solid content in the composition of the present invention.
- the composition of the present invention preferably 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 has a hydroxyl group in a structure may be used as an organic solvent, you may use the mixed solvent which mixed the solvent which has a hydroxyl group in a structure, and the solvent which does not have a hydroxyl group.
- the solvent having a hydroxyl group and the solvent not having a hydroxyl group the above-described exemplary compounds can be selected as appropriate.
- the solvent containing a hydroxyl group an alkylene glycol monoalkyl ether, an alkyl lactate or the like is preferable, and propylene glycol monomethyl ether ( PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred.
- alkylene glycol monoalkyl ether acetate alkyl alkoxypropionate, monoketone compound which may have a ring, cyclic lactone, alkyl acetate, etc. are preferable.
- propylene More preferred are glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, cyclopentanone or butyl acetate, propylene glycol monomethyl ether acetate, ⁇ -butyrolactone, ethyl ethoxypropionate, More preferred are cyclohexanone, cyclopentanone or 2-heptanone.
- the solvent having no hydroxyl group propylene carbonate is also preferable.
- the mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is preferably from 1/99 to 99/1, more preferably from 10/90 to 90/10, and from 20/80 to 60/40. Further preferred.
- a mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable in terms 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 this invention may contain the compound (henceforth a crosslinking agent (G)) which bridge
- a crosslinking agent (G) a known compound can be appropriately used.
- known compounds disclosed in paragraphs ⁇ 0379> to ⁇ 0431> of US Patent Application Publication No. 2016 / 0147154A1 and paragraphs ⁇ 0064> to ⁇ 0141> of US Patent Application Publication No. 2016 / 0282720A1 Can be suitably used as the crosslinking agent (G).
- the crosslinking agent (G) is a compound having a crosslinkable group capable of crosslinking the resin, and examples of the crosslinkable group include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, an oxirane ring, And an oxetane ring.
- the crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring or an oxetane ring.
- the crosslinker (G) is preferably a compound (including a resin) having two or more crosslinkable groups.
- the cross-linking agent (G) is more preferably a phenol derivative, a urea compound (a compound having a urea structure) or a melamine compound (a compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group.
- a crosslinking agent may be used individually by 1 type, and may use 2 or more types together.
- the content of the crosslinking agent (G) is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and still more preferably 5 to 30% by mass with respect to the total solid content of the resist composition.
- composition of the present invention contains a surfactant that preferably contains a surfactant, it contains 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 pattern with low adhesion and development defects with good sensitivity and resolution.
- 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 content of the surfactant is 10 ppm or more based on the total solid content of the composition, the surface uneven distribution of the hydrophobic resin (E) 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 solid content concentration of the composition of the present invention is usually preferably 1.0 to 50% by mass, more preferably 10 to 50% by mass, and still more preferably 30 to 50% 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 film thickness of the actinic ray-sensitive or radiation-sensitive film comprising the composition of the present invention is 1 ⁇ m or more, and is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and further preferably 10 ⁇ m or more for the purpose of increasing the number of processing steps. preferable. Although an upper limit is not specifically limited, For example, it is 100 micrometers or less.
- a pattern can be formed from the composition of the present invention.
- the film thickness of the pattern to be formed is 1 ⁇ m or more.
- it is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and further preferably 10 ⁇ m or more.
- An upper limit is not specifically limited, For example, it is 100 micrometers or less.
- 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 preferably has a viscosity of 100 to 500 mPa ⁇ s.
- the viscosity of the composition of the present invention is more preferably 100 to 300 mPa ⁇ s from the viewpoint of excellent coating properties.
- the viscosity can be measured with an E-type viscometer.
- 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 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 of the present invention will also be described.
- the pattern forming method of the present invention comprises: (I) a step of forming a resist film (actinic light sensitive or radiation sensitive film) on a support with the above-mentioned actinic ray sensitive or radiation sensitive resin composition (resist film forming step); (Ii) exposing the resist film (irradiating actinic rays or radiation) (exposure step); and (Iii) a step of developing the exposed resist film using 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: PreBake) step before (ii) 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 (iii) before 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), and antireflection film
- SOG Spin On Glass
- SOC Spin On Carbon
- antireflection film As a material constituting the resist underlayer film, a known organic or inorganic material can be appropriately used.
- a protective film (top coat) may be formed on the upper layer of the resist 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 resist film containing the hydrophobic resin described above.
- the support is not particularly limited, and a substrate 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 is used. be able to.
- 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 even more preferably 1 to 200 nm.
- KrF excimer laser (248 nm), ArF excimer laser (193 nm), F 2 excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc.
- KrF excimer laser, ArF excimer laser EUV or electron beam is preferable, and KrF excimer laser is more preferable.
- 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, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, 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 acid, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
- the solvents disclosed in paragraphs ⁇ 0715> to ⁇ 0718> of US Patent Application Publication No. 2016 / 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 entire developer 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 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total amount of the developer. % Is particularly preferred.
- the organic developer may 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 controller 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
- 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
- a substrate Examples include a method of spraying developer on the surface (spray method) or a method of continuously discharging developer while scanning a developer discharge nozzle on a substrate rotating at a constant speed (dynamic dispensing method). It is done.
- 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.
- 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 for 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 liquid may contain an appropriate amount of a surfactant.
- the substrate that has been developed using the organic developer is washed with a rinse that contains 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), or immersing the substrate in a bath filled with the rinse liquid for a certain period of time. Examples thereof include a method (dip method) and a method (spray method) of spraying a rinsing liquid on the substrate surface.
- 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 or less, still more preferably 10 ppt or less, and substantially not (less than the detection limit of the measuring device). 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.
- the filter material is preferably a polytetrafluoroethylene, polyethylene, or nylon filter.
- 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.
- 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.
- 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.
- Teflon registered trademark
- the preferable conditions for filter filtration performed on the raw materials constituting the various materials 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 pattern with a plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/0104957 is cited.
- Japanese Patent Application Publication No. 2004-235468 JP 2004-235468 A
- US Patent Application Publication No. 2010/0020297 Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement”
- the pattern formed by the above method is disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/0209941. It can be used as a core material for the spacer process.
- 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.
- PMEA propylene glycol monomethyl ether acetate
- the obtained polymer solution 1A-1 was transferred to a 5 L three-necked flask, and 300 g of propylene glycol monomethyl ether, 600 g of methanol, 35 g of pure water, and 149.96 g of triethylamine were placed in an oil bath set at 80 ° C. for 12 hours. Reacted. It was confirmed from 1 H-NMR (nuclear magnetic resonance) that the acetyl group protection was removed, and the reaction solution was cooled to room temperature. The reaction solution was transferred to a separatory funnel, and ethyl acetate and dilute hydrochloric acid were added thereto, and the extraction operation was repeated three times (removal of basic impurities).
- the organic layer was washed about three times with pure water, and then heptane was added to the viscous liquid concentrated by evaporation to precipitate a solid (first precipitation purification).
- the powder obtained by decanting the supernatant was dissolved in ethyl acetate, and the ethyl acetate solution was slowly dropped into heptane for precipitation purification (second precipitation purification).
- the precipitated powder was filtered, washed with heptane, and dried under reduced pressure at 40 ° C. It was confirmed by 1 H-NMR and GPC that the desired resin 1A was obtained.
- Resin 1B was synthesized by the following method (hereinafter also referred to as “PHS method”).
- parahydroxystyrene was synthesized in good yield by hydrolysis under the condition of sodium hydroxide using paraacetoxystyrene as a starting material.
- 60 g of propylene glycol monomethyl ether acetate (PGMEA) was placed in a four-necked flask equipped with a thermometer, a gas blowing tube, a cooling tube, a stirrer, and a water bath, and the temperature was raised to 80 ° C. after purging with nitrogen.
- PGMEA propylene glycol monomethyl ether acetate
- Resin 2A having the following structure was synthesized by the same method except that the monomer species was changed in the synthesis method of resin 1A (PACST method) described above. It was confirmed by 1 H-NMR and GPC that the desired resin 2A was obtained.
- Resin 3A having the following structure was synthesized by the same method except that the monomer species was changed in the synthesis method of resin 1A (PACST method) described above. It was confirmed by 1 H-NMR and GPC that the desired resin 3A was obtained.
- Resin 3B having the following structure was synthesized by the same method except that the monomer species was changed in the synthesis method of resin 1B (PHS method) described above. It was confirmed by 1 H-NMR and GPC that the desired resin 3B was obtained.
- Resin 4 was synthesized by the following method (polymer reaction).
- parahydroxystyrene was synthesized in good yield by hydrolysis under the condition of sodium hydroxide using paraacetoxystyrene as a starting material.
- a four-necked flask equipped with a thermometer, a gas blowing tube, a cooling tube, a stirrer, and a water bath 210 g of parahydroxystyrene and 45 g of t-butyl vinyl ether are dissolved in 1000 mL of dehydrated tetrahydrofuran (THF).
- THF dehydrated tetrahydrofuran
- Resin 5 having the following structure was synthesized by the same method except that the monomer species was changed in the synthesis method of resin 1B (PHS method) described above. It was confirmed by 1 H-NMR and GPC that the desired resin 5 was obtained.
- Resin 1A ′ was synthesized by the same method except that the precipitation purification was performed once in the synthesis method of resin 1A (PACST method) described above.
- Resin 3B ′ was synthesized by the same method except that the basic impurities were not removed and precipitation purification was performed once in the synthesis method of resin 3B (PHS method) described above.
- Resin 2A ′ was synthesized by the same method as described above except that basic impurities were not removed in the synthesis method of Resin 2A (PACST method).
- Resin 4 was synthesized by the same method as described above except that basic impurities were not removed in the synthesis method of resin 4 (polymer reaction).
- Table 1 shows the molar ratio of repeating units, weight average molecular weight (Mw), and dispersity (Mw / Mn) in the various resins synthesized.
- the weight average molecular weight (Mw) and dispersity (Mw / Mn) of various resins shown in Table 1 were measured by GPC (carrier: THF) (in terms of polystyrene).
- the composition ratio (mol% ratio) of the resin was measured by 13 C-NMR.
- the resin 1A ′, the resin 2A ′, the resin 3B ′, and the resin 4 ′ are respectively composed of the resin 1A, the resin 2A, the resin 3B, and the molar ratio of repeating units similar to the resin 4, Mw, and , Mw / Mn.
- each composition 25 types contained in each composition (Na, K, Ca, Fe, Cu, Mg, Mn, Al, Li, Cr, Ni, Sn, Zn, Ag, As, Au, Ba, Cd, Co, Pb , Ti, V, W, Mo, Zr) were measured with an ICP-MS apparatus (inductively coupled plasma mass spectrometer) “Agilent 7500cs” manufactured by Agilent Technologies, and the content of each metal species was Each was less than 10 ppb.
