Classifications

• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor

Definitions

• the present invention relates to a pattern forming method, an electronic device manufacturing method, an actinic ray-sensitive or radiation-sensitive resin composition, and a resist film.
• a pattern forming method using chemical amplification has been used in order to compensate for the sensitivity reduction due to light absorption.
• a photoacid generator contained in an exposed area is decomposed by light irradiation to generate an acid.
• PEB Post Exposure Bake
• the alkali-insoluble groups of the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition are rendered alkali-soluble by the catalytic action of the generated acid.
• the solubility in the developer is changed by, for example, changing the base.
• the wavelength of the exposure light source is shortened and the numerical aperture (NA) of the projection lens is increased.
• NA numerical aperture
• an exposure machine using an ArF excimer laser with a wavelength of 193 nm as a light source has been developed. ing. Under such circumstances, various structures have been proposed as actinic ray-sensitive or radiation-sensitive resin compositions.
• Patent Document 1 discloses a positive photosensitive resin composition suitable for fine processing of semiconductor elements using an ArF excimer laser.
• a thick resist film having a thickness of 500 nm is formed.
• the present inventors investigated the positive photosensitive resin composition described in Patent Document 1, and found that ArF liquid immersion lithography was applied to a resist film having a thickness of 500 nm or more formed from the positive photosensitive resin composition. When implemented, it was found that many defects occurred in the formed pattern. In other words, the present inventors have clarified that there is still room for further improvement in the defect suppression properties of patterns.
• Another object of the present invention is to provide a pattern forming method capable of forming a pattern with excellent defect suppression properties. Another object of the present invention is to provide a method for manufacturing an electronic device, an actinic ray-sensitive or radiation-sensitive resin composition, and a resist film.
• Step 1 of forming a resist film having a film thickness of 500 nm or more using an actinic ray-sensitive or radiation-sensitive resin composition Step 2 of subjecting the resist film to immersion exposure with radiation or actinic rays having a wavelength of 200 nm or less and performing heat treatment;
• a pattern forming method comprising a step 3 of developing the exposed resist film with an alkaline developer to form a pattern
• the actinic ray-sensitive or radiation-sensitive resin composition contains the following components (A) to (D), (A) a resin having a hydrophilic group and an acid-decomposable group and having a weight average molecular weight of 8,000 or less; (B) a photoacid generator; (D) a solvent and, A pattern forming method, wherein the solid content in the actinic ray-sensitive or radiation-sensitive resin composition is 10.0% by mass or more.
• Requirement 1 When the compound has a group that generates a polar group by the action of an acid, the entire surface of the film made of the compound is exposed under the same exposure conditions as in step 2, and heat treatment is performed. The difference between the water contact angle on the surface of the film made of the compound before exposure and the water contact angle on the surface of the film made of the compound after the heat treatment is 10° or more
• Requirement 2 The compound is alkaline. When the film made of the compound is brought into contact with the alkaline developer used in step 3, the film made of the compound before being brought into contact with the alkaline developer.
• the difference between the water contact angle on the surface and the water contact angle on the surface of the film made of the compound after contact with the alkaline developer is 10° or more [5]
• the resin represented by the above (A) is hydrophilic. any one of [1] to [4], wherein two or more repeating units having a group are included, and at least two of the two or more repeating units have hydrophilic groups different from each other; The patterning method described. [6] The pattern formation according to any one of [1] to [5], wherein the resin represented by (A) contains at least one repeating unit having a carboxy group and at least one repeating unit having a hydroxyl group. Method.
• the acid-decomposable group of the resin represented by the above (A) has a structure in which a polar group is protected by a leaving group that leaves under the action of an acid, and the number of carbon atoms in the leaving group is 8 or more, the pattern forming method according to any one of [1] to [6].
• the photoacid generator represented by the above (B) contains a compound represented by the formula (ZI-3) described later or a compound represented by the formula (ZI-4) described later, [1] The pattern forming method according to any one of [7].
• the pattern forming method according to any one of [1] to [8], wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains a compound represented by (E) below.
• (E) Acid diffusion control agent having no basicity [10] The pattern according to any one of [1] to [9], wherein the resin represented by the above (A) does not contain a fluorine atom and a silicon atom. Forming method. [11] The pattern formation according to any one of [1] to [10], wherein the content of the component represented by (C) above is 10.0% by mass or less with respect to the total solid content of the composition. Method. [12] A method for manufacturing an electronic device, comprising the pattern forming method according to any one of [1] to [11]. [13] An actinic ray-sensitive or radiation-sensitive resin composition containing the following components (A) to (D) and having a solid content of 10.0% by mass or more.
• the above compound represented by (C) is a group that produces a polar group by the action of an acid or a group that produces a polar group by the action of an alkali.
• the difference between the water contact angle on the surface of the film made of the compound before exposure and the water contact angle on the surface of the film made of the compound after the heat treatment is 10° or more Requirement 2:
• the compound is alkaline.
• the film made of the compound is brought into contact with the alkaline developer used in step 3
• the film made of the compound before being brought into contact with the alkaline developer is 10° or more [17]
• the resin represented by (A) above is hydrophilic.
• Light sensitive or radiation sensitive resin composition is any one of [13] to [16], comprising two or more repeating units having a group, and at least two of the two or more repeating units having hydrophilic groups different from each other; Actinic ray-sensitive or radiation-sensitive resin composition as described.
• the acid-decomposable group of the resin represented by the above (A) has a structure in which a polar group is protected by a leaving group that leaves under the action of an acid, and the number of carbon atoms in the leaving group is 8 or more, the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [13] to [18].
• the photoacid generator represented by the above (B) contains a compound represented by the formula (ZI-3) described later or a compound represented by the formula (ZI-4) described later, [13] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [19].
• (E) Acid diffusion control agent having no basicity [22] The sensor according to any one of [13] to [21], wherein the resin represented by (A) does not contain a fluorine atom or a silicon atom. Actinic ray or radiation sensitive resin composition. [23] The activator according to any one of [13] to [22], wherein the content of the component represented by (C) above is 10.0% by mass or less with respect to the total solid content of the composition. Light sensitive or radiation sensitive resin composition. [24] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [13] to [23].
• the pattern formation method which can form the pattern which is excellent in defect suppression property can be provided.
• the manufacturing method of an electronic device, actinic-ray-sensitive or radiation-sensitive resin composition, and a resist film can also be provided.
• an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• organic group refers to a group containing at least one carbon atom.
• the substituent is preferably a monovalent substituent unless otherwise specified.
• actinic rays or “radiation” as used herein means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB : Electron Beam) and the like.
• light means actinic rays or radiation.
• exposure means, unless otherwise specified, not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also electron beams, and It also includes drawing with particle beams such as ion beams.
• ⁇ is used to include the numerical values before and after it as lower and upper limits.
• the bonding direction of the divalent groups described herein is not limited unless otherwise specified. For example, in the compound represented by the formula "XYZ", when Y is -COO-, Y may be -CO-O- or -O-CO- good too. Further, the above compound may be "X--CO--O--Z" or "X--O--CO--Z.”
• (meth)acrylate refers to acrylate and methacrylate
• (meth)acryl refers to acrylic and methacrylic.
• Mw weight average molecular weight
• Mn number average molecular weight
• Mw/Mn dispersity
• the acid dissociation constant (pKa) represents the pKa in an aqueous solution. , is a calculated value. All pKa values described herein are calculated using this software package.
• pKa can also be obtained by molecular orbital calculation.
• H + dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in literature, etc., and are not limited to this. .
• DFT density functional theory
• Gaussian 16 is an example.
• the pKa in the present specification refers to a value obtained by calculating a value based on a database of Hammett's substituent constants and known literature values using software package 1, as described above. If it cannot be calculated, a value obtained by Gaussian 16 based on DFT (Density Functional Theory) is adopted.
• pKa in this specification refers to "pKa in aqueous solution” as described above, but when pKa in aqueous solution cannot be calculated, “pKa in dimethyl sulfoxide (DMSO) solution” is adopted. It shall be.
• solid content means all components other than the solvent contained in the composition.
• solid content means the content (% by mass) of the solid content in the composition.
• halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
• the pattern forming method of the present invention has steps 1 to 3 below.
• Step 1 Step of forming a resist film having a thickness of 500 nm or more using an actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as “resist composition”) described later
• Step 2 The resist film is coated with a wavelength of 200 nm
• Step 3 A step of developing the exposed resist film with an alkaline developer to form a pattern
• the resist composition used in (1) contains the following components (A) to (D) and has a solid content of 10.0% by mass or more.
• the pattern forming method of the present invention having the above configuration, even when immersion exposure lithography is performed on a thick resist film having a thickness of 500 nm or more using radiation with a wavelength of 200 nm or less or actinic rays, the occurrence of defects is suppressed.
• a pattern excellent in defect suppression
• the resist composition contains a specific acid-decomposable resin and a specific polarity conversion compound.
• the mechanism of action of the present invention by the specific acid-decomposable resin and the specific polarity conversion compound will be described below. Since the specific acid-decomposable resin has a hydrophilic group and a small weight-average molecular weight, it is easily dissolved and removed during alkaline development treatment. It is presumed that development residue defects due to remaining as a residue are less likely to occur.
• the pattern formed by the specific acid-decomposable resin has a hydrophilicity with a close-packed structure compared to the pattern formed by the acid-decomposable resin having a hydrophilic group and a relatively large weight-average molecular weight.
• the base tends to protrude on the surface.
• the substrate used for pattern formation is generally relatively hydrophilic, it has excellent affinity with the hydrophilic groups projecting from the pattern. As a result, it is presumed that the adhesion between the pattern and the substrate is likely to be excellent, and that the formed pattern is less prone to defects due to peeling and cracking.
• the specific acid-decomposable resin tends to have poor conformability to immersion liquid during immersion exposure lithography using radiation with a wavelength of 200 nm or less or actinic light due to its hydrophilic group.
• the resist composition contains a specific polarity conversion compound to complement the followability to the immersion liquid.
• the specific polarity conversion compound tends to exist on the film surface of the resist film due to its structure having fluorine atoms and/or silicon atoms, and forms a relatively hydrophobic layer on the surface of the resist film. Due to this, the followability to the immersion liquid is improved during immersion exposure lithography.
• the specific polarity conversion compound can control the water contact angle only on the film surface of the resist film without impairing the effect of improving the adhesion between the pattern and the substrate due to the specific acid-decomposable resin.
• the pattern forming method of the present invention is mainly used for defects resulting from development residues and lack of conformability to immersion liquids during immersion exposure lithography using radiation with a wavelength of 200 nm or less or actinic rays. It is presumed that the watermark defect caused by the heat treatment and the defect caused by peeling of the substrate from the pattern and cracking of the pattern are suppressed.
• the specific polarity conversion compound is a compound having a group that generates a polar group by the action of an acid
• the acid generated from the photoacid generator as the component (C) A polar group is generated by the action, and the suitability for alkali development is improved.
• the specific polarity conversion compound is a compound having a group which generates a polar group by the action of an alkali
• the polar group is generated by the action of the alkaline developer in step 3, thereby improving suitability for alkali development.
• the resist composition used in the pattern forming method of the present invention is suitable for both immersion exposure lithography using radiation with a wavelength of 200 nm or less or actinic rays and alkali development treatment. Therefore, in the pattern forming method of the present invention, both liquid immersion exposure treatment and alkali development treatment with radiation having a wavelength of 200 nm or less or actinic rays can proceed appropriately.