- ICP-MS apparatus inductively coupled plasma mass spectrometer
- the compounds a to e are parahydroxystyrene and modified products thereof (compounds a and c), paraacetoxystyrene and modified products thereof (compounds b and d), and 4- (tert-butoxy) styrene (compound e, respectively). It was speculated that all were derived from resin raw material components. Specific structures of the compounds a to e are shown below.
- This resist film is subjected to a KrF excimer laser scanner (manufactured by ASML, through a mask having a line and space pattern such that the space width of the pattern formed after reduced projection exposure and development is 5 ⁇ m and the pitch width is 25 ⁇ m.
- TMAH tetramethylammonium hydroxide
- the pattern exposure is exposure through a mask having a line-and-space pattern such that the space width after reduced projection exposure is 5 ⁇ m and the pitch width is 25 ⁇ m.
- the exposure amount is 5 ⁇ m for the space width and 25 ⁇ m for the pitch width.
- the optimum exposure amount (sensitivity) for forming an isolated space pattern was used. In the determination of the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM (Scanning Electron Microscope)) (9380II manufactured by Hitachi High-Technologies Corporation).
- N is the one that has not been resolved to the substrate
- B is the one that has been resolved to the substrate but the pattern has poor linearity
- A is the one that has good pattern linearity. evaluated. Examples of the determination are shown in FIGS. 1 is an example in which the determination is N, FIG. 2 is an example in which the determination is B, and FIG. 3 is an example in which the determination is A. The evaluation results are shown in Table 3.
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Abstract
Description
このようなレジスト組成物として、例えば、特許文献1にはp-ヒドロキシスチレン系繰り返し単位を有する樹脂を含有するポジ型のレジスト組成物が記載されている。
本発明者らは、特許文献1に記載されるp-ヒドロキシスチレン系繰り返し単位を有する樹脂を用いて厚膜(1μm以上)のレジスト膜を作製してその露光現像後のパターンの性能について検討していたところ、解像性が必ずしも十分ではなく、更に改善する余地があることを明らかとした。
また、本発明は、上記感活性光線性又は感放射線性樹脂組成物を用いたレジスト膜、パターン形成方法、及び電子デバイスの製造方法を提供することを課題とする。
すなわち、以下の構成により上記目的を達成することができることを見出した。
樹脂を含有し、
波長248nmに吸収を有する不純物の含有量が、上記樹脂に対して1.00質量%以下である、感活性光線性又は感放射線性樹脂組成物。
〔2〕 上記樹脂が、酸の作用により分解して極性が増大する基を有する繰り返し単位を含有する、〔1〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔3〕 上記樹脂が、フェノール性水酸基を有する繰り返し単位を含有する、〔1〕又は〔2〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔4〕 上記不純物が、芳香族化合物である、〔1〕~〔3〕のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
〔5〕 上記樹脂が、後述する一般式(I)で表される繰り返し単位を含有し、
上記不純物が、後述する一般式(X)で表される化合物である、〔1〕~〔4〕のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
〔6〕 上記樹脂が塩基性化合物の存在下で合成された樹脂であり、
上記塩基性化合物に由来する塩基性不純物の含有量が、上記樹脂に対して0.10質量%以下である、〔5〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔7〕 更に、光酸発生剤を含有する、〔1〕~〔6〕のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
〔8〕 粘度が100~500mPa・sである、〔1〕~〔7〕のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
〔9〕 〔1〕~〔8〕のいずれかに記載の感活性光線性又は感放射線性樹脂組成物により形成されたレジスト膜。
〔10〕 〔1〕~〔8〕のいずれかに記載の感活性光線性又は感放射線性樹脂組成物を用いて膜厚が1μm以上のレジスト膜を形成するレジスト膜形成工程と、
上記レジスト膜を露光する露光工程と、
露光された上記レジスト膜を、現像液を用いて現像する現像工程と、
を含むパターン形成方法。
〔11〕 〔10〕に記載のパターン形成方法を含む、電子デバイスの製造方法。
また、本発明によれば、上記感活性光線性又は感放射線性樹脂組成物を用いたレジスト膜、パターン形成方法、及び電子デバイスの製造方法を提供することができる。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されない。
本明細書中における基(原子団)の表記について、置換及び無置換を記していない表記は、置換基を有さない基と共に置換基を有する基をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含する。また、本明細書中における「有機基」とは、少なくとも1個の炭素原子を含む基をいう。
本明細書中における「活性光線」又は「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光:Extreme Ultraviolet)、X線、及び電子線(EB:Electron Beam)等を意味する。本明細書中における「光」とは、活性光線又は放射線を意味する。
本明細書中における「露光」とは、特に断らない限り、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、及びX線等による露光のみならず、電子線、及びイオンビーム等の粒子線による描画も含む。
本明細書において、「~」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。
本明細書において、樹脂の重量平均分子量(Mw)、数平均分子量(Mn)、及び分散度(分子量分布ともいう)(Mw/Mn)は、GPC(Gel Permeation Chromatography)装置(東ソー製HLC-8120GPC)によるGPC測定(溶媒:テトラヒドロフラン、流量(サンプル注入量):10μL、カラム:東ソー社製TSK gel Multipore HXL-M、カラム温度:40℃、流速:1.0mL/分、検出器:示差屈折率検出器(Refractive Index Detector))によるポリスチレン換算値として定義される。
本発明の感活性光線性又は感放射線性樹脂組成物(以後、単に「本発明の組成物」とも称する)は、膜厚が1μm以上のパターンの形成に用いられる感活性光線性又は感放射線性樹脂組成物であって、
樹脂を含有し、
波長248nmに吸収を有する不純物の含有量が、上記樹脂に対して1.00質量%以下である。
本発明の組成物は、いわゆるレジスト組成物であり、ポジ型のレジスト組成物であっても、ネガ型のレジスト組成物であってもよい。また、アルカリ現像用のレジスト組成物であっても、有機溶剤現像用のレジスト組成物であってもよい。
本発明の組成物は、典型的には、化学増幅型のレジスト組成物である。
本発明者らは、上記不純物について更なる検討をしたところ、特に、レジスト膜中の波長248nmに吸収を有する不純物の含有量を樹脂に対して1.00質量%以下とすることにより、形成されるパターンの解像性に優れることを明らかとした。
本発明において、不純物とは、本発明の組成物中に含まれ得る、樹脂、光酸発生剤、酸拡散制御剤、界面活性剤、溶剤、疎水性樹脂、及び架橋剤以外の成分を意図し、例えば、上記各成分を通じて組成物中に持ち込まれる原材料等の成分(例えば、樹脂から持ち込まれる未反応モノマー及び上記未反応モノマーの変性物、並びに、樹脂の合成において脱保護反応に用いられた塩基性化合物等)等が挙げられる。
本発明の組成物は、不純物のうち、特に波長248nmに吸収を有する不純物の含有量が、樹脂に対して1.00質量%以下である。
波長248nmに吸収を有する不純物は、波長248nmに吸収を有しさえすれば特に限定されず、なかでも、吸収ピークを波長220~280nmに有しているものが好ましい。特に、不純物が芳香族化合物(例えばベンゼン環を有する化合物等)である場合には、芳香環に由来する高い吸収を波長248nm付近に有するため、精製により除去されることが望ましい。
上記波長248nmに吸収を有する不純物は、例えば、樹脂(例えば、酸の作用により分解して極性が増大する基を有する繰り返し単位(特に、フェノール性水酸基が酸の作用により分解して脱離する脱離基で保護された構造(酸分解性基)を有する繰り返し単位)、及び/又は、フェノール性水酸基を有する繰り返し単位(特に、ヒドロキシスチレンに由来する繰り返し単位)を有する樹脂)の合成原料である未反応モノマー及び未反応モノマーの変性物が該当する。未反応モノマー及び未反応モノマーの変性物は、樹脂を介して組成物中に持ち込まれる。したがって、上述の樹脂を使用する場合には、精製処理により未反応モノマー及び未反応モノマーの変性物を低減する必要がある。
また、Raは、一般式(Y1)で表される基、又は、一般式(Y2)で表される基を表す。一般式(Y1)及び一般式(Y2)中、R41、R42及びR43の定義は、後述する一般式(I)中の各基の定義と同義である。
R44は、アルキル基を表す。アルキル基の炭素数は、1~5が好ましく、1~3がより好ましく、1が更に好ましい。
Rbは、水素原子、又は、保護基を表す。保護基としては、アルキル基、又は、-CO-Rc等が挙げられる。
Rcは、アルキル基を表す。
Rbで表されるアルキル基、及び、Rcで表されるアルキル基の炭素数は、1~5が好ましく、1~3がより好ましく、1が更に好ましい。
*は結合位置を表す。
つまり、波長248nmに吸収を有する化合物は、本発明の組成物中に含有されないか、又は、含有される場合(波長248nmに吸収を有する化合物の含有量が、樹脂に対して0質量%超である場合)は1.00質量%以下である。
本発明の組成物は、不純物のうち、塩基性不純物の含有量が、樹脂に対して低減されていることが好ましい。本発明の組成物が塩基性不純物を含有すると、放射線及び活性光線の照射により光酸発生剤から発生した酸の失活が生じるためである。
ここで、塩基性不純物とは、アミン化合物及び金属水酸化物(金属としては、例えば、アルカリ金属イオン等)等の塩基性化合物を意図する。
なお、塩基性不純物が波長248nmに吸収を有する場合は、その塩基性不純物は上記「波長248nmに吸収を有する不純物」に該当し、「塩基性不純物」には含まれないものとする。
上記塩基性不純物は、本発明の組成物中に、フェノール性水酸基を有する繰り返し単位(特に、一般式(I)で表される繰り返し単位)を有する樹脂を含有する場合に、上記樹脂を介して持ち込まれる場合が多い。フェノール性水酸基を有する繰り返し単位を有する樹脂、例えば、ヒドロキシスチレンに由来する繰り返し単位を有する樹脂は、一般的に、アセトキシスチレンを原材料として合成される。そのため、モノマーの合成時、及び、樹脂の合成後のいずれかにおいて、塩基性化合物の存在下にてアセトキシ基を脱保護してフェノール性水酸基とする脱保護反応を経る必要がある。つまり、上記アミン化合物及び金属水酸化物等の塩基性化合物は、主にこの脱保護の際に使用した塩基性化合物に由来する。したがって、上述の樹脂を使用する場合には、精製処理により脱保護の際に使用した塩基性化合物を除去する必要がある。
本発明の組成物は、塩基性化合物の存在下にて合成された樹脂を含有する場合には、上記塩基性化合物に由来する塩基性不純物の含有量が、樹脂に対して0.10質量%以下であることが好ましい。上記塩基性化合物に由来する塩基性不純物の含有量が樹脂に対して0.10質量%以下である場合、パターンの解像性により優れる。上記塩基性化合物に由来する塩基性不純物の含有量は、樹脂に対して、0.05質量%以下がより好ましく、0.01質量%以下が更に好ましく、0質量%が特に好ましい。
つまり、塩基性不純物は、本発明の組成物中に含有されないか、又は、含有される場合(塩基性不純物の含有量が、樹脂に対して0質量%超である場合)は、0.10質量%以下であることが好ましい。
本発明の組成物は、樹脂を含有する。
上記樹脂は、酸の作用により分解して極性が増大する基(以下、「酸分解性基」とも言う)を有する樹脂(以下、「酸分解性樹脂」又は「樹脂(A)」ともいう)を含有することが好ましい。
この場合、本発明のパターン形成方法において、典型的には、現像液としてアルカリ現像液を採用した場合には、ポジ型パターンが好適に形成され、現像液として有機系現像液を採用した場合には、ネガ型パターンが好適に形成される。
極性基としては、カルボキシル基、フェノール性水酸基、フッ素化アルコール基、スルホン酸基、スルホンアミド基、スルホニルイミド基、(アルキルスルホニル)(アルキルカルボニル)メチレン基、(アルキルスルホニル)(アルキルカルボニル)イミド基、ビス(アルキルカルボニル)メチレン基、ビス(アルキルカルボニル)イミド基、ビス(アルキルスルホニル)メチレン基、ビス(アルキルスルホニル)イミド基、トリス(アルキルカルボニル)メチレン基、及びトリス(アルキルスルホニル)メチレン基等の酸性基(2.38質量%テトラメチルアンモニウムヒドロキシド水溶液中で解離する基)、並びにアルコール性水酸基等が挙げられる。
酸の作用により脱離する基(脱離基)としては、例えば、-C(R36)(R37)(R38)、-C(R36)(R37)(OR39)、及び-C(R01)(R02)(OR39)等が挙げられる。
式中、R36~R39は、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。R36とR37とは、互いに結合して環を形成してもよい。
R01及びR02は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。
R36~R39、R01及びR02のシクロアルキル基は、単環でも、多環でもよい。単環のシクロアルキル基としては、炭素数3~8のシクロアルキル基が好ましく、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基、及びシクロオクチル基等が挙げられる。多環のシクロアルキル基としては、炭素数6~20のシクロアルキル基が好ましく、例えば、アダマンチル基、ノルボルニル基、イソボルニル基、カンファニル基、ジシクロペンチル基、α-ピネル基、トリシクロデカニル基、テトラシクロドデシル基、及びアンドロスタニル基等が挙げられる。なお、シクロアルキル基中の少なくとも1つの炭素原子が酸素原子等のヘテロ原子によって置換されていてもよい。
R36~R39、R01及びR02のアリール基は、炭素数6~10のアリール基が好ましく、例えば、フェニル基、ナフチル基、及びアントリル基等が挙げられる。
R36~R39、R01及びR02のアラルキル基は、炭素数7~12のアラルキル基が好ましく、例えば、ベンジル基、フェネチル基、及びナフチルメチル基等が挙げられる。
R36~R39、R01及びR02のアルケニル基は、炭素数2~8のアルケニル基が好ましく、例えば、ビニル基、アリル基、ブテニル基、及びシクロへキセニル基等が挙げられる。
R36とR37とが互いに結合して形成される環としては、シクロアルキル基(単環又は多環)であることが好ましい。シクロアルキル基としては、シクロペンチル基、及びシクロヘキシル基等の単環のシクロアルキル基、又はノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の多環のシクロアルキル基が好ましい。
Xa1は、水素原子、ハロゲン原子、又は1価の有機基を表す。
Tは、単結合又は2価の連結基を表す。
Rx1~Rx3は、それぞれ独立に、アルキル基又はシクロアルキル基を表す。
Rx1~Rx3のいずれか2つが結合して環構造を形成してもよく、形成しなくてもよい。
Tは、単結合又は-COO-Rt-が好ましい。Rtは、炭素数1~5の鎖状アルキレン基が好ましく、-CH2-、-(CH2)2-、又は-(CH2)3-がより好ましい。Tは、単結合であることがさらに好ましい。
Xa1のアルキル基は、置換基を有していてもよく、置換基としては、例えば、水酸基、及びハロゲン原子(好ましくは、フッ素原子)が挙げられる。
Xa1のアルキル基は、炭素数1~4が好ましく、メチル基、エチル基、プロピル基、ヒドロキシメチル基及びトリフルオロメチル基等が挙げられる。Xa1のアルキル基は、メチル基であることが好ましい。
Rx1、Rx2及びRx3のシクロアルキル基としては、シクロペンチル基、及びシクロヘキシル基等の単環のシクロアルキル基、又は、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の多環のシクロアルキル基が好ましい。
樹脂(A)は、下記一般式(LC1-1)~(LC1-21)のいずれかで表されるラクトン構造、又は、下記一般式(SL1-1)~(SL1-3)のいずれかで表されるスルトン構造を有する繰り返し単位を有することが更に好ましい。また、ラクトン構造又はスルトン構造が主鎖に直接結合していてもよい。好ましい構造としては、一般式(LC1-1)、一般式(LC1-4)、一般式(LC1-5)、一般式(LC1-8)、一般式(LC1-16)、若しくは一般式(LC1-21)で表されるラクトン構造、又は、一般式(SL1-1)で表されるスルトン構造が挙げられる。
Aは、エステル結合(-COO-で表される基)又はアミド結合(-CONH-で表される基)を表す。
nは、-R0-Z-で表される構造の繰り返し数であり、0~5の整数を表し、0又は1であることが好ましく、0であることがより好ましい。nが0である場合、-R0-Z-は存在せず、単結合となる。
R0は、アルキレン基、シクロアルキレン基、又はその組み合わせを表す。R0が複数個ある場合、R0は、各々独立に、アルキレン基、シクロアルキレン基、又はその組み合わせを表す。
Zは、単結合、エーテル結合、エステル結合、アミド結合、ウレタン結合又はウレア結合を表す。Zが複数個ある場合には、Zは、各々独立に、単結合、エーテル結合、エステル結合、アミド結合、ウレタン結合又はウレア結合を表す。
R8は、ラクトン構造又はスルトン構造を有する1価の有機基を表す。
R7は、水素原子、ハロゲン原子又は1価の有機基(好ましくはメチル基)を表す。
Zとしては、エーテル結合、又はエステル結合が好ましく、エステル結合がより好ましい。
環状炭酸エステル構造を有する繰り返し単位は、下記一般式(A-1)で表される繰り返し単位であることが好ましい。
nは0以上の整数を表す。
RA 2は、置換基を表す。nが2以上の場合、RA 2は、各々独立して、置換基を表す。
Aは、単結合、又は2価の連結基を表す。
Zは、式中の-O-C(=O)-O-で表される基と共に単環構造又は多環構造を形成する原子団を表す。
極性基としては、水酸基、シアノ基、カルボキシル基、及びフッ素化アルコール基等が挙げられる。
極性基を有する繰り返し単位としては、極性基で置換された脂環炭化水素構造を有する繰り返し単位が好ましい。また、極性基を有する繰り返し単位は、酸分解性基を有さないことが好ましい。極性基で置換された脂環炭化水素構造における、脂環炭化水素構造としては、アダマンチル基、又はノルボルナン基が好ましい。
樹脂(A)は、極性基を有する繰り返し単位を、1種単独で有していてよく、2種以上を併用して有していてもよい。
極性基を有する繰り返し単位の含有量は、樹脂(A)中の全繰り返し単位に対して、5~40モル%が好ましく、5~30モル%がより好ましく、10~25モル%が更に好ましい。
樹脂(A)は、酸分解性基及び極性基のいずれも有さない繰り返し単位を、1種単独で有していてもよく、2種以上を併用して有していてもよい。
酸分解性基及び極性基のいずれも有さない繰り返し単位の含有量は、樹脂(A)中の全繰り返し単位に対して、5~40モル%が好ましく、5~30モル%がより好ましく、5~25モル%が更に好ましい。
このような繰り返し構造単位としては、所定の単量体に相当する繰り返し構造単位を挙げることができるが、これらに限定されない。
その他にも、上記種々の繰り返し構造単位に相当する単量体と共重合可能である付加重合性の不飽和化合物を用いてもよい。
樹脂(A)において、各繰り返し構造単位の含有モル比は、種々の性能を調節するために適宜設定される。
本明細書において、フェノール性水酸基とは、芳香族炭化水素基の水素原子をヒドロキシル基で置換してなる基である。芳香族炭化水素基の芳香環は単環又は多環の芳香環であり、ベンゼン環及びナフタレン環等が挙げられる。
R41、R42及びR43は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。但し、R42はAr4と結合して環を形成していてもよく、その場合のR42は単結合又はアルキレン基を表す。
X4は、単結合、-COO-、又は-CONR64-を表し、R64は、水素原子又はアルキル基を表す。