• the resist composition used in the pattern forming method of the present invention has a solid content in the composition (in other words, solid content with respect to the total mass of the composition) of 10.0% by mass or more, Suitable for forming a thick resist film having a thickness of 500 ⁇ m or more.
• the pattern forming method of the present invention will be described below. First, the resist composition used in the pattern forming method of the present invention will be described, and then each step of the pattern forming method will be described.
• the resist composition will be described in detail below.
• the resist composition is preferably a positive resist composition capable of alkali development.
• the resist composition is typically a chemically amplified resist composition.
• the resist composition contains the following components (A) to (D). Moreover, the solid content in the resist composition is 10.0% by mass or more.
• D Solvent
• the resist composition may contain other components in addition to the components (A) to (D) described above.
• the following components (E) to (F) can be preferably used.
• (F) Surfactant First, various components of the resist composition will be described in detail below.
• the resist composition contains a resin (specific acid-decomposable resin) having a hydrophilic group and an acid-decomposable group and a weight average molecular weight of 8,000 or less.
• An acid-decomposable group is a group that is decomposed (including elimination) by the action of an acid to generate a polar group. It is preferable to have A specific embodiment of the acid-decomposable group will be described later.
• the specific acid-decomposable resin corresponds to a resin that contains the acid-decomposable group described above and is decomposed by the action of an acid to increase its polarity. That is, in the pattern forming method of the present invention, when an alkaline developer is used as the developer, a positive pattern can be preferably formed.
• the specific acid-decomposable resin preferably contains a repeating unit having an acid-decomposable group. Specific aspects of the repeating unit having an acid-decomposable group will be described later.
• the hydrophilic group includes, for example, a hydroxy group, a cyano group, an alkoxy group, a carboxy group, an amino group, a fluorinated alcohol group, etc. Among them, a hydroxy group or a carboxy group is preferable.
• the specific acid-decomposable resin preferably contains a repeating unit having a hydrophilic group.
• the specific acid-decomposable resin may contain only one type of repeating unit having a hydrophilic group, or may contain two or more types thereof. Among them, the number of types of repeating units having a hydrophilic group contained in the specific acid-decomposable resin is preferably 2 to 3 in terms of the effect of the present invention being more excellent.
• the specific acid-decomposable resin preferably contains two or more types of repeating units having a hydrophilic group in order to enhance the effects of the present invention. and at least two of the two or more repeating units preferably have hydrophilic groups different from each other, and a repeating unit having a carboxy group and a repeating unit having a hydroxyl group More preferably, it contains one or more.
• the content of the repeating unit having a hydrophilic group is preferably 1 mol % or more, more preferably 5 mol % or more, still more preferably 10 mol % or more, relative to all repeating units in the specific acid-decomposable resin.
• the upper limit thereof is preferably 50 mol % or less, more preferably 40 mol % or less, and even more preferably 35 mol % or less.
• the repeating unit having a hydrophilic group means that each repeating unit contained in the specific acid-decomposable resin contains a hydrophilic group. Therefore, for example, when the repeating unit having an acid-decomposable group to be described later contains a hydrophilic group, the repeating unit having this acid-decomposable group also corresponds to the repeating unit having a hydrophilic group.
• the weight average molecular weight of the specific acid-decomposable resin is 8,000 or less as a polystyrene equivalent value by GPC method, and is preferably 1,000 to 8,000, more preferably 3,000 to 3,000, in terms of further improving film-forming properties. 8,000 is more preferred, 5,000 to 8,000 is even more preferred, and 6,500 to 8,000 is particularly preferred.
• the degree of dispersion (molecular weight distribution) of the specific acid-decomposable resin is usually from 1.0 to 5.0, preferably from 1.0 to 3.0, more preferably from 1.2 to 3.0, and from 1.2 to 2.0 is more preferred. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the side walls of the resist pattern, and the better the roughness.
• the acid-decomposable group refers to a group that is decomposed by the action of an acid to form a polar group. Among them, it preferably has a structure in which the polar group is protected by a leaving group that is released by the action of an acid. Furthermore, in the specific acid-decomposable resin, the acid-decomposable group is preferably contained in a repeating unit. That is, the specific acid-decomposable resin preferably contains a repeating unit having an acid-decomposable group. When the specific acid-decomposable resin contains a repeating unit having an acid-decomposable group, the action of an acid increases the polarity, increases the solubility in an alkaline developer, and decreases the solubility in an organic solvent.
• repeating unit having an acid-decomposable group the repeating unit mentioned later in (Repeating unit having an acid-decomposable group) or the repeating unit mentioned in (Repeating unit having an acid-decomposable group containing an unsaturated bond) can be used. preferable.
• An acid-decomposable group is a group that is decomposed by the action of an acid to form a polar group.
• the acid-decomposable group preferably has a structure in which the polar group is protected with a leaving group that leaves under the action of an acid.
• the polar group is preferably an alkali-soluble group such as a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a 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, acidic group such as tris(alkylsulfonyl)methylene group, and alcoholic hydroxyl group.
• alkali-soluble group such as a carboxy group, a phenolic hydroxyl group
• the polar group is preferably a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.
• Examples of the leaving group that 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 (Y3) -C(R 36 )(R 37 )(OR 38 )
• each of Rx 1 to Rx 3 is independently an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched chain), or an aryl group (monocyclic or polycyclic).
• Rx 1 to Rx 3 are alkyl groups (linear or branched)
• at least two of Rx 1 to Rx 3 are preferably methyl groups.
• Rx 1 to Rx 3 preferably each independently represent a linear or branched alkyl group, and Rx 1 to Rx 3 each independently represent a linear alkyl group. is more preferred.
• Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring.
• the alkyl group of Rx 1 to Rx 3 is preferably an alkyl group having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. .
• the cycloalkyl groups represented by Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl and adamantyl groups. is preferred.
• the aryl group represented by Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
• a vinyl group is preferable as the alkenyl group for Rx 1 to Rx 3 .
• the ring formed by combining two of Rx 1 to Rx 3 is preferably a cycloalkyl group.
• the cycloalkyl group formed by combining two of Rx 1 to Rx 3 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. or a polycyclic cycloalkyl group such as an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.
• 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, a heteroatom such as a carbonyl group, or a vinylidene group may be substituted.
• these cycloalkyl groups one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
• Rx 1 is a methyl group or an ethyl group
• Rx 2 and Rx 3 combine to form the above-described cycloalkyl group. is preferred.
• R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group.
• R 37 and R 38 may combine with each other to form a ring.
• Monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl groups, and the like. It is also preferred that R 36 is a hydrogen atom.
• the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and/or a group having a heteroatom such as a carbonyl group.
• one or more methylene groups are replaced with a heteroatom such as an oxygen atom and/or a group having a heteroatom such as a carbonyl group.
• R 38 may combine with another substituent of the main chain of the repeating unit to form a ring.
• the group formed by bonding R 38 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
• L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group).
• M represents a single bond or a divalent linking group.
• Q is an alkyl group optionally containing a heteroatom, a cycloalkyl group optionally containing a heteroatom, an aryl group optionally containing a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group in which these are combined (for example, a group in which an alkyl group and a cycloalkyl group are combined).
• Alkyl and cycloalkyl groups may, for example, have one of the methylene groups replaced by a heteroatom such as an oxygen atom or a heteroatom-bearing group such as a carbonyl group.
• L 1 and L 2 is preferably a hydrogen atom, and the other is preferably an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined. At least two of Q, M, and L1 may combine to form a ring (preferably a 5- or 6-membered ring).
• L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group.
• Secondary alkyl groups include isopropyl, cyclohexyl and norbornyl groups, and tertiary alkyl groups include tert-butyl and adamantane groups.
• the Tg (glass transition temperature) and the activation energy are increased, so that the film strength can be ensured and fogging can be suppressed.
• Ar represents an aromatic ring group.
• Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
• Rn and Ar may combine with each other to form a non-aromatic ring.
• Ar is more preferably an aryl group.
• the ring member atoms adjacent to the ring member atoms directly bonded to the polar group (or residue thereof) do not have halogen atoms such as fluorine atoms as substituents.
• other leaving groups that leave by the action of an acid include a 2-cyclopentenyl group having a substituent (such as an alkyl group) such as a 3-methyl-2-cyclopentenyl group, and a 1,1 A cyclohexyl group having a substituent (such as an alkyl group) such as ,4,4-tetramethylcyclohexyl group is also preferred.
• Another preferred embodiment of the acid-decomposable group is an embodiment in which the leaving group has 8 or more carbon atoms.
• the leaving group of the acid-decomposable group has 8 or more carbon atoms, the effect of the present invention tends to be more excellent.
• the number of carbon atoms is preferably 8 to 20, more preferably 8 to 15.
• repeating units having an acid-decomposable group examples include repeating units represented by formula (AI).
• Xa 1 represents a hydrogen atom or an optionally substituted alkyl group.
• T represents a single bond or a divalent linking group.
• Each of Rx 1 to Rx 3 is independently an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl (single ring or polycyclic) group. 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. Two of Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).
• Examples of the optionally substituted alkyl group represented by Xa 1 include a methyl group and a group represented by -CH 2 -R 11 .
• R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, for example, an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, or an alkyl group which may be substituted with a halogen atom Examples include acyl groups having 5 or less carbon atoms and alkoxy groups having 5 or less carbon atoms which may be substituted with halogen atoms, preferably alkyl groups having 3 or less carbon atoms, and more preferably methyl groups.
• Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• the divalent linking group of T includes an alkylene group, an aromatic ring group, a --COO--Rt-- group, an --O--Rt-- group and the like.
• Rt represents an alkylene group or a cycloalkylene group.
• T is preferably a single bond or a -COO-Rt- group.
• Rt is preferably an alkylene group having 1 to 5 carbon atoms, a -CH 2 - group, a -(CH 2 ) 2 - group, or a -(CH 2 ) 3 - group is more preferred.
• the alkyl group for Rx 1 to Rx 3 is preferably an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group.
• Cycloalkyl groups for Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. is preferred.
• the aryl group represented by Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
• a vinyl group is preferable as the alkenyl group for Rx 1 to Rx 3 .
• the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group.
• a polycyclic cycloalkyl group such as a cyclododecanyl group and an adamantyl group is preferred.
• cycloalkyl groups having 5 to 6 carbon atoms are preferred.
• 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, a heteroatom such as a carbonyl group, or a vinylidene group may be substituted.
• one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
• Rx 1 is a methyl group or an ethyl group
• Rx 2 and Rx 3 combine to form the above cycloalkyl group. A certain aspect is mentioned.
• substituents include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxy group, and an alkoxycarbonyl group ( 2 to 6 carbon atoms) and the like.
• the number of carbon atoms in the substituent is preferably 8 or less.
• the repeating unit represented by formula (AI) is preferably an acid-decomposable (meth)acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T represents a single bond It is a repeating unit that represents
• the number of carbon atoms contained in —C(Rx 1 )(Rx 2 )(Rx 3 ) is preferably 8 or more, such as 8 to 20. is more preferred, and 8 to 15 are even more preferred.
• the repeating unit having an acid-decomposable group may be contained alone or in combination of two or more.
• the content of repeating units having an acid-decomposable group is preferably 15 mol % or more, more preferably 20 mol % or more, and still more preferably 30 mol % or more, based on all repeating units in the specific acid-decomposable resin.
• the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly preferably 60 mol% or less.
• repeating units having an acid-decomposable group are shown below, but the present invention is not limited thereto.
• Xa 1 is any one of H, CH 3 , CF 3 and CH 2 OH
• Rxa and Rxb each represent a linear or branched alkyl group having 1 to 5 carbon atoms.