L4は、単結合又は2価の連結基を表す。
Ar4は、(n+1)価の芳香族炭化水素基を表し、R42と結合して環を形成する場合には(n+2)価の芳香族炭化水素基を表す。
nは、1~5の整数を表す。
一般式(I)で表される繰り返し単位を高極性化する目的では、nが2以上の整数、又はX4が-COO-、又は-CONR64-であることも好ましい。
一般式(I)におけるR41、R42、及びR43で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子等が挙げられ、フッ素原子が好ましい。
一般式(I)におけるR41、R42、及びR43で表されるアルコキシカルボニル基に含まれるアルキル基としては、上記R41、R42、及びR43におけるアルキル基と同様のものが好ましい。
(n+1)価の芳香族炭化水素基は、更に置換基を有していてもよい。
X4により表される-CONR64-(R64は、水素原子又はアルキル基を表す)におけるR64のアルキル基としては、置換基を有していてもよい、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、ヘキシル基、2-エチルヘキシル基、オクチル基、及びドデシル基等の炭素数20以下のアルキル基が好ましく、炭素数8以下のアルキル基がより好ましい。
X4としては、単結合、-COO-、又は-CONH-が好ましく、単結合、又は-COO-がより好ましい。
Ar4としては、置換基を有していてもよい炭素数6~18の芳香族炭化水素基が好ましく、ベンゼン環基、ナフタレン環基、又はビフェニレン環基がより好ましい。なかでも、一般式(I)で表される繰り返し単位は、ヒドロキシスチレンに由来する繰り返し単位であることが好ましい。即ち、Ar4は、ベンゼン環基であることが好ましい。
式(Y1):-C(Rx1)(Rx2)(Rx3)
式(Y2):-C(=O)OC(Rx1)(Rx2)(Rx3)
式(Y3):-C(R36)(R37)(OR38)
式(Y4):-C(Rn)(H)(Ar)
なかでも、Rx1~Rx3は、各々独立に、直鎖状又は分岐鎖状のアルキル基を表す繰り返し単位であることがより好ましく、Rx1~Rx3が、各々独立に、直鎖状のアルキル基を表す繰り返し単位であることが更に好ましい。
Rx1~Rx3の2つが結合して、単環若しくは多環を形成してもよい。
Rx1~Rx3のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、及びt-ブチル基等の炭素数1~4のアルキル基が好ましい。
Rx1~Rx3のシクロアルキル基としては、シクロペンチル基、シクロヘキシル基等の単環のシクロアルキル基、又は、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の多環のシクロアルキル基が好ましい。
Rx1~Rx3の2つが結合して形成されるシクロアルキル基としては、シクロペンチル基、及びシクロヘキシル基等の単環のシクロアルキル基、又は、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の多環のシクロアルキル基が好ましい。なかでも、炭素数5~6の単環のシクロアルキル基がより好ましい。
Rx1~Rx3の2つが結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の1つが、酸素原子等のヘテロ原子、又は、カルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。
式(Y1)及び(Y2)で表される基は、例えば、Rx1がメチル基又はエチル基であり、Rx2とRx3とが結合して上述のシクロアルキル基を形成している態様が好ましい。
R61、R62及びR63は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基、又はアルコキシカルボニル基を表す。但し、R62はAr6と結合して環を形成していてもよく、その場合のR62は単結合又はアルキレン基を表す。
X6は、単結合、-COO-、又は-CONR64-を表す。R64は、水素原子又はアルキル基を表す。
L6は、単結合又はアルキレン基を表す。
Ar6は、(n+1)価の芳香族炭化水素基を表し、R62と結合して環を形成する場合には(n+2)価の芳香族炭化水素基を表す。
Y2は、n≧2の場合には各々独立に、水素原子又は酸の作用により脱離する基を表す。但し、Y2の少なくとも1つは、酸の作用により脱離する基を表す。Y2としての酸の作用により脱離する基は、式(Y1)~(Y4)であることが好ましい。
nは、1~4の整数を表す。
以下、繰り返し単位(a2)の具体例を示すが、本発明は、これに限定されない。
本発明の組成物が後述する架橋剤(G)を含有する場合、本発明の組成物はフェノール性水酸基を有するアルカリ可溶性樹脂(B)(以下、「樹脂(B)」ともいう)を含有することが好ましい。樹脂(B)は、フェノール性水酸基を有する繰り返し単位を有することが好ましい。
この場合、典型的には、ネガ型パターンが好適に形成される。
架橋剤(G)は、樹脂(B)に担持された形態であってもよい。
樹脂(B)は、前述した酸分解性基を有していてもよい。
R2は、水素原子、アルキル基(好ましくはメチル基)、又はハロゲン原子(好ましくはフッ素原子)を表す。
B’は、単結合又は2価の連結基を表す。
Ar’は、芳香環基を表す。
mは1以上の整数を表す。
樹脂(B)は、1種単独で使用してもよいし、2種以上を併用してもよい。
樹脂(B)としては、米国特許出願公開2016/0282720A1号明細書の段落<0142>~<0347>に開示された樹脂を好適に挙げられる。
但し、樹脂の製造に際しては、樹脂から組成物中に取り込まれる不純物(例えば、波長248nmに吸収を有する不純物、及び塩基性不純物等)をより低減するため、精製処理を充分に実施する必要がある。
上記不純物(特に波長248nmに吸収を有する不純物)を低減する精製方法としては、良溶媒に溶解した樹脂含有溶液と貧溶媒とを接触させて固形物を析出させる方法(沈殿精製)が挙げられる。沈殿精製を複数回繰り返すことが好ましい。
なお、上記良溶媒としては、樹脂と未反応モノマー等が溶解する溶媒であれば特に限定されない。また、上記貧溶媒としては、樹脂を析出させる溶媒であれば特に限定されない。
上記不純物(特に塩基性不純物)を低減する精製方法としては、希塩酸等の弱酸を含有する溶液を用いて樹脂を洗浄する方法、及び、水洗により塩基性不純物を除去する方法等が挙げられる。
本発明の組成物は、典型的には、光酸発生剤(以下、「光酸発生剤(C)」ともいう)を含有することが好ましい。
光酸発生剤は、活性光線又は放射線の照射により酸を発生する化合物である。
光酸発生剤としては、活性光線又は放射線の照射により有機酸を発生する化合物が好ましい。例えば、スルホニウム塩化合物、ヨードニウム塩化合物、ジアゾニウム塩化合物、ホスホニウム塩化合物、イミドスルホネート化合物、オキシムスルホネート化合物、ジアゾジスルホン化合物、ジスルホン化合物、及びo-ニトロベンジルスルホネート化合物が挙げられる。
R201、R202及びR203は、各々独立に、有機基を表す。
R201、R202及びR203としての有機基の炭素数は、一般的に1~30であり、好ましくは1~20である。
また、R201~R203のうち2つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、エステル結合、アミド結合、又はカルボニル基を含んでいてもよい。R201~R203の内の2つが結合して形成する基としては、アルキレン基(例えば、ブチレン基、ペンチレン基)及び-CH2-CH2-O-CH2-CH2-が挙げられる。
Z-は、アニオンを表す。
なお、光酸発生剤(C)は、一般式(ZI)で表される構造を複数有する化合物であってもよい。例えば、一般式(ZI)で表される化合物のR201~R203の少なくとも1つと、一般式(ZI)で表されるもうひとつの化合物のR201~R203の少なくとも一つとが、単結合又は連結基を介して結合した構造を有する化合物であってもよい。
化合物(ZI-1)は、上記一般式(ZI)のR201~R203の少なくとも1つがアリール基である、アリールスルホニウム化合物、すなわち、アリールスルホニウムをカチオンとする化合物である。
アリールスルホニウム化合物は、R201~R203の全てがアリール基でもよいし、R201~R203の一部がアリール基であり、残りがアルキル基又はシクロアルキル基であってもよい。
アリールスルホニウム化合物としては、例えば、トリアリールスルホニウム化合物、ジアリールアルキルスルホニウム化合物、アリールジアルキルスルホニウム化合物、ジアリールシクロアルキルスルホニウム化合物、及びアリールジシクロアルキルスルホニウム化合物が挙げられる。
アリールスルホニウム化合物が必要に応じて有しているアルキル基又はシクロアルキル基は、炭素数1~15の直鎖状アルキル基、炭素数3~15の分岐鎖状アルキル基、又は炭素数3~15のシクロアルキル基が好ましく、例えば、メチル基、エチル基、プロピル基、n-ブチル基、sec-ブチル基、t-ブチル基、シクロプロピル基、シクロブチル基、及びシクロヘキシル基等が挙げられる。
化合物(ZI-2)は、式(ZI)におけるR201~R203が、各々独立に、芳香環を有さない有機基を表す化合物である。ここで芳香環とは、ヘテロ原子を含む芳香族環も包含する。
R201~R203としての芳香環を有さない有機基は、一般的に炭素数1~30であり、炭素数1~20が好ましい。
R201~R203は、各々独立に、好ましくはアルキル基、シクロアルキル基、アリル基、又はビニル基であり、より好ましくは直鎖状又は分岐鎖状の2-オキソアルキル基、2-オキソシクロアルキル基、又はアルコキシカルボニルメチル基、さらに好ましくは直鎖状又は分岐鎖状の2-オキソアルキル基である。
R201~R203は、ハロゲン原子、アルコキシ基(例えば炭素数1~5)、水酸基、シアノ基、又はニトロ基によって更に置換されていてもよい。
化合物(ZI-3)は、下記一般式(ZI-3)で表され、フェナシルスルフォニウム塩構造を有する化合物である。
R1c~R5cは、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アルキルカルボニルオキシ基、シクロアルキルカルボニルオキシ基、ハロゲン原子、水酸基、ニトロ基、アルキルチオ基又はアリールチオ基を表す。
R6c及びR7cは、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアリール基を表す。
Rx及びRyは、各々独立に、アルキル基、シクロアルキル基、2-オキソアルキル基、2-オキソシクロアルキル基、アルコキシカルボニルアルキル基、アリル基又はビニル基を表す。
上記環構造としては、芳香族又は非芳香族の炭化水素環、芳香族又は非芳香族の複素環、及びこれらの環が2つ以上組み合わされてなる多環縮合環が挙げられる。環構造としては、3~10員環が挙げられ、4~8員環が好ましく、5又は6員環がより好ましい。
R5cとR6c、及びR5cとRxが結合して形成する基としては、単結合又はアルキレン基が好ましい。アルキレン基としては、メチレン基、及びエチレン基等が挙げられる。
Zc-は、アニオンを表す。
化合物(ZI-4)は、下記一般式(ZI-4)で表される。
lは0~2の整数を表す。
rは0~8の整数を表す。
R13は、水素原子、フッ素原子、水酸基、アルキル基、シクロアルキル基、アルコキシ基、アルコキシカルボニル基、又はシクロアルキル基を有する基を表す。これらの基は置換基を有してもよい。
R14は、水酸基、アルキル基、シクロアルキル基、アルコキシ基、アルコキシカルボニル基、アルキルカルボニル基、アルキルスルホニル基、シクロアルキルスルホニル基、又はシクロアルキル基を有する基を表す。これらの基は置換基を有してもよい。R14は、複数存在する場合は各々独立して、水酸基等の上記基を表す。