• repeating unit having an acid-decomposable group containing an unsaturated bond As the repeating unit having an acid-decomposable group containing an unsaturated bond, a repeating unit represented by formula (B) is preferable.
• Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group.
• L represents a single bond or a divalent linking group which may have a substituent.
• Ry 1 to Ry 3 are each independently a hydrogen atom, a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl represents a group. Also, any two of Ry 1 to Ry 3 may combine to form a monocyclic or polycyclic group (eg, monocyclic or polycyclic cycloalkyl group, cycloalkenyl group, etc.).
• At least one of Ry 1 to Ry 3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group, or Ry 1 to Ry 3 Any two of these combine to form a monocyclic or polycyclic alicyclic ring (eg, monocyclic or polycyclic cycloalkyl group, cycloalkenyl group, etc.).
• Two or more of Ry 1 to Ry 3 are not hydrogen atoms, and when any one of Ry 1 to Ry 3 is a hydrogen atom, the other two of Ry 1 to Ry 3 are are bonded to each other to form a ring having one or more vinylene groups in the ring structure, and at least one of the vinylene groups is bonded to a hydrogen atom represented by any one of Ry 1 to Ry 3 adjacent to the carbon atom that
• the alkyl group of Ry 1 to Ry 3 is preferably an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group.
• Cycloalkyl groups represented by Ry 1 to Ry 3 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. is preferred.
• the aryl groups represented by Ry 1 to Ry 3 are preferably aryl groups having 6 to 15 carbon atoms, more preferably aryl groups having 6 to 10 carbon atoms, such as phenyl, naphthyl and anthryl groups.
• a vinyl group is preferable as the alkenyl group for Ry 1 to Ry 3 .
• An ethynyl group is preferred as the alkynyl group for Ry 1 to Ry 3 .
• As the cycloalkenyl groups represented by Ry 1 to Ry 3 monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups having a structure partially containing a double bond are preferred.
• the cycloalkyl group formed by combining two of Ry 1 to Ry 3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group.
• a polycyclic cycloalkyl group such as a cyclododecanyl group and an adamantyl group is preferred.
• monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred.
• one of the methylene groups constituting the ring is a hetero atom such as an oxygen atom, a carbonyl group, a —SO 2 — group , and a group having a heteroatom such as —SO 3 —, a vinylidene group, or a combination thereof.
• one or more of the ethylene groups constituting the cycloalkane ring and cycloalkene ring may be replaced with a vinylene group.
• a preferred embodiment of the combination of Ry 1 to Ry 3 is, for example, that Ry 1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry 2 and Rx 3 are combined to form the above-mentioned Forming a cycloalkyl group or cycloalkenyl group, and Ry 1 is a hydrogen atom, and Ry 2 and Ry 3 are bonded to each other to form a ring having one or more vinylene groups in the ring structure. and at least one of the vinylene groups is present adjacent to the carbon atom to which the hydrogen atom represented by Ry 1 is bonded.
• Ry 1 to Ry 3 further have a substituent
• substituents include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxy group, and an alkoxy group.
• a carbonyl group (having 2 to 6 carbon atoms) and the like can be mentioned.
• the number of carbon atoms in the substituent is preferably 8 or less.
• the optionally substituted alkyl group represented by Xb includes, for example, a methyl group and a group represented by —CH 2 —R 11 .
• R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, for example, an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, or an alkyl group which may be substituted with a halogen atom Examples include acyl groups having 5 or less carbon atoms and alkoxy groups having 5 or less carbon atoms which may be substituted with halogen atoms, preferably alkyl groups having 3 or less carbon atoms, and more preferably methyl groups.
• Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, preferably an aromatic ring group.
• L is preferably -Rt-, -CO-, -COO-Rt-CO- or -Rt-CO-.
• Rt may have a substituent such as a halogen atom, a hydroxyl group, an alkoxy group, or the like. Aromatic groups are preferred.
• substituents include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), A carboxy group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), and the like can be mentioned.
• the number of carbon atoms in the substituent is preferably 8 or less.
• the repeating unit represented by the formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester repeating unit (Xb represents a hydrogen atom or a methyl group, and L represents a -CO- group repeating unit represented), acid-decomposable hydroxystyrene tertiary alkyl ether-based repeating unit (repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), acid-decomposable styrene carboxylic acid tertiary ester It is a repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)).
• the leaving group contained in the acid-decomposable group contained in formula (B) has 8 or more carbon atoms.
• the number of carbon atoms in the leaving group contained in the acid-decomposable group is more preferably 8-20, still more preferably 8-15.
• the total number of carbon atoms in the group represented by —C(Ry 1 )(Ry 2 )(Ry 3 ) is 8 or more. is preferred, 8 to 20 is more preferred, and 8 to 15 is even more preferred.
• the repeating unit having an acid-decomposable group containing an unsaturated bond may be contained alone or in combination of two or more.
• the content of repeating units having an acid-decomposable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and 30 mol% of all repeating units in the specific acid-decomposable resin. The above is more preferable.
• the upper limit thereof is preferably 80 mol % or less, more preferably 70 mol % or less, and particularly preferably 60 mol % or less.
• Xb and L represent any one of the substituents and linking groups described above
• Ar represents an aromatic group
• R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, alkenyl group, hydroxyl group, alkoxy group, acyloxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR''' or -COOR''': R''' is alkyl having 1 to 20 carbon atoms group or fluorinated alkyl group), or a substituent such as a carboxy group, where R′ is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, a monocyclic represents
• the specific acid-decomposable resin may contain repeating units other than the repeating units described above.
• the specific acid-decomposable resin preferably contains at least one repeating unit selected from the group consisting of (X1) to (X4) below.
• (X1) a repeating unit having an acid group, described later
• (X2) a repeating unit having at least one group selected from a lactone group, a sultone group, and a carbonate group, described later
• X3 an alcoholic hydroxyl group and a cyano group, described later
• Repeating unit (X4) having at least one group selected from the following repeating unit represented by formula (III)
• the specific acid-decomposable resin it is also preferable to adopt a mode in which neither fluorine atoms nor silicon atoms are contained, from the point of view of further improving suitability for ArF immersion lithography. Moreover, it is preferable that the specific acid-decomposable resin does not have an aromatic group from the viewpoint of further improving suitability for ArF immersion lithography.
• alcoholic A repeating unit or the like having a hydroxyl group corresponds to a repeating unit having a hydrophilic group.
• ⁇ repeating units having an acid-decomposable group> ⁇ repeating units having a lactone group, a sultone group, or a carbonate group>, and ⁇ having at least one group selected from an alcoholic hydroxyl group and a cyano group>
• a repeating unit having a hydrophilic group as a substituent also corresponds to a repeating unit having a hydrophilic group.
• the specific acid-decomposable resin preferably contains a repeating unit having an acid group.
• As the acid group an acid group having a pKa of 13 or less is preferable.
• the acid dissociation constant of the acid group is preferably 13 or less, more preferably 3-13, even more preferably 5-10.
• the content of acid groups in the specific acid-decomposable resin is not particularly limited, but is often 0.2 to 6.0 mmol/g.
• the acid group is preferably, for example, a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
• one or more (preferably 1 to 2) fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group).
• —C(CF 3 )(OH)—CF 2 — thus formed is also preferred as an acid group.
• one or more of the fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF 3 )(OH)-CF 2 -.
• the repeating unit having an acid group is at least one type selected from repeating units having an acid-decomposable group described above, repeating units having a lactone group, a sultone group, or a carbonate group described later, and alcoholic hydroxyl groups and cyano groups described later. and a repeating unit different from the repeating unit represented by formula (III), which will be described later.
• a repeating unit having an acid group may have a fluorine atom or an iodine atom.
• repeating units having an acid group examples include repeating units represented by formula (B).
• R3 represents a hydrogen atom or a monovalent organic group.
• a group represented by -L 4 -R 8 is preferable.
• L4 represents a single bond or an ester group.
• R 8 includes an alkyl group, a cycloalkyl group optionally having a fluorine atom or an iodine atom, an aryl group, or a group combining these.
• R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group optionally having a fluorine atom or an iodine atom.
• L 2 is a single bond, an ester group, or —CO—, —O—, or an alkylene group (preferably having 1 to 6 carbon atoms; it may be linear or branched; and —CH 2 — is a halogen It may be substituted with an atom.) represents a divalent group formed by combining.
• L 3 represents an (n+m+1)-valent aromatic hydrocarbon ring group or (n+m+1)-valent alicyclic hydrocarbon ring group.
• Aromatic hydrocarbon ring groups include benzene ring groups and naphthalene ring groups.
• the alicyclic hydrocarbon ring group may be monocyclic or polycyclic, and examples thereof include cycloalkyl ring groups, norbornene ring groups, and adamantane ring groups.
• L3 preferably represents an (n+m+1) -valent alicyclic hydrocarbon ring group.
• R6 represents a hydroxyl group or a fluorinated alcohol group.
• the fluorinated alcohol group is preferably a monovalent group represented by the following formula (3L).
• L6X represents a single bond or a divalent linking group.
• the divalent linking group is not particularly limited, examples thereof include -CO-, -O-, -SO-, -SO 2 -, -NR A -, an alkylene group (preferably having 1 to 6 carbon atoms, linear or a branched chain), and a divalent linking group combining a plurality of these.
• RA includes a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• the said alkylene group may have a substituent.
• substituents include halogen atoms (preferably fluorine atoms) and hydroxyl groups.
• R6X represents a hexafluoroisopropanol group.
• L 3 is also preferably an (n+m+1)-valent aromatic hydrocarbon ring group.
• R7 represents a halogen atom.
• a halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
• m represents an integer of 1 or more.
• m is preferably an integer of 1-3, more preferably an integer of 1-2.
• n represents an integer of 0 or 1 or more.
• n is preferably an integer of 1-4. (n+m+1) is preferably an integer of 1-5.
• repeating units having an acid group include the following repeating units.
• the repeating unit having an acid group may be contained alone or in combination of two or more.
• the content of repeating units having an acid group is preferably 1 mol % or more, more preferably 5 mol % or more, relative to all repeating units in the specific acid-decomposable resin.
• the upper limit thereof is preferably 50 mol % or less, more preferably 40 mol % or less, and even more preferably 30 mol % or less.
• the specific acid-decomposable resin is a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group (hereinafter collectively referred to as "a repeating unit having a lactone group, a sultone group, or a carbonate group. )).
• a repeating unit having a lactone group, a sultone group, or a carbonate group preferably does not have an acid group such as a hydroxyl group and a hexafluoropropanol group.
• the lactone group or sultone group may have a lactone structure or sultone structure.
• the lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure.
• a 5- to 7-membered lactone structure in which another ring structure is condensed to form a bicyclo structure or spiro structure, or a 5- to 7-membered ring sultone in a form to form a bicyclo structure or spiro structure More preferably, the structure is condensed with another ring structure.
• the specific acid-decomposable resin has a lactone structure represented by any of the following formulas (LC1-1) to (LC1-21), or any of the following formulas (SL1-1) to (SL1-3). It preferably contains a repeating unit having a lactone group or a sultone group obtained by extracting one or more hydrogen atoms from the ring member atoms of the sultone structure. Also, a lactone group or a sultone group may be directly bonded to the main chain. For example, ring member atoms of a lactone group or a sultone group may constitute the main chain of the specific acid-decomposable resin.
• the lactone structure or sultone structure portion may have a substituent (Rb 2 ).
• Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxy group. , a halogen atom, a cyano group, an acid-decomposable group, and the like.
• n2 represents an integer of 0-4. When n2 is 2 or more, multiple Rb 2 may be different, and multiple Rb 2 may combine to form a ring.
• Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom.
• a halogen atom for Rb 0 includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Rb 0 is preferably a hydrogen atom or a methyl group.
• Ab is a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxy group, or a divalent group combining these show.
• a single bond or a linking group represented by -Ab 1 -CO 2 - is preferred.
• Ab 1 is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, ethylene group, cyclohexylene group, adamantylene group or norbornylene group.
• V is a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-21), or formulas (SL1-1) to (SL1- 3) represents a group obtained by removing one hydrogen atom from a ring member atom of the sultone structure represented by any one of 3).
• any optical isomer may be used.
• one kind of optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
• its optical purity (ee) is preferably 90 or more, more preferably 95 or more.
• a cyclic carbonate group is preferred.
• a repeating unit having a cyclic carbonate group a repeating unit represented by the following formula (A-1) is preferable.
• R A 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
• n represents an integer of 0 or more.
• R A 2 represents a substituent. When n is 2 or more, a plurality of R A 2 may be the same or different.
• A represents a single bond or a divalent linking group.
• the divalent linking group includes an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxy group, or a combination of these. is preferred.
• Z represents an atomic group forming a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.
• the number of ring member atoms of the ring formed by the group represented by -O-CO-O- in the formula and the atomic group represented by Z is not particularly limited, for example, preferably 5 to 10, 5 to 8 is more preferred, and 5 is even more preferred.
• repeating units having a lactone group, a sultone group, or a carbonate group are shown below.
• a repeating unit having a lactone group, a sultone group, or a carbonate group may be contained alone or in combination of two or more.
• the content of repeating units having a lactone group, a sultone group, or a carbonate group is preferably 1 mol % or more, more preferably 10 mol % or more, based on all repeating units in the specific acid-decomposable resin.
• the upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly preferably 60 mol% or less.
• the specific acid-decomposable resin preferably contains repeating units having at least one type of group selected from alcoholic hydroxyl groups and cyano groups. This improves the adhesion to the substrate and the compatibility with the developer.
• a repeating unit having an alcoholic hydroxyl group or a cyano group is more preferably a repeating unit having an alicyclic hydrocarbon structure substituted with an alcoholic hydroxyl group or a cyano group.
• a repeating unit having an alcoholic hydroxyl group or a cyano group preferably does not have an acid-decomposable group.
• Repeating units having an alcoholic hydroxyl group or a cyano group include, for example, repeating units represented by the following formulas (AIIa) to (AIId).
• R 1 c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• Each of R 2 c to R 4 c independently represents a hydrogen atom, a hydroxyl group (alcoholic hydroxyl group), or a cyano group. However, at least one of R 2 c to R 4 c represents a hydroxyl group or a cyano group.
• One or two of R 2 c to R 4 c preferably represent a hydroxyl group and the rest are hydrogen atoms.
• the repeating unit having an alcoholic hydroxyl group or a cyano group is particularly preferably a repeating unit represented by the formula (AIIa), two of R 2 c to R 4 c being hydroxyl groups, and the rest being A repeating unit represented by formula (AIIa) representing a hydrogen atom is more preferable.
• repeating units having a hydroxyl group or a cyano group are listed below, but the present invention is not limited thereto.
• repeating unit having an alcoholic hydroxyl group other than the above, a repeating unit having a linear or branched alkyl group substituted with an alcoholic hydroxyl group can also be mentioned.
• Examples of such repeating units having an alcoholic hydroxyl group include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 10 carbon atoms substituted with one or more hydroxyl groups at the alkyl moiety. be done.
• the repeating unit having an alcoholic hydroxyl group or a cyano group may be contained alone or in combination of two or more.
• the content of repeating units having an alcoholic hydroxyl group or a cyano group is preferably 1 mol % or more, more preferably 5 mol % or more, based on all repeating units in the specific acid-decomposable resin.
• the upper limit thereof is preferably 40 mol % or less, more preferably 30 mol % or less, and even more preferably 25 mol % or less.
• the specific acid-decomposable resin may contain a repeating unit represented by formula (III).
• R5 represents a hydrocarbon group having a cyclic structure and no polar group.
• Ra represents a hydrogen atom, an alkyl group, or a —CH 2 —O—Ra 2 group.
• Ra2 represents a hydrogen atom, an alkyl group, or an acyl group.
• Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group.
• the cyclic structure of R 5 may be either monocyclic or polycyclic. That is, R5 may be either a monocyclic hydrocarbon group or a polycyclic hydrocarbon group.
• Examples of monocyclic hydrocarbon groups include cycloalkyl groups having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group, and 3 to 12 carbon atoms such as cyclohexenyl group. 12 cycloalkenyl groups, preferably a monocyclic hydrocarbon group having 3 to 7 carbon atoms, more preferably a cyclopentyl group or a cyclohexyl group.
• Polycyclic hydrocarbon groups include ring-assembled hydrocarbon groups and bridged cyclic hydrocarbon groups.
• the ring-assembled hydrocarbon group includes a bicyclohexyl group, a perhydronaphthalenyl group, and the like.
• the bridged cyclic hydrocarbon ring includes, for example, pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo[2.2.2]octane ring, bicyclo[3.2.1]octane ring, etc.).
• cyclic hydrocarbon rings cyclic hydrocarbon rings
• tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo[5.2.1.0 2,6 ]decane, and tricyclo[4.3.1.1 2,5 ]undecane rings
• Tetracyclo[4.4.0.1 2,5 . 1 7,10 ]dodecane and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring
• Condensed rings in which multiple 5- to 8-membered cycloalkane rings such as naphthene, perhydrofluorene, perhydroindene, and perhydrophenalene rings are condensed;
• the polycyclic hydrocarbon group is preferably a norbornyl group, an adamantyl group, a bicyclooctanyl group, or a tricyclo[5,2,1,0 2,6 ]decanyl group, more preferably a norbornyl group or an adamantyl group.
• the cyclic structure of R 5 may further have a substituent.
• substituents include halogen atoms, alkyl groups, cycloalkyl groups, aralkyl groups, alkoxy groups, amino groups, alkoxycarbonyl groups, and aralkyloxycarbonyl groups.
• Ra represents H, CH3 , CH2OH , or CF3 .
• 1 type of repeating units represented by Formula (III) may be contained, or 2 or more types may be contained.
• the content of the repeating unit represented by formula (III) is preferably 1 mol % or more, more preferably 5 mol % or more, relative to all repeating units in the specific acid-decomposable resin.
• the upper limit thereof is preferably 40 mol % or less, more preferably 30 mol % or less, and even more preferably 25 mol % or less.
• the specific acid-decomposable resin contains various repeating structural units for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc. may have.
• all of the repeating units are composed of (meth)acrylate repeating units.
• all repeating units may be methacrylate repeating units, all repeating units may be acrylate repeating units, or all repeating units may be methacrylate repeating units and acrylate repeating units.
• the acrylate type repeating unit is 50 mol % or less of the total repeating units.
• the specific acid-decomposable resin can be synthesized according to conventional methods (for example, radical polymerization).
• the content of the specific acid-decomposable resin is preferably 50.0 to 99.9% by mass, more preferably 60.0 to 99.0% by mass, based on the total solid content of the composition. 70.0 to 99.0% by mass is more preferable. Also, the specific acid-decomposable resin may be used singly or in combination.
• the resist composition contains a photoacid generator.
• a photoacid generator is a compound that generates an acid upon exposure to actinic rays or radiation.
• a compound that generates an organic acid upon exposure to actinic rays or radiation is preferred. Examples include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imidosulfonate compounds, oximesulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzylsulfonate compounds.
• a known compound that generates an acid upon exposure to actinic rays or radiation can be appropriately selected and used either singly or as a mixture thereof.
• paragraphs [0125]-[0319] of US Patent Application Publication No. 2016/0070167A1 paragraphs [0086]-[0094] of US Patent Application Publication No. 2015/0004544A1
• US Patent Application Publication No. 2016/0237190A1 paragraphs [0125]-[0319] of US Patent Application Publication No. 2016/0070167A1
• paragraphs [0086]-[0094] of US Patent Application Publication No. 2015/0004544A1 paragraphs [0086]-[0094] of US Patent Application Publication No. 2015/0004544A1
• US Patent Application Publication No. 2016/0237190A1 The known compounds disclosed in paragraphs [0323] to [0402] of the specification can be suitably used as the photoacid generator.
• photoacid generator for example, compounds represented by the following formula (ZI), formula (ZII), or formula (ZIII) are preferable.
• R 201 , R 202 and R 203 each independently represent an organic group.
• the number of carbon atoms in the organic group as R 201 , R 202 and R 203 is generally 1-30, preferably 1-20.
• two of R 201 to R 203 may combine 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.
• Groups formed by combining two of R 201 to R 203 include an alkylene group (e.g., butylene group, pentylene group, etc.) and —CH 2 —CH 2 —O—CH 2 —CH 2 —. mentioned.
• Z ⁇ represents an anion.
• Preferred embodiments of the cation in formula (ZI) include corresponding groups in compound (ZI-1), compound (ZI-2), compound (ZI-3), and compound (ZI-4) described later.
• the photoacid generator may be a compound having a plurality of structures represented by formula (ZI). For example, at least one of R 201 to R 203 of the compound represented by formula (ZI) and at least one of R 201 to R 203 of another compound represented by formula (ZI) are single bonds or linked It may be a compound having a structure bonded via a 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 an arylsulfonium cation.
• R 201 to R 203 may be aryl groups, or part of R 201 to R 203 may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
• Arylsulfonium compounds include, for example, triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.
• the aryl group contained in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues, and the like.
• the two or more aryl groups may be the same or different.
• the alkyl group or cycloalkyl group optionally possessed by the arylsulfonium compound is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms. is preferred, and examples thereof include methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, cyclopropyl, cyclobutyl and cyclohexyl groups.
• the aryl group, alkyl group, and cycloalkyl group represented by R 201 to R 203 are each independently an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 15 carbon atoms), an aryl group. (eg, 6 to 14 carbon atoms), an alkoxy group (eg, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent.
• 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 also includes an aromatic ring containing a heteroatom.
• the organic group having no aromatic ring as R 201 to R 203 generally has 1 to 30 carbon atoms, 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, and a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group or alkoxy
• a carbonylmethyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.
• the alkyl group and cycloalkyl group represented by R 201 to R 203 include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl group and pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group and norbornyl group) are preferred.
• R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, 1-5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
• Compound (ZI-3) is a compound represented by the following formula (ZI-3).
• R 1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or an alkenyl group.
• the number of carbon atoms in the alkyl group represented by R 1 is preferably 1-10, more preferably 1-6.
• the number of carbon atoms in the cycloalkyl group represented by R 1 is preferably 3-10.
• Cycloalkyl groups include, for example, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and the like.
• the number of carbon atoms in the alkoxy group represented by R 1 (the alkyl group portion may be linear or branched) is preferably 1-10, more preferably 1-6.
• the number of carbon atoms in the cycloalkoxy group represented by R 1 is preferably 3-10, more preferably 3-6.
• the aryl group represented by R 1 is preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, such as phenyl, naphthyl and anthryl groups.
• a vinyl group is preferred as the alkenyl group represented by R 1 .
• the alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, and alkenyl group represented by R 1 may further have a substituent.
• Substituents include alkyl groups, cycloalkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, alkylcarbonyloxy groups, cycloalkylcarbonyloxy groups, halogen atoms, hydroxyl groups, nitro groups, alkylthio groups, and arylthio groups. groups.
• the number of carbon atoms in the alkyl portion (either linear or branched) in the alkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyloxy group, and alkylthio group is preferably 1 to 10, for example. , 1 to 6 are more preferred.
• the number of carbon atoms in the alkyl portion of the cycloalkyl group and cycloalkylcarbonyloxy group is, for example, preferably 3-20, more preferably 5-10, even more preferably 6-10.
• the aryl group in the aryl group, aryloxy group and arylthio group is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
• R2 and R3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or an aryl group.
• Specific examples of the alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group and aryl group represented by R 2 and R 3 include the alkyl group, cycloalkyl group and alkoxy group represented by R 1 above, The same specific examples as those shown for the cycloalkoxy group and the aryl group can be mentioned.
• R 1 and R 2 may combine with each other to form a ring.
• R 2 and R 3 may combine with each other to form a ring.
• the ring formed by combining R 1 and R 2 and R 2 and R 3 may be either an aromatic ring or an alicyclic ring.
• the number of ring members is, for example, 3 to 10, preferably 4 to 8, more preferably 5 or 6.
• R X and R y each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxycarbonylcycloalkyl group; represents Specific examples of the alkyl group, cycloalkyl group, alkenyl group, and aryl group represented by R X and R y include the alkyl group, cycloalkyl group, alkenyl group, and aryl group represented by R 1 above. Specific examples similar to those described above can be mentioned.
• the number of carbon atoms in the 2-oxoalkyl group (either linear or branched) represented by R X and R y is preferably 1 to 10, more preferably 1 to 6, for example.
• the number of carbon atoms in the alkoxycarbonylalkyl group (either linear or branched) represented by R X and R y is, for example, preferably 2 to 12, more preferably 2 to 10, and 2 to 6 is more preferred.
• the number of carbon atoms in the 2-oxocycloalkyl group represented by R X and R y is, for example, preferably 3-20, more preferably 5-10, even more preferably 6-10.
• the number of carbon atoms in the alkoxycarbonylcycloalkyl group (the alkoxy moiety may be linear or branched) represented by R X and R y is preferably, for example, 5 to 20, more preferably 5 to 10. Preferably, 6 to 10 is more preferable.
• R X and R y may combine with each other to form a ring.
• the ring formed by combining R X and R y may be either an aromatic ring or an alicyclic ring.
• the number of ring members is, for example, 3 to 10, preferably 4 to 8, more preferably 5 or 6.
• the ring may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or an amide bond.
• Z ⁇ represents an anion
• l represents an integer of 0 to 2, preferably 0 or 1.
• r represents an integer of 0-8, preferably an integer of 0-4.
• R a1 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxycarbonyl group. These groups may have a substituent.
• Specific examples of the alkyl group, cycloalkyl group, and alkoxy group represented by R a1 are the alkyl group, cycloalkyl group, and alkoxy group represented by R 1 in the above formula (ZI-3). Specific examples similar to those described above can be mentioned.
• the number of carbon atoms in the alkoxycarbonyl group represented by R a1 is preferably 2 to 10, more preferably 2 to 6.
• Each R b1 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have a substituent.
• Specific examples of the alkyl group and cycloalkyl group represented by R a1 are the same as the specific examples of the alkyl group and cycloalkyl group represented by R 1 in the above formula (ZI-3). mentioned.
• examples of the substituent include the same substituents as the alkyl group for R 1 in formula (ZI-3) above. Note that two R b1 may be bonded to each other to form a ring.
• R b1 When two R b1 are bonded together to form a ring, this ring may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or an amide bond.
• a preferred embodiment of R b1 is an embodiment in which two R b1 are alkylene groups and are bonded together to form a ring structure (alicyclic structure).
• the ring structure is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.
• R c1 represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, or a cycloalkylsulfonyl group. These groups may have a substituent. When r is an integer of 2 or more, a plurality of R c1 may be the same or different.
• X ⁇ represents an anion
• R 204 to R 207 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
• the aryl group represented by R 204 to R 207 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group represented by R 204 to R 207 may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
• Skeletons of aryl groups having a heterocyclic structure include, for example, pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
• Alkyl groups and cycloalkyl groups represented by R 204 to R 207 include linear alkyl groups having 1 to 10 carbon atoms and branched alkyl groups having 3 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, etc.) or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, norbornyl group, etc.) is preferred.
• the aryl group, alkyl group and cycloalkyl group represented by R 204 to R 207 may each independently have a substituent.
• substituents that the aryl group, alkyl group and cycloalkyl group represented by R 204 to R 207 may have include an alkyl group (eg, 1 to 15 carbon atoms) and a cycloalkyl group (eg, carbon 3 to 15), aryl groups (eg, 6 to 15 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.
• Z ⁇ represents an anion.
• Z ⁇ in formula (ZI), Z ⁇ in formula (ZII), Z ⁇ in formula (ZI-3), and X ⁇ in formula (ZI-4) are anions represented by the following formula (3) : preferable.
• Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
• the number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4.
• a perfluoroalkyl group is preferable as the alkyl group substituted with at least one fluorine atom.
• Xf is preferably a fluorine atom or a C 1-4 perfluoroalkyl group, more preferably a fluorine atom or CF 3 . In particular, it is more preferable that both Xf are fluorine atoms.
• R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When multiple R 4 and R 5 are present, each of R 4 and R 5 may be the same or different.
• the alkyl groups represented by R 4 and R 5 may have substituents and preferably have 1 to 4 carbon atoms.
• R 4 and R 5 are preferably hydrogen atoms. Specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred aspects of Xf in formula (3).
• L represents a divalent linking group.
• divalent linking groups include -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2 -, and alkylene groups (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 a divalent linking group combining a plurality of these groups.
• -COO-, -CONH-, -CO-, -O-, -SO 2 -, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group-, or -NHCO -Alkylene group- is preferred, and -COO-, -CONH-, -SO 2 -, -COO-alkylene group- or -OCO-alkylene group- is more preferred.
• W represents an organic group containing a cyclic structure.
• a cyclic organic group is preferable.
• Cyclic organic groups include, for example, alicyclic groups, aryl groups, and heterocyclic groups.
• Alicyclic groups may be monocyclic or polycyclic.
• Monocyclic alicyclic groups include, for example, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
• polycyclic alicyclic groups examples include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.
• polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.
• alicyclic groups having a bulky structure with 7 or more carbon atoms such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.
• Aryl groups may be monocyclic or polycyclic.
• the aryl group includes, for example, phenyl group, naphthyl group, phenanthryl group, and anthryl group.
• a heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further suppress acid diffusion. Moreover, the heterocyclic group may or may not have aromaticity. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring.
• Non-aromatic heterocycles include, for example, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
• lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the above-mentioned specific acid-decomposable resin.
• the heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.
• the cyclic organic group may have a substituent.
• substituents include alkyl groups (either linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic, and spirocyclic preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group , and sulfonate ester groups.
• carbonyl carbon may be sufficient as carbon (carbon which contributes to ring formation) which comprises a cyclic
• Examples of anions represented by 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)qW, or SO 3 - -CF 2 -CH(CF 3 )-OCO-(L)q'-W is preferred.
• L, q, and W are the same as in formula (3).
• q' represents an integer from 0 to 10;
• Z ⁇ in formula (ZI), Z ⁇ in formula (ZII), Z ⁇ in formula (ZI-3), and X ⁇ in formula (ZI-4) are represented by the following formula (4)
• the represented anions are also preferred.
• 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 preferably a fluorine atom or a monovalent organic group having a fluorine atom, and both of X B3 and X B4 are a fluorine atom or a monovalent organic group having a fluorine atom is more preferred.
• both X B3 and X B4 are fluorine-substituted alkyl groups.
• L, q, and W are the same as in formula (3).
• Z ⁇ in formula (ZI), Z ⁇ in formula (ZII), Z ⁇ in formula (ZI-3), and X ⁇ in formula (ZI - 4) include anions represented by the following formula (5). preferable.
• each Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
• Each Xb independently represents a hydrogen atom or an organic group having no fluorine atom.
• Z ⁇ in formula (ZI), Z ⁇ in formula (ZII), Z ⁇ in formula (ZI-3), and X ⁇ in formula (ZI-4) may be a benzenesulfonate anion and branched Also preferred are benzenesulfonate anions substituted by monoalkyl or cycloalkyl groups.
• Z ⁇ in formula (ZI), Z ⁇ in formula (ZII), Z ⁇ in formula (ZI-3), and X ⁇ in formula (ZI-4) are aromatics represented by the following formula (SA1) Group sulfonate anions are also preferred.
• Ar represents an aryl group and may further have a substituent other than the sulfonate anion and -(D-B) group.
• Substituents which may be further included include a fluorine atom and a hydroxyl group.
• n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, and still more preferably 3.
• D represents a single bond or a divalent linking group.
• divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate ester groups, ester groups, and groups consisting of combinations 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-weight compound, or may be in the form of being incorporated into a part of the polymer. Moreover, the form of a low-molecular-weight compound and the form incorporated into a part of a polymer may be used in combination.
• the photoacid generator is preferably in the form of a low molecular weight compound. When the photoacid generator is in the form of a low-molecular-weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,000 or less.
• the photoacid generator When the photoacid generator is in the form of being incorporated into a part of the polymer, it may be incorporated into a part of the above-mentioned specific acid-decomposable resin, or may be incorporated into a resin different from the specific acid-decomposable resin. good too.
• 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 (the total if multiple types are present) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total solid content of the composition. Preferably, 1.0% by mass or more is more preferable.
• the content of the photoacid generator contained in the resist composition is preferably 5 to 35% by mass (preferably 7 to 30% by mass) relative to the total solid content of the composition.
• the acid dissociation constant pKa of the acid (generated acid) generated by decomposing the photoacid generator upon irradiation with actinic rays or radiation is, for example, ⁇ 0.01 or less, preferably ⁇ 1.00 or less, and ⁇ 1. 0.50 or less is more preferable, and -2.00 or less is even more preferable.
• the lower limit of pKa is not particularly limited, it is -10.0 or higher, for example. pKa can be measured by the method described above.
• the resist composition contains a compound (specific polarity conversion compound) having a fluorine atom or a silicon atom and having a group that produces a polar group by the action of an acid or a group that produces a polar group by the action of an alkali.
• the resist composition includes, as the specific polarity conversion compound, a compound having a fluorine atom or a silicon atom and a group that generates a polar group by the action of an acid (hereinafter also referred to as "specific polarity conversion compound A”), or , a compound having a fluorine atom or a silicon atom and a group that generates a polar group by the action of an alkali (hereinafter also referred to as "specific polarity conversion compound B").
• Specific polarity conversion compound A and specific polarity conversion compound B are described below.
• the specific polar conversion compound A is a compound having a fluorine atom or a silicon atom and a group (acid-decomposable group) that generates a polar group by the action of an acid.
• group that generates a polar group by the action of an acid as used herein has the same meaning as the acid-decomposable group possessed by the specific acid-decomposable resin, and the preferred embodiment is also the same.
• the specific polarity conversion compound A can be decomposed by the action of an acid generated during the heat treatment performed after the exposure in step 2 to increase the solubility in an alkaline developer.
• the specific polarity conversion compound A is preferably a polymer, and the polymer preferably contains a repeating unit (repeating unit X) having an acid-decomposable group.
• a fluorine atom or a silicon atom may be contained in the main chain of the resin or may be contained in a side chain.