R15は、各々独立して、アルキル基、シクロアルキル基又はナフチル基を表す。これらの基は置換基を有してもよい。2つのR15が互いに結合して環を形成してもよい。2つのR15が互いに結合して環を形成するとき、環骨格内に、酸素原子、又は窒素原子等のヘテロ原子を含んでもよい。一態様において、2つのR15がアルキレン基であり、互いに結合して環構造を形成することが好ましい。
Z-は、アニオンを表す。
一般式(ZII)、及び(ZIII)中、R204~R207は、各々独立に、アリール基、アルキル基又はシクロアルキル基を表す。
R204~R207のアリール基としてはフェニル基、又はナフチル基が好ましく、フェニル基がより好ましい。R204~R207のアリール基は、酸素原子、窒素原子、又は硫黄原子等を有する複素環構造を有するアリール基であってもよい。複素環構造を有するアリール基の骨格としては、例えば、ピロール、フラン、チオフェン、インドール、ベンゾフラン、及びベンゾチオフェン等が挙げられる。
R204~R207のアルキル基及びシクロアルキル基としては、炭素数1~10の直鎖状アルキル基又は炭素数3~10の分岐鎖状アルキル基(例えば、メチル基、エチル基、プロピル基、ブチル基、及びペンチル基)、又は、炭素数3~10のシクロアルキル基(例えばシクロペンチル基、シクロヘキシル基、及びノルボルニル基)が好ましい。
Z-は、アニオンを表す。
oは、1~3の整数を表す。pは、0~10の整数を表す。qは、0~10の整数を表す。
Xfは、フッ素原子又は炭素数1~4のパーフルオロアルキル基であることが好ましく、フッ素原子又はCF3であることがより好ましい。特に、双方のXfがフッ素原子であることが更に好ましい。
R4及びR5で表されるアルキル基は、置換基を有していてもよく、炭素数1~4が好ましい。R4及びR5は、好ましくは水素原子である。
少なくとも一つのフッ素原子で置換されたアルキル基の具体例及び好適な態様は一般式(3)中のXfの具体例及び好適な態様と同じである。
2価の連結基としては、例えば、-COO-(-C(=O)-O-)、-OCO-、-CONH-、-NHCO-、-CO-、-O-、-S-、-SO-、-SO2-、アルキレン基(好ましくは炭素数1~6)、シクロアルキレン基(好ましくは炭素数3~15)、アルケニレン基(好ましくは炭素数2~6)及びこれらの複数を組み合わせた2価の連結基等が挙げられる。これらの中でも、-COO-、-OCO-、-CONH-、-NHCO-、-CO-、-O-、-SO2-、-COO-アルキレン基-、-OCO-アルキレン基-、-CONH-アルキレン基-又は-NHCO-アルキレン基-が好ましく、-COO-、-OCO-、-CONH-、-SO2-、-COO-アルキレン基-又は-OCO-アルキレン基-がより好ましい。
環状の有機基としては、例えば、脂環基、アリール基、及び複素環基が挙げられる。
脂環基は、単環式であってもよく、多環式であってもよい。単環式の脂環基としては、例えば、シクロペンチル基、シクロヘキシル基、及びシクロオクチル基等の単環のシクロアルキル基が挙げられる。多環式の脂環基としては、例えば、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の多環のシクロアルキル基が挙げられる。中でも、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の炭素数7以上の嵩高い構造を有する脂環基が好ましい。
複素環基は、単環式であってもよく、多環式であってもよい。多環式の方がより酸の拡散を抑制可能である。また、複素環基は、芳香族性を有していてもよいし、芳香族性を有していなくてもよい。芳香族性を有している複素環としては、例えば、フラン環、チオフェン環、ベンゾフラン環、ベンゾチオフェン環、ジベンゾフラン環、ジベンゾチオフェン環、及びピリジン環が挙げられる。芳香族性を有していない複素環としては、例えば、テトラヒドロピラン環、ラクトン環、スルトン環及びデカヒドロイソキノリン環が挙げられる。ラクトン環及びスルトン環の例としては、前述の樹脂において例示したラクトン構造及びスルトン構造が挙げられる。複素環基における複素環としては、フラン環、チオフェン環、ピリジン環、又はデカヒドロイソキノリン環が特に好ましい。
XB1及びXB2は、各々独立に、水素原子、又はフッ素原子を有さない1価の有機基を表す。XB1及びXB2は、水素原子であることが好ましい。
XB3及びXB4は、各々独立に、水素原子、又は1価の有機基を表す。XB3及びXB4の少なくとも一方がフッ素原子又はフッ素原子を有する1価の有機基であることが好ましく、XB3及びXB4の両方がフッ素原子又はフッ素原子を有する1価の有機基であることがより好ましい。XB3及びXB4の両方が、フッ素原子で置換されたアルキル基であることが更に好ましい。
L、q及びWは、一般式(3)と同様である。
Arは、アリール基を表し、スルホン酸アニオン及び-(D-B)基以外の置換基を更に有していてもよい。更に有してもよい置換基としては、フッ素原子及び水酸基等が挙げられる。
光酸発生剤は、低分子化合物の形態であることが好ましい。
光酸発生剤が、低分子化合物の形態である場合、分子量は3,000以下が好ましく、2,000以下がより好ましく、1,000以下が更に好ましい。
光酸発生剤が、重合体の一部に組み込まれた形態である場合、前述した樹脂(A)の一部に組み込まれてもよく、樹脂(A)とは異なる樹脂に組み込まれてもよい。
光酸発生剤は、1種単独で使用してもよいし、2種以上を併用してもよい。
本発明の組成物中、光酸発生剤の含有量(複数種存在する場合はその合計)は、組成物の全固形分を基準として、0.1~35質量%が好ましく、0.5~25質量%がより好ましく、1~20質量%が更に好ましく、1~15質量%が特に好ましい。
光酸発生剤として、上記一般式(ZI-3)又は(ZI-4)で表される化合物を含有する場合、組成物中に含まれる光酸発生剤の含有量(複数種存在する場合はその合計)は、組成物の全固形分を基準として、1~35質量%が好ましく、1~30質量%がより好ましい。
本発明の組成物は、酸拡散制御剤(D)を含有することが好ましい。酸拡散制御剤(D)は、露光時に光酸発生剤等から発生する酸をトラップし、余分な発生酸による、未露光部における酸分解性樹脂の反応を抑制するクエンチャーとして作用する。例えば、塩基性化合物(DA)、活性光線又は放射線の照射により塩基性が低下又は消失する塩基性化合物(DB)、酸発生剤に対して相対的に弱酸となるオニウム塩(DC)、窒素原子を有し、酸の作用により脱離する基を有する低分子化合物(DD)、又はカチオン部に窒素原子を有するオニウム塩化合物(DE)等を酸拡散制御剤として使用できる。本発明の組成物においては、公知の酸拡散制御剤を適宜使用できる。例えば、米国特許出願公開2016/0070167A1号明細書の段落<0627>~<0664>、米国特許出願公開2015/0004544A1号明細書の段落<0095>~<0187>、米国特許出願公開2016/0237190A1号明細書の段落<0403>~<0423>、及び、米国特許出願公開2016/0274458A1号明細書の段落<0259>~<0328>に開示された公知の化合物を酸拡散制御剤(D)として好適に使用できる。
R200、R201及びR202は、同一でも異なってもよく、各々独立に、水素原子、アルキル基(好ましくは炭素数1~20)、シクロアルキル基(好ましくは炭素数3~20)又はアリール基(炭素数6~20)を表す。R201とR202は、互いに結合して環を形成してもよい。
R203、R204、R205及びR206は、同一でも異なってもよく、各々独立に、炭素数1~20のアルキル基を表す。
上記アルキル基について、置換基を有するアルキル基としては、炭素数1~20のアミノアルキル基、炭素数1~20のヒドロキシアルキル基、又は炭素数1~20のシアノアルキル基が好ましい。
一般式(A)及び(E)中のアルキル基は、無置換であることがより好ましい。
プロトンアクセプター性は、pH測定を行うことによって確認することができる。
光酸発生剤と、光酸発生剤から生じた酸に対して相対的に弱酸である酸を発生するオニウム塩とを混合して用いた場合、活性光線性又は放射線の照射により光酸発生剤から生じた酸が未反応の弱酸アニオンを有するオニウム塩と衝突すると、塩交換により弱酸を放出して強酸アニオンを有するオニウム塩を生じる。この過程で強酸がより触媒能の低い弱酸に交換されるため、見かけ上、酸が失活して酸拡散の制御を行うことができる。
化合物(DCA)としては、下記一般式(C-1)~(C-3)のいずれかで表される化合物が好ましい。
R1、R2、及びR3は、各々独立に炭素数1以上の置換基を表す。
L1は、カチオン部位とアニオン部位とを連結する2価の連結基又は単結合を表す。
-X-は、-COO-、-SO3 -、-SO2 -、及び-N--R4から選択されるアニオン部位を表す。R4は、隣接するN原子との連結部位に、カルボニル基(-C(=O)-)、スルホニル基(-S(=O)2-)、及びスルフィニル基(-S(=O)-)のうち少なくとも1つを有する1価の置換基を表す。
R1、R2、R3、R4、及びL1は、互いに結合して環構造を形成してもよい。また、一般式(C-3)において、R1~R3のうち2つを合わせて1つの2価の置換基を表し、N原子と2重結合により結合していてもよい。
酸の作用により脱離する基としては、アセタール基、カルボネート基、カルバメート基、3級エステル基、3級水酸基、又はヘミアミナールエーテル基が好ましく、カルバメート基、又はヘミアミナールエーテル基がより好ましい。
化合物(DD)の分子量は、100~1000が好ましく、100~700がより好ましく、100~500が更に好ましい。
化合物(DD)は、窒素原子上に保護基を有するカルバメート基を有してもよい。カルバメート基を構成する保護基としては、下記一般式(d-1)で表される。
Rbは、各々独立に、水素原子、アルキル基(好ましくは炭素数1~10)、シクロアルキル基(好ましくは炭素数3~30)、アリール基(好ましくは炭素数3~30)、アラルキル基(好ましくは炭素数1~10)、又はアルコキシアルキル基(好ましくは炭素数1~10)を表す。Rbは相互に連結して環を形成していてもよい。
Rbが示すアルキル基、シクロアルキル基、アリール基、及びアラルキル基は、各々独立にヒドロキシル基、シアノ基、アミノ基、ピロリジノ基、ピペリジノ基、モルホリノ基、オキソ基等の官能基、アルコキシ基、又はハロゲン原子で置換されていてもよい。Rbが示すアルコキシアルキル基についても同様である。
2つのRbが相互に連結して形成する環としては、脂環式炭化水素、芳香族炭化水素、複素環式炭化水素及びその誘導体等が挙げられる。
一般式(d-1)で表される基の具体的な構造としては、米国特許公報US2012/0135348A1号明細書の段落<0466>に開示された構造が挙げられるが、これに限定されない。
lは0~2の整数を表し、mは1~3の整数を表し、l+m=3を満たす。
Raは、水素原子、アルキル基、シクロアルキル基、アリール基又はアラルキル基を表す。lが2のとき、2つのRaは同じでも異なっていてもよく、2つのRaは相互に連結して式中の窒素原子と共に複素環を形成していてもよい。この複素環には式中の窒素原子以外のヘテロ原子を含んでいてもよい。
Rbは、上記一般式(d-1)におけるRbと同義であり、好ましい例も同様である。
一般式(6)において、Raとしてのアルキル基、シクロアルキル基、アリール基、及びアラルキル基は、各々独立にRbとしてのアルキル基、シクロアルキル基、アリール基、及びアラルキル基が置換されていてもよい基として前述した基と同様な基で置換されていてもよい。
本発明における特に好ましい化合物(DD)の具体例としては、米国特許出願公開2012/0135348A1号明細書の段落<0475>に開示された化合物が挙げられるが、これに限定されない。
化合物(DE)の好ましい具体例としては、米国特許出願公開2015/0309408A1号明細書の段落<0203>に開示された化合物が挙げられるが、これに限定されない。
酸拡散制御剤(D)の組成物中の含有量(複数種存在する場合はその合計)は、組成物の全固形分を基準として、0.1~10質量%が好ましく、0.1~5質量%がより好ましい。
本発明の組成物は、疎水性樹脂(E)を含有することが好ましい。なお、疎水性樹脂(E)は、樹脂(A)及び樹脂(B)とは異なる樹脂であることが好ましい。
本発明の組成物が、疎水性樹脂(E)を含有することにより、感活性光線性又は感放射線性膜の表面における静的/動的な接触角を制御できる。これにより、現像特性の改善、アウトガスの抑制、液浸露光における液浸液追随性の向上、及び液浸欠陥の低減等が可能となる。
疎水性樹脂(E)は、レジスト膜の表面に偏在するように設計されることが好ましいが、界面活性剤とは異なり、必ずしも分子内に親水基を有する必要はなく、極性/非極性物質を均一に混合することに寄与しなくてもよい。
疎水性樹脂(E)が、フッ素原子及び/又はケイ素原子を含む場合、疎水性樹脂(E)における上記フッ素原子及び/又はケイ素原子は、樹脂の主鎖中に含まれていてもよく、側鎖中に含まれていてもよい。
(x)酸基
(y)アルカリ現像液の作用により分解してアルカリ現像液に対する溶解度が増大する基(以下、極性変換基ともいう)
(z)酸の作用により分解する基
酸基としては、フッ素化アルコール基(好ましくはヘキサフルオロイソプロパノール)、スルホンイミド基、又はビス(アルキルカルボニル)メチレン基が好ましい。
これらの基を含んだ繰り返し単位としては、例えば、樹脂の主鎖にこれらの基が直接結合している繰り返し単位であり、例えば、アクリル酸エステル及びメタクリル酸エステルによる繰り返し単位等が挙げられる。この繰り返し単位は、これらの基が連結基を介して樹脂の主鎖に結合していてもよい。又は、この繰り返し単位は、これらの基を有する重合開始剤又は連鎖移動剤を重合時に用いて、樹脂の末端に導入されていてもよい。
ラクトン基を有する繰り返し単位としては、例えば、先に樹脂(A)の項で説明したラクトン構造を有する繰り返し単位と同様のものが挙げられる。
疎水性樹脂(E)は、更に、上述した繰り返し単位とは別の繰り返し単位を有していてもよい。
表面エネルギーが異なる2種以上の疎水性樹脂(E)を混合して使用することが、液浸露光における液浸液追随性と現像特性の両立の観点から好ましい。
疎水性樹脂(E)の組成物中の含有量は、本発明の組成物中の全固形分に対し、0.01~10質量%が好ましく、0.05~8質量%がより好ましい。
本発明の組成物は、溶剤を含有することが好ましい。
本発明の組成物においては、公知のレジスト溶剤を適宜使用できる。例えば、米国特許出願公開2016/0070167A1号明細書の段落<0665>~<0670>、米国特許出願公開2015/0004544A1号明細書の段落<0210>~<0235>、米国特許出願公開2016/0237190A1号明細書の段落<0424>~<0426>、及び、米国特許出願公開2016/0274458A1号明細書の段落<0357>~<0366>に開示された公知の溶剤を好適に使用できる。
組成物を調製する際に使用できる溶剤としては、例えば、アルキレングリコールモノアルキルエーテルカルボキシレート、アルキレングリコールモノアルキルエーテル、乳酸アルキルエステル、アルコキシプロピオン酸アルキル、環状ラクトン(好ましくは炭素数4~10)、環を有してもよいモノケトン化合物(好ましくは炭素数4~10)、アルキレンカーボネート、アルコキシ酢酸アルキル、及びピルビン酸アルキル等の有機溶剤が挙げられる。
水酸基を有する溶剤、及び水酸基を有さない溶剤としては、前述の例示化合物を適宜選択できるが、水酸基を含む溶剤としては、アルキレングリコールモノアルキルエーテル、又は乳酸アルキル等が好ましく、プロピレングリコールモノメチルエーテル(PGME)、プロピレングリコールモノエチルエーテル(PGEE)、2-ヒドロキシイソ酪酸メチル、又は乳酸エチルがより好ましい。また、水酸基を有さない溶剤としては、アルキレングリコールモノアルキルエーテルアセテート、アルキルアルコキシプロピオネート、環を有していてもよいモノケトン化合物、環状ラクトン、又は酢酸アルキル等が好ましく、これらの中でも、プロピレングリコールモノメチルエーテルアセテート(PGMEA)、エチルエトキシプロピオネート、2-ヘプタノン、γ-ブチロラクトン、シクロヘキサノン、シクロペンタノン又は酢酸ブチルがより好ましく、プロピレングリコールモノメチルエーテルアセテート、γ-ブチロラクトン、エチルエトキシプロピオネート、シクロヘキサノン、シクロペンタノン又は2-ヘプタノンが更に好ましい。水酸基を有さない溶剤としては、プロピレンカーボネートも好ましい。
水酸基を有する溶剤と水酸基を有さない溶剤との混合比(質量比)は、1/99~99/1が好ましく、10/90~90/10がより好ましく、20/80~60/40がさらに好ましい。水酸基を有さない溶剤を50質量%以上含有する混合溶剤が、塗布均一性の点で好ましい。
溶剤は、プロピレングリコールモノメチルエーテルアセテートを含有することが好ましく、プロピレングリコールモノメチルエーテルアセテート単独溶剤でもよいし、プロピレングリコールモノメチルエーテルアセテートを含有する2種類以上の混合溶剤でもよい。
本発明の組成物は、酸の作用により樹脂を架橋する化合物(以下、架橋剤(G)ともいう)を含有してもよい。架橋剤(G)としては、公知の化合物を適宜に使用することができる。例えば、米国特許出願公開2016/0147154A1号明細書の段落<0379>~<0431>、及び、米国特許出願公開2016/0282720A1号明細書の段落<0064>~<0141>に開示された公知の化合物を架橋剤(G)として好適に使用できる。
架橋剤(G)は、樹脂を架橋しうる架橋性基を有している化合物であり、架橋性基としては、ヒドロキシメチル基、アルコキシメチル基、アシルオキシメチル基、アルコキシメチルエーテル基、オキシラン環、及びオキセタン環等が挙げられる。
架橋性基は、ヒドロキシメチル基、アルコキシメチル基、オキシラン環又はオキセタン環であることが好ましい。
架橋剤(G)は、架橋性基を2個以上有する化合物(樹脂も含む)であることが好ましい。
架橋剤(G)は、ヒドロキシメチル基又はアルコキシメチル基を有する、フェノール誘導体、ウレア系化合物(ウレア構造を有する化合物)又はメラミン系化合物(メラミン構造を有する化合物)であることがより好ましい。
架橋剤は1種単独で用いてもよく、2種以上を併用してもよい。
架橋剤(G)の含有量は、レジスト組成物の全固形分に対して、1~50質量%が好ましく、3~40質量%が好ましく、5~30質量%が更に好ましい。
本発明の組成物は、界面活性剤を含有することが好ましい界面活性剤を含有する場合、フッ素系及び/又はシリコン系界面活性剤(具体的には、フッ素系界面活性剤、シリコン系界面活性剤、又はフッ素原子とケイ素原子との両方を有する界面活性剤)が好ましい。
フッ素系及び/又はシリコン系界面活性剤として、米国特許出願公開第2008/0248425号明細書の段落<0276>に記載の界面活性剤が挙げられる。
また、米国特許出願公開第2008/0248425号明細書の段落<0280>に記載の、フッ素系及び/又はシリコン系界面活性剤以外の他の界面活性剤を使用することもできる。
本発明の組成物が界面活性剤を含有する場合、界面活性剤の含有量は、組成物の全固形分に対して、0.0001~2質量%が好ましく、0.0005~1質量%がより好ましい。
一方、界面活性剤の含有量が、組成物の全固形分に対して10ppm以上とすることにより、疎水性樹脂(E)の表面偏在性が上がる。それにより、感活性光線性又は感放射線性膜の表面をより疎水的にすることができ、液浸露光時の水追随性が向上する。
本発明の組成物は、更に、酸増殖剤、染料、可塑剤、光増感剤、光吸収剤、アルカリ可溶性樹脂、溶解阻止剤、又は溶解促進剤等を含有してもよい。
本発明の組成物の固形分濃度は、通常1.0~50質量%であることが好ましく、10~50質量%がより好ましく、30~50質量%が更に好ましい。固形分濃度とは、組成物の総質量に対する、溶剤を除く他のレジスト成分の質量の質量百分率である。
なお、後述するように、本発明の組成物からパターンを形成することができる。
形成されるパターンの膜厚は、1μm以上であり、加工段数を増やす目的として、3μm以上が好ましく、5μm以上がより好ましく、10μm以上が更に好ましい。上限は特に限定されず、例えば100μm以下である。
なお、粘度は、E型粘度計により測定することができる。
本発明の組成物は、活性光線又は放射線の照射により反応して性質が変化する感活性光線性又は感放射線性樹脂組成物に関する。更に詳しくは、本発明の組成物は、IC(Integrated Circuit)等の半導体製造工程、液晶若しくはサーマルヘッド等の回路基板の製造、インプリント用モールド構造体の作製、その他のフォトファブリケーション工程、又は平版印刷版、若しくは酸硬化性組成物の製造に使用される感活性光線性又は感放射線性樹脂組成物に関する。本発明において形成されるパターンは、エッチング工程、イオンインプランテーション工程、バンプ電極形成工程、再配線形成工程、及びMEMS(Micro Electro Mechanical Systems)等において使用できる。
本発明は上記感活性光線性又は感放射線性樹脂組成物を用いたパターン形成方法にも関する。以下、本発明のパターン形成方法について説明する。また、パターン形成方法の説明と併せて、本発明の感活性光線性又は感放射線性膜についても説明する。
(i)上述した感活性光線性又は感放射線性樹脂組成物によってレジスト膜(感活性光線性又は感放射線性膜)を支持体上に形成する工程(レジスト膜形成工程)、
(ii)上記レジスト膜を露光する(活性光線又は放射線を照射する)工程(露光工程)、及び、
(iii)上記露光されたレジスト膜を、現像液を用いて現像する工程(現像工程)、
を有する。
本発明のパターン形成方法は、(ii)露光工程における露光方法が、液浸露光であってもよい。
本発明のパターン形成方法は、(ii)露光工程の前に、(iv)前加熱(PB:PreBake)工程を含むことが好ましい。
本発明のパターン形成方法は、(ii)露光工程の後、かつ、(iii)現像工程の前に、(v)露光後加熱(PEB:Post Exposure Bake)工程を含むことが好ましい。
本発明のパターン形成方法は、(ii)露光工程を、複数回含んでいてもよい。
本発明のパターン形成方法は、(iv)前加熱工程を、複数回含んでいてもよい。
本発明のパターン形成方法は、(v)露光後加熱工程を、複数回含んでいてもよい。
また、必要に応じて、レジスト膜と支持体との間にレジスト下層膜(例えば、SOG(Spin On Glass)、SOC(Spin On Carbon)、及び、反射防止膜)を形成してもよい。レジスト下層膜を構成する材料としては、公知の有機系又は無機系の材料を適宜用いることができる。
レジスト膜の上層に、保護膜(トップコート)を形成してもよい。保護膜としては、公知の材料を適宜用いることができる。例えば、米国特許出願公開第2007/0178407号明細書、米国特許出願公開第2008/0085466号明細書、米国特許出願公開第2007/0275326号明細書、米国特許出願公開第2016/0299432号明細書、米国特許出願公開第2013/0244438号明細書、国際特許出願公開第2016/157988A号明細書に開示された保護膜形成用組成物を好適に使用することができる。保護膜形成用組成物としては、上述した酸拡散制御剤を含有するものが好ましい。