• repeating units having an acid-decomposable group that the specific polar-converting compound A may contain include the following types.
• b A * having an acid-decomposable group and not having a fluorine atom and a silicon atom
• a repeating unit (b A ′′) having an acid-decomposable group on one side chain and at least one of a fluorine atom and a silicon atom on a side chain different from the side chain in the same repeating unit
• the repeating unit (the repeating unit (b A ′), (b A ′′) having at least one of a fluorine atom and a silicon atom) is different repeating units).
• the side chain having an acid-decomposable group and the side chain having at least one of a fluorine atom and a silicon atom in the repeating unit (b A ′′) are bonded to the same carbon atom in the main chain, i.e. It is preferable that they have a positional relationship such as the following formula (K1).
• B1 represents a partial structure having the acid-decomposable group
• B2 represents a partial structure having at least one of a fluorine atom and a silicon atom.
• the specific polar-converting compound A more preferably has repeating units (b A ′) or repeating units (b A *).
• a repeating unit represented by the following formula (II) is particularly preferable.
• the embodiment in which A represents a silicon atom corresponds to the repeating unit (b A ')
• R 11 to R 14 in the repeating unit are fluorine atoms or When it contains a silicon atom, it corresponds to the repeating unit (b A ′), and when R 11 to R 14 in the repeating unit do not contain a fluorine atom, it corresponds to the repeating unit (b A *).
• A represents a carbon atom or a silicon atom.
• R 11 represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group.
• R 12 , R 13 and R 14 each independently represent an optionally substituted linear, branched or cyclic alkyl group. R 12 and R 13 may combine with each other to form a ring.
• Linear or branched alkyl groups represented by R 12 , R 13 and R 14 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and an alkyl group having 1 to 5 carbon atoms such as a t-butyl group.
• the cyclic alkyl group represented by R 12 , R 13 and R 14 may be either monocyclic or polycyclic.
• monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups
• alkyl groups and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.
• the ring formed by combining R 12 and R 13 is preferably a cycloalkyl group.
• the cycloalkyl group formed by combining R 12 and R 13 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, Alternatively, a polycyclic cycloalkyl group such as an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
• one of the methylene groups constituting the ring is a group having a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group. may be replaced.
• one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
• R 12 , R 13 and R 14 are linear or branched alkyl groups
• at least two of R 12 , R 13 and R 14 are preferably methyl groups.
• R 12 , R 13 and R 14 preferably each independently represent a linear or branched alkyl group
• R 12 , R 13 and R 14 each independently represent a linear More preferably, it represents a triangular alkyl group.
• the repeating unit having an acid-decomposable group preferably takes the form of a copolymer with a repeating unit having at least one of a fluorine atom and a silicon atom. preferable.
• the repeating unit having an acid-decomposable group has at least one of a fluorine atom and a silicon atom (hereinafter referred to as "another repeating unit ), the other repeating unit has a fluorine atom-containing partial structure, for example, a group represented by formulas (F2) to (F4) described later, or a silicon atom
• the partial structure it is preferable to have, for example, groups represented by formulas (CS-1) to (CS-3) described later.
• Other repeating units are also preferably (meth)acrylate repeating units.
• R 57 to R 68 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (linear or branched). provided that at least one of R 57 to R 61 , at least one of R 62 to R 64 , and at least one of R 65 to R 68 is a fluorine atom or a fluorinated alkyl group (one or more of the alkyl groups is is a group substituted with a fluorine atom, may be a perfluoroalkyl group, and preferably has 1 to 4 carbon atoms). All of R 57 to R 61 and R 65 to R 67 are preferably fluorine atoms.
• R 62 , R 63 and R 68 are preferably fluoroalkyl groups (preferably having 1 to 4 carbon atoms), more preferably perfluoroalkyl groups having 1 to 4 carbon atoms. Also, R 62 and R 63 may be linked together to form a ring. As a preferred embodiment of the group represented by formula (F3), when R 62 and R 63 represent a perfluoroalkyl group, R 64 is a hydrogen atom.
• Specific examples of the group represented by formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, a 3,5-di(trifluoromethyl)phenyl group, and the like.
• Specific examples of the group represented by formula (F3) include a trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro(2- methyl)isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro(trimethyl)hexyl group, 2,2, 3,3-tetra
• R 12 to R 26 each independently represent a linear or branched alkyl group (having preferably 1 to 20 carbon atoms, preferably 1 to 10 is more preferable, and 1 to 6 are more preferable.) or a cycloalkyl group (the number of carbon atoms is preferably 3 to 20, and more preferably 6 to 10).
• L 3 to L 5 each represent a single bond or a divalent linking group.
• n represents an integer of 1 to 5; n is preferably an integer of 2-4.
• repeating units examples include the following repeating units.
• R 10 and R 11 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group optionally substituted with a fluorine atom (having 1 to 4 carbon atoms is preferred.).
• W 3 to W 6 are each independently a group represented by (F2) to (F4) above, a group represented by (CS-1) to (CS-3) above, or *-L A group represented by A-R F may be mentioned.
• LA represents a divalent linking group.
• R 2 F represents a group represented by (F2) to (F4) above or a group represented by (CS-1) to (CS-3) above.
• L A is not particularly limited, but includes, for example, an alkyl group in which -CH 2 - is substituted with -O- or -COO-.
• the number of carbon atoms in the alkyl group represented by L A is preferably 1-12, more preferably 1-10, and even more preferably 1-8.
• repeating units having at least one of a fluorine atom and a silicon atom are listed below, but the present invention is not limited thereto.
• X 1 represents a hydrogen atom, -CH 3 , -F or -CF 3 and X 2 represents -F or -CF 3 .
• the content of the repeating unit represented by the above formula (II) is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total repeating units in the specific polarity conversion compound A.
• the upper limit is, for example, preferably 60 mol % or less, more preferably 50 mol % or less.
• the content of repeating units having a fluorine atom or a silicon atom is preferably 5 mol% or more, more preferably 10 mol% or more, based on all repeating units in the specific polarity conversion compound A. 20 mol % or more is more preferable.
• the upper limit is, for example, preferably 100 mol% or less, more preferably 80 mol% or less, and even more preferably 60 mol% or less.
• the weight average molecular weight of the specific polarity conversion compound A is preferably 1,000 to 35,000, more preferably 3,000 to 20,000, more preferably 3,000 to 3,000, as a polystyrene equivalent molecular weight by GPC. More preferably 10,000.
• the specific polarity conversion compound A preferably satisfies the following requirements (requirement 1) in that the effects of the present invention are more excellent.
• Requirement 1 When the film (single film) made of the specific polarity conversion compound A is exposed to the entire surface under the same exposure conditions as in step 2 in the pattern forming method of the present invention, and the heat treatment is performed, the specific polarity conversion compound before the entire surface is exposed.
• the difference between the water contact angle on the surface of the film composed of the polarity conversion compound A and the water contact angle on the surface of the film composed of the specific polarity conversion compound A after the heat treatment is 10° or more.
• the water contact angle is measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.) in a measurement environment with a temperature of 23° C. and a relative humidity of 45%.
• the difference in water contact angle before and after the heat treatment is more preferably 10° or more, and even more preferably 15° or more.
• as an upper limit it is 30 degrees or less, for example.
• baking for example, 120° C. for 60 seconds may be performed at the time of forming the single film.
• the specific polar conversion compound B is a compound having a fluorine atom or a silicon atom and a group that forms a polar group by the action of an alkali (hereinafter also referred to as an "alkali-decomposable group").
• the specific polarity conversion compound B can be decomposed by the action of an alkaline developer during the development processing of step 3 to increase the solubility in the alkaline developer.
• the specific polarity conversion compound B is preferably a polymer, and the polymer preferably contains a repeating unit (repeating unit X) having an alkali-decomposable group.
• a fluorine atom or a silicon atom may be contained in the main chain of the resin or may be contained in a side chain.
• repeating unit having an alkali-decomposable group examples include the following types.
• the specific polar conversion compound B more preferably has a repeating unit (b B ′).
• the repeating unit (b B *) when the specific polarity conversion compound B has the repeating unit (b B *), the repeating unit (the repeating unit (b B ′), (b B ′′) having at least one of a fluorine atom and a silicon atom) different repeating units).
• the side chain having an alkali-decomposable group and the side chain having at least one of a fluorine atom and a silicon atom in the repeating unit (b B ′′) are bonded to the same carbon atom in the main chain, i.e. It is preferable that they have a positional relationship such as the following formula (K1).
• B1 represents the partial structure having the alkali-decomposable group
• B2 represents the partial structure having at least one of a fluorine atom and a silicon atom.
• alkali-decomposable groups include lactone group, carboxylic acid ester group (-COO-), acid anhydride group (-C(O)OC(O)-), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (-OSO 2 O-), sulfonate group (-SO 2 O-), etc. Lactone groups are preferred.
• the alkali-decomposable group is, for example, introduced into the side chain of the resin by being included in the repeating unit of (meth)acrylic acid ester, or polymerizing a polymerization initiator or chain transfer agent having an alkali-decomposable group. Any form that is sometimes used and introduced at the end of the polymer chain is preferred.
• repeating units having an alkali-decomposable group include repeating units having a lactone structure represented by formulas (KA-1-1) to (KA-1-17) described below.
• the repeating unit having an alkali-decomposable group is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, corresponding to the above repeating units (b B ′) and (b B ′′)). preferable.
• Examples of repeating units having an alkali-decomposable group include repeating units represented by formula (K0).
• R k1 represents a group containing a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or an alkali-decomposable group.
• R k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group containing an alkali-decomposable group.
• at least one of R k1 and R k2 represents a group containing an alkali-decomposable group.
• the alkali-decomposable group is preferably a group represented by X in the partial structure represented by formula (KA-1) or (KB-1).
• X in the formula (KA-1) or (KB-1) is a carboxylic acid ester group: -COO-, an acid anhydride group: -C(O)OC(O)-, an acid imide group: -NHCONH-, carboxylic It represents an acid thioester group: -COS-, a carbonate group: -OC(O)O-, a sulfate group: -OSO 2 O-, and a sulfonate group: -SO 2 O-.
• Y 1 and Y 2 each independently represent an electron-withdrawing group.
• the repeating unit having an alkali-decomposable group has a group having a partial structure represented by formula (KA-1) or (KB-1), so that the alkali-decomposable group is introduced into the repeating unit. structure, but as in the substructure represented by formula (KA-1) and the substructure represented by formula (KB-1) when Y 1 and Y 2 are monovalent,
• the group having the partial structure is a group having a monovalent or higher valence group from which at least one arbitrary hydrogen atom in the partial structure is removed.
• the partial structure represented by formula (KA-1) or (KB-1) is linked to the main chain of the specific polarity conversion compound B directly or via a substituent at any position.
• the partial structure represented by formula (KA-1) is a structure that forms a ring structure together with a group as X.
• X in formula (KA-1) is preferably a carboxylate group (that is, when KA-1 forms a lactone ring structure), an acid anhydride group, or a carbonate group, more preferably a carboxylate group. .
• the ring structure represented by formula (KA-1) may have a substituent, for example, it may have nka substituents Z ka1 .
• Z ka1 each independently represents a halogen atom, an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group.
• Z ka1 may be linked together to form a ring. Examples of the ring formed by combining Z ka1 include a cycloalkyl ring and a hetero ring (cyclic ether ring, lactone ring, etc.).
• nka represents an integer of 0 to 10, preferably an integer of 0 to 8, more preferably an integer of 0 to 5, even more preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 3.
• the electron-withdrawing group as Z ka1 is the same as the electron-withdrawing group as Y 1 and Y 2 described later. In addition, the electron-withdrawing group may be substituted with another electron-withdrawing group.
• Z ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron-withdrawing group, more preferably an alkyl group, a cycloalkyl group, or an electron-withdrawing group.
• the ether group one substituted with an alkyl group, a cycloalkyl group, or the like, that is, an alkyl ether group or the like is preferable.
• the electron-withdrawing group is the same as the electron-withdrawing group for Y 1 and Y 2 described later.
• the halogen atom as Z ka1 includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferred.
• the alkyl group as Z ka1 may have a substituent and may be linear or branched.
• the number of carbon atoms in the linear alkyl group is preferably 1-30, more preferably 1-20.
• the number of carbon atoms in the branched alkyl group is preferably 3-30, more preferably 3-20.
• Branched alkyl groups include those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and t-butyl group. preferable.
• the cycloalkyl group as Z ka1 may have a substituent and may be monocyclic or polycyclic. If polycyclic, the cycloalkyl group may be bridged. That is, in this case, the cycloalkyl group may have a bridged structure.
• Preferred monocyclic groups are, for example, cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclobutyl and cyclooctyl groups.
• Examples of polycyclic groups include groups having a bicyclo, tricyclo, or tetracyclo structure having 5 or more carbon atoms.
• adamantyl group for example, adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, ⁇ -pinel group, tricyclodecanyl group, tetocyclododecyl group, and androstanyl group.
• Alkyl groups are preferred.
• a group derived from a cycloalkane shown below is also preferable. At least one carbon atom in the cycloalkane may be substituted with a heteroatom such as an oxygen atom.
• Examples of the cycloalkane-derived group include adamantyl group, noradamantyl group, decalin group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, A cyclooctyl group, a cyclodecanyl group, or a cyclododecanyl group is preferable, and an adamantyl group, a decalin group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, or a tricyclodecanyl group.
• Nyl groups are more preferred.
• the above cycloalkane-derived group may have a substituent, and examples of the substituent include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group.
• the number of carbon atoms in the alkyl group and the alkyl group portion in the alkoxy group and alkoxycarbonyl group is preferably 1 to 6, more preferably 1 to 4.
• the alkyl group, alkoxy group, and alkoxycarbonyl group may further have a substituent, and examples of the substituent include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms). be done.
• the above group may further have a substituent, and examples of further substituents include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an alkyl group, an alkoxy group, and an alkoxy group.
• substituents include carbonyl groups, aralkyl groups, acyl groups, alkenyl groups, alkenyloxy groups, aryl groups, aryloxy groups, and aryloxycarbonyl groups.
• X in formula (KA-1) is a carboxylic acid ester group, and the partial structure represented by formula (KA-1) is preferably a lactone ring, and X in formula (KA-1) is a carboxylic acid ester. group and the partial structure represented by formula (KA-1) is more preferably a 5- to 7-membered lactone ring.
• a 5- to 7-membered lactone ring as a partial structure represented by formula (KA-1) has a bicyclo structure or a spiro structure. It is preferred that the other ring structure is condensed to form
• the structure represented by the formula (KA-1) having a lactone ring structure is preferably selected from the group consisting of the following (KA-1-1) to (KA-1-17), (KA-1- 1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1-14), or (KA-1-17 ) is more preferred.
• the structure represented by formula (KA-1) having a lactone ring structure may be directly bonded to the main chain.
• the above (KA-1-1) to (KA-1-17) may further have a substituent.
• substituents include those similar to the substituent Z ka1 that the ring structure represented by the above formula (KA-1) may have.
• the structure represented by the formula (KA-1) having a lactone ring structure represents, for example, a monovalent group
• one of the hydrogen atoms possessed by the member atoms of the lactone ring is removed to form a bond.
• a divalent group it is preferable that two of the hydrogen atoms of the member atoms of the lactone ring are removed to form a bond.
• a carboxylic acid ester group (-COO-) is preferable as X in formula (KB-1).
• Y 1 and Y 2 in formula (KB-1) each independently represent an electron-withdrawing group.
• electron-withdrawing groups include groups represented by the following formula (EW). * in formula (EW) represents a bond directly linked to (KA-1) or a bond directly linked to X in (KB-1).
• Rew1 and Rew2 each independently represent a hydrogen atom or a substituent. Preferred substituents are alkyl groups, cycloalkyl groups, and aryl groups.
• n ew is the repeating number of the linking group represented by —C(R ew1 )(R ew2 )— and represents an integer of 0 or 1; When new is 0, it represents a single bond, indicating that Yew1 is directly bonded .
• Y ew1 is a halogen atom, a cyano group, a nitrile group, a nitro group, a halo(cyclo)alkyl group represented by —C(R f1 )(R f2 )—R f3 , a haloaryl group, an oxy group, an ether group, a carbonyl group, a sulfonyl group, a sulfinyl group, and a combination thereof, or a bond.
• halo(cyclo)alkyl group refers to an at least partially halogenated alkyl group and cycloalkyl group
• haloaryl group refers to an at least partially halogenated aryl group
• the electron-withdrawing group may have, for example, the following structural formula.
• R ew3 and R ew4 each independently represent an arbitrary structure. Regardless of the structure of Rew3 and Rew4 , the site derived from the partial structure represented by formula (EW) has electron-withdrawing properties.
• Rew3 and Rew4 may be, for example, a bond connecting to the main chain of the resin, or may represent an alkyl group, a cycloalkyl group, or a fluorinated alkyl group.
• Y ew1 represents a bond
• the bond forms a bond with any atom or substituent.
• At least one group of Y ew1 , R ew1 and R ew2 may be linked to the main chain of the specific polarity conversion compound B via a further substituent.
• Y ew1 is one or two selected from the group consisting of an ether group, a carbonyl, a halogen atom, a halo(cyclo)alkyl group represented by —C(R f1 )(R f2 )—R f3 , and a haloaryl group. Groups in which more than one species are combined are preferred, and -COO-C(R f1 )(R f2 )-R f3 or -COO-haloaryl groups are more preferred.
• R ew4 is preferably a halogen atom, a halo(cyclo)alkyl group represented by —C(R f1 )(R f2 )—R f3 , or a haloaryl group.
• R f1 preferably represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group. More preferably, it represents a fluorine atom or a trifluoromethyl group.
• R f2 and R f3 each independently represent a hydrogen atom, a halogen atom, or an organic group.
• the organic group include an alkyl group, a cycloalkyl group, an alkoxy group, and the like, and examples include a perhaloalkyl group, a perhalocycloalkyl group, and a perhaloaryl group.
• R f2 preferably represents the same group as R f1 or is linked to R f3 to form a ring.
• R f2 and R f3 may combine with each other to form a ring.
• Examples of the ring formed by combining R f2 and R f3 include a (halo)cycloalkyl ring and a (halo)aryl ring.
• the (halo)alkyl group for R f1 to R f3 includes, for example, the alkyl group for Z ka1 described above and a halogenated structure thereof.
• the (per)halocycloalkyl group and (per)haloaryl group in R f1 to R f3 or in the ring formed by combining R f2 and R f3 with each other include, for example, the above-mentioned cycloalkyl group in Z ka1 is a halogenated structure, and a fluorocycloalkyl group represented by -C (n) F (2n-2) H, or a perfluoroaryl represented by -C (n) F (n-1) A group is preferred.
• the number of carbon atoms n is not particularly limited, 5 to 13 is preferable, and 6 is more preferable.
• R ew1 , R ew2 and Y ew1 may be linked to each other to form a ring.
• the ring which may be formed by combining at least two of Rew1 , Rew2 and Yew1 is preferably a cycloalkyl group or a heterocyclic group.
• a lactone ring group is preferred. Examples of the lactone ring include structures represented by the above formulas (KA-1-1) to (KA-1-17).
• Part or all of the partial structure of formula (KA-1) may also serve as an electron-withdrawing group as Y 1 or Y 2 in formula (KB-1).
• X in formula (KA-1) is a carboxylic acid ester group
• the carboxylic acid ester group may function as an electron-withdrawing group as Y 1 or Y 2 in formula (KB-1).
• the repeating unit having an alkali-decomposable group corresponds to the repeating unit (b B *) or the repeating unit (b B ′′) and has a partial structure represented by formula (KA-1)
• the alkali-decomposable group is more preferably a partial structure represented by -COO- in the structure represented by formula (KA-1).
• a repeating unit having an alkali-decomposable group can be a repeating unit having a partial structure represented by formula (KY-0).
• R 2 represents a linear, branched, or cyclic alkylene group, and when there are more than one, they may be the same or different.
• R 3 represents a linear, branched or cyclic hydrocarbon group in which some or all of the hydrogen atoms on the constituent carbon atoms are substituted with fluorine atoms.
• X represents an alkylene group, an oxygen atom, or a sulfur atom.
• Z and Za each independently represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond, and when there are multiple of them, they may be the same or different.
• * represents a bond to the main chain or side chain of the specific polarity conversion compound B; o is the number of substituents and represents an integer of 1 to 7; m is the number of substituents and represents an integer of 0 to 7; n represents the number of repetitions and represents an integer of 0 to 5;
• the structure of -R 2 -Z- is preferably a structure represented by -(CH 2 ) 1 -COO- (l represents an integer of 1 to 5).
• the linear or branched alkylene group represented by R 2 preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
• the number of carbon atoms in the cyclic alkylene group represented by R 2 is preferably 6-20, more preferably 6-10.
• the number of carbon atoms in the linear or branched hydrocarbon group for R 3 is preferably 1-30, more preferably 1-20, even more preferably 1-10.
• the number of carbon atoms in the cyclic hydrocarbon group for R 3 is preferably 6-20, more preferably 6-10.
• Specific examples of R 3 include the same specific examples of the alkyl group and cycloalkyl group as Z ka1 described above.
• Preferred numbers of carbon atoms and specific examples of the alkyl group and cycloalkyl group as R 4 and R are the same as those described above for the alkyl group and cycloalkyl group as Z ka1 .
• the acyl group for R 4 preferably has 1 to 6 carbon atoms, such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, and pivaloyl.
• the alkyl moiety in the alkoxy group and alkoxycarbonyl group as R 4 includes a linear, branched, or cyclic alkyl moiety, and the preferred number of carbon atoms and specific examples of the alkyl moiety are the alkyl are the same as those described for groups and cycloalkyl groups.
• the alkylene group as X includes a linear, branched, or cyclic alkylene group, and the number of carbon atoms and specific examples thereof are the linear, branched, or cyclic alkylene represented by R 2 It is the same as that explained in the first section.
• repeating unit having an alkali-decomposable group is more preferably a repeating unit having at least two or more alkali-decomposable groups.
• the repeating unit having an alkali-decomposable group has at least two alkali-decomposable groups, it preferably has a group having a partial structure having two alkali-decomposable groups, represented by the following formula (KY-1).
• the structure represented by formula (KY-1) does not have a bond, it is a group having a monovalent or higher valence group from which at least one arbitrary hydrogen atom in the above structure is removed.
• R ky1 and R ky4 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, an amide group, or an aryl represents a group, or R ky1 and R ky4 are attached to the same atom to form a double bond.
• R ky1 and R ky4 are bonded to the same atom to form a double bond
• the mode to do corresponds.
• R ky2 and R ky3 each independently represent an electron-withdrawing group, or R ky1 and R ky2 combine to form a lactone ring and R ky3 represents an electron-withdrawing group.