上述した疎水性樹脂を含有するレジスト膜の上層に保護膜を形成してもよい。
加熱時間は、(iv)前加熱工程及び(v)露光後加熱工程のいずれにおいても、30~300秒が好ましく、30~180秒がより好ましく、30~90秒が更に好ましい。
加熱は、露光装置及び現像装置に備わっている手段で行うことができ、ホットプレート等を用いて行ってもよい。
更に、上記アルカリ現像液は、アルコール類、及び/又は界面活性剤を適当量含有していてもよい。アルカリ現像液のアルカリ濃度は、通常0.1~20質量%である。アルカリ現像液のpHは、通常10~15である。
アルカリ現像液を用いて現像を行う時間は、通常10~300秒である。
アルカリ現像液のアルカリ濃度、pH、及び現像時間は、形成するパターンに応じて、適宜調整できる。
有機系現像液に対する有機溶剤の含有量は、現像液の全量に対して、50~100質量%が好ましく、80~100質量%がより好ましく、90~100質量%が更に好ましく、95~100質量%が特に好ましい。
炭化水素系溶剤、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤、及びエーテル系溶剤の具体例としては、有機溶剤を含有する現像液において説明したものと同様のものが挙げられる。
この場合のリンス工程に用いるリンス液としては、1価アルコールを含有するリンス液がより好ましい。
リンス液中の含水率は、10質量%以下が好ましく、5質量%以下がより好ましく、3質量%以下が更に好ましい。含水率を10質量%以下とすることで、良好な現像特性が得られる。
リンス工程においては、有機系現像液を用いる現像を行った基板を、有機溶剤を含有するリンス液を用いて洗浄処理する。洗浄処理の方法は特に限定されず、例えば、一定速度で回転している基板上にリンス液を吐出しつづける方法(回転塗布法)、リンス液が満たされた槽中に基板を一定時間浸漬する方法(ディップ法)、又は基板表面にリンス液を噴霧する方法(スプレー法)等が挙げられる。中でも、回転塗布法で洗浄処理を行い、洗浄後に基板を2,000~4,000rpm(revolution per minute)の回転数で回転させ、リンス液を基板上から除去することが好ましい。また、リンス工程の後に加熱工程(Post Bake)を含むことも好ましい。この加熱工程によりパターン間及びパターン内部に残留した現像液及びリンス液が除去される。リンス工程の後の加熱工程において、加熱温度は通常40~160℃であり、70~95℃が好ましく、加熱時間は通常10秒~3分であり、30秒~90秒が好ましい。
フィルター濾過のほか、吸着材による不純物の除去を行ってもよく、フィルター濾過と吸着材を組み合わせて使用してもよい。吸着材としては、公知の吸着材を用いることができ、例えば、シリカゲル若しくはゼオライト等の無機系吸着材、又は活性炭等の有機系吸着材を使用できる。金属吸着剤としては、例えば、日本国特許出願公開第2016-206500号明細書(特開2016-206500号公報)に開示されるものが挙げられる。
また、上記各種材料に含まれる金属等の不純物を低減する方法としては、各種材料を構成する原料として金属含有量が少ない原料を選択する、各種材料を構成する原料に対してフィルター濾過を行う、又は装置内をテフロン(登録商標)でライニングする等してコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法が挙げられる。各種材料を構成する原料に対して行うフィルター濾過における好ましい条件は、上記した条件と同様である。
また、上記の方法によって形成されたパターンは、例えば日本国特許出願公開第1991-270227号明細書(特開平3-270227号公報)及び米国特許出願公開第2013/0209941号明細書に開示されたスペーサープロセスの芯材(Core)として使用できる。
また、本発明は、上記したパターン形成方法を含む、電子デバイスの製造方法にも関する。本発明の電子デバイスの製造方法により製造された電子デバイスは、電気電子機器(例えば、家電、OA(Office Automation)関連機器、メディア関連機器、光学用機器、及び通信機器等)に、好適に搭載される。
以下の手順により、各種樹脂を合成した。
<樹脂1Aの合成>
樹脂1Aは、下記の方法(以下、「PACST法」ともいう。)により合成した。
得られたポリマー溶液1A-1を5L三口フラスコへ移し、そこにプロピレングリコールモノメチルエーテル300g、メタノール600g、純水35g、及びトリエチルアミン149.96gを入れ、80℃に設定した油浴に付けて12時間反応させた。1H-NMR(nuclear magnetic resonance)よりアセチル基保護が外れている事を確認し、反応液を室温まで冷却した。反応液を分液ロートへ移し、そこに酢酸エチルと希塩酸を入れ抽出操作を3回繰り返した(塩基性不純物除去)。続いて純水で3回ほど有機層を洗浄した後、エバポレーションにて濃縮した粘性の液体にヘプタンを投入して固体を析出させた(1回目の沈殿精製)。上澄み液をデカンテーションして得られた粉体を酢酸エチルに溶解し、その酢酸エチル溶液をヘプタン中へゆっくりと滴下して沈殿精製を行った(2回目の沈殿精製)。析出した粉体をろ過後、ヘプタンで掛け洗いし、40℃で減圧乾燥した。目的の樹脂1Aが得られたことは1H-NMR及びGPCにて確認した。
樹脂1Bは、下記の方法(以下、「PHS法」ともいう。)により合成した。
温度計、ガス吹込み管、冷却管、攪拌装置及び水浴を備えた四つ口フラスコにプロピレングリコールモノメチルエーテルアセテート(PGMEA)を60g入れ、窒素置換後80℃まで昇温した。そこにパラヒドロキシスチレン276.35g、メタクリル酸t-ブチル(和光純薬製)67.55g、メタクリル酸ベンジル(和光純薬製)33.48g、及び、V-601(重合開始剤、和光純薬製)13.12gを241.1gのPGMEAに溶解した混合溶液を4時間かけて滴下した。滴下後、80℃で3時間撹拌させた反応溶液を分液ロートへ移し、そこに酢酸エチルと希塩酸を入れ抽出操作を3回繰り返した(塩基性不純物除去)。続いて純水で3回ほど有機層を洗浄した後、エバポレーションにて濃縮した粘性の液体にヘプタンを投入して固体を析出させた(1回目の沈殿精製)。上澄み液をデカンテーションして得られた粉体を酢酸エチルに溶解し、その酢酸エチル溶液をヘプタン中へゆっくりと滴下して沈殿精製を行った(2回目の沈殿精製)。析出した粉体をろ過後、ヘプタンで掛け洗いし、40℃で減圧乾燥した。目的の樹脂1Aが得られたことは1H-NMR及びGPCにて確認した。
上述の樹脂1A(PACST法)の合成方法において、モノマー種をかえた以外は同様の方法により、下記構造の樹脂2Aを合成した。目的の樹脂2Aが得られたことは1H-NMR及びGPCにて確認した。
上述の樹脂1B(PHS法)の合成方法において、モノマー種をかえた以外は同様の方法により、下記構造の樹脂2Bを合成した。目的の樹脂2Bが得られたことは1H-NMR及びGPCにて確認した。
上述の樹脂1A(PACST法)の合成方法において、モノマー種をかえた以外は同様の方法により、下記構造の樹脂3Aを合成した。目的の樹脂3Aが得られたことは1H-NMR及びGPCにて確認した。
上述の樹脂1B(PHS法)の合成方法において、モノマー種をかえた以外は同様の方法により、下記構造の樹脂3Bを合成した。目的の樹脂3Bが得られたことは1H-NMR及びGPCにて確認した。
樹脂4は、下記の方法(高分子反応)により合成した。
温度計、ガス吹込み管、冷却管、攪拌装置及び水浴を備えた四つ口フラスコにパラヒドロキシスチレン210gと45gのt-ブチルビニルエーテルを1000mLの脱水テトラヒドロフラン(THF)に溶解し、そこへ脱水パラトルエンスルホン酸1gを加え、更に脱水剤としてモレキュラーシーブ3Aを30g添加し、室温にて4時間撹拌した。反応液をろ過した後、ろ液を水3リットルに投入し(塩基性不純物除去)、析出した粉体をろ取した(1回目の沈殿精製)。得られた粉体は室温で減圧乾燥した後に2リットルの酢酸エチルに溶解させ、50Lのヘプタンへと滴下し、沈殿精製した(2回目の沈殿精製)。目的の樹脂4が得られたことは1H-NMR及びGPCにて確認した。
上述の樹脂1B(PHS法)の合成方法において、モノマー種をかえた以外は同様の方法により、下記構造の樹脂5を合成した。目的の樹脂5が得られたことは1H-NMR及びGPCにて確認した。
上述の樹脂1A(PACST法)の合成方法において、沈殿精製を1回とした以外は同様の方法により、樹脂1A’を合成した。
上述の樹脂3B(PHS法)の合成方法において、塩基性不純物除去を実施せず、沈殿精製を1回とした以外は同様の方法により、樹脂3B’を合成した。
上述の樹脂2A(PACST法)の合成方法において、塩基性不純物除去を実施しなかった以外は同様の方法により、樹脂2A’を合成した。
上述の樹脂4(高分子反応)の合成方法において、塩基性不純物除去を実施しなかった以外は同様の方法により、樹脂4を合成した。
なお、上記樹脂1A’、樹脂2A’、樹脂3B’、及び、樹脂4’は、それぞれ、樹脂1A、樹脂2A、樹脂3B、及び、樹脂4と同程度の繰り返し単位のモル比率、Mw、及び、Mw/Mnを示した。
以下に、第2表に示す感活性光線性又は感放射線性樹脂組成物に含まれる各種成分を示す。
第2表に示される樹脂として、上段で合成した樹脂を用いた。
第2表に示される光酸発生剤の構造を以下に示す。
第2表に示される酸拡散制御剤の構造を以下に示す。
第2表に示される界面活性剤を以下に示す。
W-1:下記構造のものを用いた。
第2表に示される溶剤を以下に示す。
PGME:プロピレングリコールモノメチルエーテル
PGMEA:プロピレングリコールモノメチルエーテルアセテート
第2表に示した各成分を、後述するパターン形成後の膜厚が11μmとなるように固形分を調整して混合した。次いで、得られた混合液を、最初に孔径50nmのポリエチレン製フィルター、次に孔径10nmのナイロン製フィルター、最後に孔径5nmのポリエチレン製フィルターの順番で濾過することにより、感活性光線性又は感放射線性樹脂組成物(以下、樹脂組成物ともいう)を調液した。なお、樹脂組成物において、固形分とは、溶剤以外の全ての成分を意味する。得られた樹脂組成物を、実施例及び比較例で使用した。
なお、各組成物に含まれる25種(Na、K、Ca、Fe、Cu、Mg、Mn、Al、Li、Cr、Ni、Sn、Zn、Ag、As、Au、Ba、Cd、Co、Pb、Ti、V、W、Mo、Zr)の金属不純物成分量をAgilent Technologies社製ICP-MS装置(誘導結合プラズマ質量分析計)「Agilent 7500cs」にて測定したところ、各金属種の含有量はそれぞれ10ppb未満であった。
感活性光線性又は感放射線性樹脂組成物が含有する波長248nmに吸収を有する不純物の種類及び含有量(質量%)を測定した。実施例1~実施例8、及び比較例1~4の感活性光線性又は感放射線性樹脂組成物では、それぞれ第2表中の「波長248nmに吸収を有する不純物」欄に示す化合物a~eが観測された。化合物a~eの構造と含有量は、液体クロマトグラフィーにより同定した。
なお、化合物a~eは、それぞれ、パラヒドロキシスチレン及びその変性物(化合物a、c)、パラアセトキシスチレン及びその変性物(化合物b、d)、並びに4-(tert-ブトキシ)スチレン(化合物e)であり、いずれも樹脂の原料成分由来であると推測された。
以下に化合物a~eの具体的な構造を示す。
感活性光線性又は感放射線性樹脂組成物が含有する塩基性不純物の種類及び含有量(質量%)を測定した。実施例1~実施例8、及び比較例1~4の感活性光線性又は感放射線性樹脂組成物では、それぞれ第2表中の「塩基性不純物」欄に示す化合物x及びzが観測された。化合物x及びzの構造と含有量は、キャピラリー電気泳動法により同定した。
なお、化合物x及びzは、それぞれ、トリエチルアミン及び水酸化ナトリウムであり、いずれも樹脂の脱保護時に使用する塩基性化合物に由来するものと推測された。
なお、表中、各成分の含有量は、固形分全量に対する含有量(質量%)に相当する。
<パターン形成:KrF露光、アルカリ現像>
東京エレクトロン製スピンコーターACT-8を利用して、ヘキサメチルジシラザン処理を施したSi基板(Advanced Materials Technology社製)上に、反射防止層を設けることなく、上記で調製した樹脂組成物を基板が静止した状態で滴下した。滴下した後、基板を回転し、その回転数を、3秒間500rpmで維持し、その後2秒間100rpmで維持し、さらに3秒間500rpmで維持し、再び2秒間100rpmで維持した後、膜厚設定回転数(1200rpm)に上げて60秒間維持した。その後、ホットプレート上で130℃にて60秒間加熱乾燥を行い、膜厚11μmのポジ型レジスト膜を形成した。このレジスト膜に対し、縮小投影露光及び現像後に形成されるパターンのスペース幅が5μm、ピッチ幅が25μmとなるような、ラインアンドスペースパターンを有するマスクを介して、KrFエキシマレーザースキャナー(ASML製、PAS5500/850C、波長248nm)を用いて、NA=0.60、σ=0.75の露光条件でパターン露光した。照射後に120℃にて60秒間ベークし、2.38質量%テトラメチルアンモニウムハイドロオキサイド(TMAH)水溶液を用いて60秒間浸漬した。その後、30秒間、純水でリンスして乾燥して、スペース幅が5μm、ピッチ幅が25μmの孤立スペースパターンを形成した。
上記パターン露光は、縮小投影露光後のスペース幅が5μm、ピッチ幅が25μmとなるような、ラインアンドスペースパターンを有するマスクを介する露光であり、露光量は、スペース幅が5μm、ピッチ幅が25μmの孤立スペースパターンを形成する最適露光量(感度)(mJ/cm2)とした。上記感度の決定において、パターンのスペース幅の測定は走査型電子顕微鏡(SEM(Scanning Electron Microscope))(株式会社日立ハイテクノロジーズ製9380II)を用いた。
以下に示す方法にて、得られたパターンの評価を行った。
現像後のウェーハの断面SEMの結果より、基板まで解像できていないものはN、基板まで解像できているがパターンの直線性が悪いものをB、パターンの直線性が良いものをAとして評価した。判定の例を図1~図3に示す。図1は、判定がNの例であり、図2は、判定がBの例であり、図3は、判定がAの例である。
評価結果を第3表に示す。
一方、比較例1~4の感活性光線性又は感放射線性樹脂組成物を用いた場合には、波長248nmに吸収を有する不純物及び塩基性不純物の影響により、基板まで解像できていないことが確認された。
Claims (11)
- 膜厚が1μm以上のパターンの形成に用いられる感活性光線性又は感放射線性樹脂組成物であって、
樹脂を含有し、
波長248nmに吸収を有する不純物の含有量が、前記樹脂に対して1.00質量%以下である、感活性光線性又は感放射線性樹脂組成物。 - 前記樹脂が、酸の作用により分解して極性が増大する基を有する繰り返し単位を含有する、請求項1に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記樹脂が、フェノール性水酸基を有する繰り返し単位を含有する、請求項1又は2に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記不純物が、芳香族化合物である、請求項1~3のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記樹脂が、一般式(I)で表される繰り返し単位を含有し、
前記不純物が、一般式(X)で表される化合物である、請求項1~4のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物。
R41、R42及びR43は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。但し、R42はAr4と結合して環を形成していてもよく、その場合のR42は単結合又はアルキレン基を表す。
X4は、単結合、-COO-、又は-CONR64-を表し、R64は、水素原子又はアルキル基を表す。
L4は、単結合又は2価の連結基を表す。
Ar4は、(n+1)価の芳香族炭化水素基を表し、R42と結合して環を形成する場合には(n+2)価の芳香族炭化水素基を表す。
nは、1~5の整数を表す。
Raは、一般式(Y1)で表される基、又は、一般式(Y2)で表される基を表す。
R44は、アルキル基を表す。
Rbは、水素原子、又は、保護基を表す。*は結合位置を表す。 - 前記樹脂が塩基性化合物の存在下で合成された樹脂であり、
前記塩基性化合物に由来する塩基性不純物の含有量が、前記樹脂に対して0.10質量%以下である、請求項5に記載の感活性光線性又は感放射線性樹脂組成物。 - 更に、光酸発生剤を含有する、請求項1~6のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物。
- 粘度が100~500mPa・sである、請求項1~7のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物。
- 請求項1~8のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物により形成されたレジスト膜。
- 請求項1~8のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物を用いて膜厚が1μm以上のレジスト膜を形成するレジスト膜形成工程と、
前記レジスト膜を露光する露光工程と、
露光された前記レジスト膜を、現像液を用いて現像する現像工程と、
を含むパターン形成方法。 - 請求項10に記載のパターン形成方法を含む、電子デバイスの製造方法。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004310121A (ja) * | 2004-05-14 | 2004-11-04 | Jsr Corp | 化学増幅型感放射線性樹脂組成物 |
JP2006276759A (ja) * | 2005-03-30 | 2006-10-12 | Fuji Photo Film Co Ltd | Euv露光用ポジ型レジスト組成物及びそれを用いたパターン形成方法 |
JP2009102659A (ja) * | 2004-04-30 | 2009-05-14 | Maruzen Petrochem Co Ltd | 半導体リソグラフィー用共重合体とその製造方法、および組成物 |
JP2010181729A (ja) * | 2009-02-06 | 2010-08-19 | Fujifilm Corp | 感活性光線性または感放射線性樹脂組成物及びそれを用いたパターン形成方法 |
JP2015057638A (ja) * | 2013-08-13 | 2015-03-26 | Jsr株式会社 | レジストパターン形成方法、基板の加工方法及びフォトレジスト組成物 |
JP2016133743A (ja) * | 2015-01-21 | 2016-07-25 | Jsr株式会社 | レジストパターン形成方法及び基板の加工方法 |
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JP5954253B2 (ja) * | 2012-05-16 | 2016-07-20 | 信越化学工業株式会社 | レジスト材料、これを用いたパターン形成方法、及び高分子化合物 |
JP6002705B2 (ja) * | 2013-03-01 | 2016-10-05 | 富士フイルム株式会社 | パターン形成方法、感活性光線性又は感放射線性樹脂組成物、レジスト膜、及び、電子デバイスの製造方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009102659A (ja) * | 2004-04-30 | 2009-05-14 | Maruzen Petrochem Co Ltd | 半導体リソグラフィー用共重合体とその製造方法、および組成物 |
JP2004310121A (ja) * | 2004-05-14 | 2004-11-04 | Jsr Corp | 化学増幅型感放射線性樹脂組成物 |
JP2006276759A (ja) * | 2005-03-30 | 2006-10-12 | Fuji Photo Film Co Ltd | Euv露光用ポジ型レジスト組成物及びそれを用いたパターン形成方法 |
JP2010181729A (ja) * | 2009-02-06 | 2010-08-19 | Fujifilm Corp | 感活性光線性または感放射線性樹脂組成物及びそれを用いたパターン形成方法 |
JP2015057638A (ja) * | 2013-08-13 | 2015-03-26 | Jsr株式会社 | レジストパターン形成方法、基板の加工方法及びフォトレジスト組成物 |
JP2016133743A (ja) * | 2015-01-21 | 2016-07-25 | Jsr株式会社 | レジストパターン形成方法及び基板の加工方法 |
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WO2019054311A1 (ja) * | 2017-09-13 | 2019-03-21 | 富士フイルム株式会社 | 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、及び電子デバイスの製造方法 |
US11687001B2 (en) | 2017-09-13 | 2023-06-27 | Fujifilm Corporation | Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and method for manufacturing electronic device |
US11835849B2 (en) | 2017-09-13 | 2023-12-05 | Fujifilm Corporation | Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and method for manufacturing electronic device |
CN113166327A (zh) * | 2018-11-22 | 2021-07-23 | 富士胶片株式会社 | 感光化射线性或感放射线性树脂组合物、抗蚀剂膜、图案形成方法及电子器件的制造方法 |
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TWI822668B (zh) | 2023-11-21 |
KR102469463B1 (ko) | 2022-11-22 |
KR102511709B1 (ko) | 2023-03-20 |
TW201835125A (zh) | 2018-10-01 |
KR20220162799A (ko) | 2022-12-08 |
JPWO2018168258A1 (ja) | 2019-12-19 |
KR20190089056A (ko) | 2019-07-29 |
JP7097873B2 (ja) | 2022-07-08 |
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