• the lactone ring is preferably a structure represented by (KA-1-1) to (KA-1-17) described above.
• Examples of the electron-withdrawing group include those similar to Y 1 and Y 2 in formula (KB-1) above, and are represented by a halogen atom, —C(R f1 )(R f2 )—R f3 .
• a halo(cyclo)alkyl group or haloaryl group is preferred.
• R ky3 is a halogen atom, a halo(cyclo)alkyl group represented by —C(R f1 )(R f2 )—R f3 described above, Alternatively, it represents a haloaryl group, and R ky2 and R ky1 combine to form a lactone ring, or R ky1 , R ky2 , and R ky3 do not have a halogen atom
• R ky1 , R ky2 and R ky4 may each be linked to each other to form a monocyclic or polycyclic structure.
• R ky1 and R ky4 include groups similar to Z ka1 in formula (KA-1).
• the above structures (KA-1-1) to (KA-1-17) are preferred.
• the electron-withdrawing group include those similar to Y 1 and Y 2 in the above formula (KB-1).
• the structure represented by formula (KY-1) is more preferably a structure represented by formula (KY-2) below.
• the structure represented by formula (KY-2) is a group having a monovalent or higher valence group from which at least one arbitrary hydrogen atom is removed from the above structure.
• R ky6 to R ky10 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, an amide group, or an aryl represents a group. Two or more of R ky6 to R ky10 may be linked together to form a monocyclic or polycyclic structure.
• R ky5 represents an electron-withdrawing group.
• Examples of the electron-withdrawing group include the same groups as Y 1 and Y 2 described above, a halogen atom, a halo(cyclo)alkyl group represented by -C(R f1 )(R f2 )-R f3 described above, or a haloaryl group is preferred.
• Specific examples of R ky5 to R ky10 include groups similar to Z ka1 in formula (KA-1).
• the structure represented by formula (KY-2) is more preferably a partial structure represented by formula (KY-3) below.
• L ky represents an alkylene group, an oxygen atom, or a sulfur atom.
• alkylene group represented by L ky include a methylene group and an ethylene group.
• L ky is preferably an oxygen atom or a methylene group, more preferably a methylene group.
• a preferred embodiment of the repeating unit having an alkali-decomposable group in the specific polarity conversion compound B is, for example, a repeating unit represented by the following formula (III).
• L represents a divalent organic group.
• R21 represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group.
• R22 represents a monovalent organic group.
• the repeating unit represented by formula (III) contains a structural site (alkali-decomposable site) that generates a polar group by the action of a fluorine atom and an alkali.
• this alkali-decomposable group may correspond to the alkali-decomposable site.
• R 22 has a strong electron-withdrawing group (eg, perfluoroalkyl group and hexafluoroisopropyl group) and L has, for example, a lactone group.
• -COOR 22 may also be applicable as an alkali-decomposable site.
• alkali-decomposable group examples include the already-described alkali-decomposable groups (e.g., lactone group, carboxylic acid ester group (-COO-), acid anhydride group (-C(O)OC(O)-), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (-OSO 2 O-), and sulfonate group (-SO 2 O-) -) etc.).
• alkali-decomposable groups e.g., lactone group, carboxylic acid ester group (-COO-), acid anhydride group (-C(O)OC(O)-), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (-OSO 2 O-), and sulfonate group (-SO
• a divalent organic group represented by L and a monovalent organic group represented by R 22 examples include an embodiment in which at least one of the organic groups has an alkali-decomposable group.
• the divalent organic group represented by L contains an alkali-decomposable group, and the monovalent organic group represented by R 22 is a fluorine atom. The aspect containing is mentioned.
• the monovalent organic group represented by R 22 is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group and an aryl group.
• the number of carbon atoms in the alkyl group is preferably 1 to 25, more preferably 1 to 20, still more preferably 1 to 12, and particularly preferably 1 to 6.
• the cycloalkyl group include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. preferable.
• the number of carbon atoms in the cycloalkyl group is preferably 5-20, more preferably 5-15.
• an aryl group having 6 to 10 carbon atoms is preferable, and examples thereof include a phenyl group, a naphthyl group, an anthryl group and the like.
• Alkyl groups, cycloalkyl groups and aryl groups further represent substituents.
• the substituent is not particularly limited, and examples thereof include a fluorine atom.
• the monovalent organic group represented by R 22 is preferably a linear, branched or cyclic alkyl group having a fluorine atom.
• Linear and branched alkyl groups having a fluorine atom represented by R 22 include linear and branched alkyl groups in which some or all of the hydrogen atoms are substituted with fluorine atoms.
• the number of carbon atoms is preferably 1-25, more preferably 1-20, still more preferably 1-12, and particularly preferably 1-6.
• the cyclic alkyl group having a fluorine atom represented by R 22 includes a cyclic alkyl group in which hydrogen atoms are partially or wholly substituted with fluorine atoms.
• the number of carbon atoms is preferably 6-20, more preferably 6-10.
• the divalent organic group represented by L is not particularly limited, and examples include an alkylene group (preferably having 1 to 20 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having a carbon number of 6 to 20), an aryl group (preferably an aromatic ring group having 6 to 10 ring members), and a divalent linking group combining a plurality of these.
• alkylene group, cycloalkylene group, and aryl group may further have a substituent.
• substituents include halogen atoms (preferably fluorine atoms) and hydroxyl groups.
• RA includes a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• Examples of the divalent organic group represented by L include, among others, the alkali-decomposable groups described above (e.g., lactone group, carboxylic acid ester group (-COO-), acid anhydride group (-C(O)OC( O)-), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (-OSO 2 O-), and sulfone
• a divalent organic group containing an acid ester group (—SO 2 O—) is preferred, and a divalent organic group formed by removing two hydrogen atoms from the partial structure represented by the above formula (KA-1) Organic radical containing groups are more preferred.
• the partial structure represented by the above formula (KA-1) is preferably a 5- to 7-membered lactone ring.
• the partial structure represented by formula (KA-1) and preferred embodiments thereof are as described above.
• L 11 represents a single bond or a divalent linking group.
• the divalent linking group represented by L 11 is not particularly limited, and examples thereof include —CO—, —O—, —SO—, —SO 2 —, —NR A —, an alkylene group (preferably a ⁇ 6. It may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an arylene group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring), and these A divalent linking group in which a plurality of groups are combined is exemplified.
• alkylene group, the cycloalkylene group, and the arylene group may have a substituent.
• substituents include halogen atoms (preferably fluorine atoms) and hydroxyl groups.
• RA includes a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• L 12 represents a divalent group formed by removing two hydrogen atoms from the partial structure represented by the above formula (KA-1).
• the partial structure represented by the above formula (KA-1) is preferably a 5- to 7-membered lactone ring.
• the partial structure represented by formula (KA-1) and preferred embodiments thereof are as described above.
• * 1 represents the bonding position with the ester group linked to the main chain
• * 2 represents the bonding position with the other ester group specified in formula (II).
• Repeating units having an alkali-decomposable group include acrylate repeating units (including systems having substituents at the ⁇ - and ⁇ -positions), styrene-based repeating units (including systems having substituents at the ⁇ - and ⁇ -positions), Vinyl ether repeating units, norbornene repeating units, repeating units of maleic acid derivatives (maleic anhydride, derivatives thereof, maleimide, etc.) are preferred, and acrylate repeating units are more preferred.
• the repeating unit having an alkali-decomposable group is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, when corresponding to the repeating unit (b B ′) or (b B ′′)), an alkali
• the specific polarity conversion compound A may have a group represented by the formulas (F2) to (F4) described above, or an alkali-decomposable group.
• the specific polarity conversion compound A has groups represented by the above formulas (CS-1) to (CS-3).
• the specific polarity conversion compound B may contain other repeating units other than the repeating unit having an alkali-decomposable group for the purpose of adjusting uneven distribution on the film surface.
• Other repeating units include, for example, repeating units having 5 or more carbon atoms (preferably 5 to 20 carbon atoms, for example) and having a hydrocarbon group having a CH 3 partial structure in the side chain.
• Examples of repeating units having a hydrocarbon group having a carbon number of 5 or more and having a CH3 partial structure in a side chain include repeating units in which these groups are directly bonded to the main chain, acrylic acid esters and methacrylic Examples thereof include repeating units of acid esters.
• the hydrocarbon group one or a combination of two or more selected from the group consisting of an aromatic hydrocarbon ring group and an alkyl group (which may be linear, branched, or cyclic) is preferably a group.
• the content of the repeating unit having an alkali-decomposable group in the specific polarity conversion compound B is preferably 10 to 100 mol%, more preferably 20 to 99 mol%, based on the total repeating units in the specific polarity conversion compound B. , more preferably 30 to 97 mol %, particularly preferably 40 to 95 mol %. Specific examples of repeating units having an alkali-decomposable group are shown below, but are not limited thereto.
• Ra represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• the content of repeating units having a fluorine atom or a silicon atom is preferably 5 mol% or more, more preferably 10 mol% or more, based on all repeating units in the specific polarity conversion compound B, 20 mol % or more is more preferable.
• the upper limit is, for example, preferably 100 mol % or less, more preferably 80 mol % or less.
• the weight average molecular weight of the specific polarity conversion compound B is preferably from 1,000 to 35,000, more preferably from 3,000 to 20,000, more preferably from 3,000 to 3,000, as a polystyrene equivalent molecular weight by GPC. More preferably 10,000.
• the specific polarity-converting compound B preferably satisfies the following requirements (requirement 2) because the effects of the present invention are more excellent.
• Requirement 2 When the film (single film) made of the specific polarity conversion compound B is brought into contact with the alkali developer used in step 3, the film (single film) made of the specific polarity conversion compound B that is brought into contact with the alkali developer.
• the difference between the water contact angle on the surface and the water contact angle on the surface of the film (single film) composed of the specific polarity conversion compound B after contact with the alkaline developer is 10° or more.
• the water contact angle is measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.) in a measurement environment with a temperature of 23° C. and a relative humidity of 45%.
• the difference in water contact angle before and after contact with the alkali developer is more preferably 10° or more, and even more preferably 15° or more. In addition, as an upper limit, it is 30 degrees or less, for example.
• the rinse treatment when the rinse treatment is performed after the alkali development treatment in the step 3, it is preferable to perform the same rinse treatment in the measurement of the requirement 2 as well.
• baking for example, 120° C. for 60 seconds may be performed during the formation of the single film.
• the specific polar conversion compound may be used singly or in combination of two or more.
• the content of the specific polarity conversion compound (the total when multiple types are present) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on the total solid content of the composition. preferable.
• 10.0 mass % or less is preferable, 8.0 mass % or less is more preferable, 5.0 mass % or less is still more preferable, and 3.0 mass % or less is especially preferable.
• the resist composition contains a solvent.
• the solvent preferably contains at least one solvent selected from the following (M1) and a solvent selected from the following (M2), and a solvent selected from the following (M1) and a solvent selected from the following (M2) It is more preferable to contain at least one or more of the solvents used.
• M1 Propylene glycol monoalkyl ether carboxylate
• M2 Propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain ketone, cyclic ketone, lactone, alkylene carbonate Further, the effects of the present invention are more excellent.
• a solvent selected from (M1) and a solvent selected from (M2) propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, and lactone and most preferably propylene glycol monoalkyl ether carboxylates, propylene glycol monoalkyl ethers, and gamma butyrolactone.
• the coatability of the resist composition is improved and the pattern can be formed with fewer development defects.
• the reason for this is that the solvent has a good balance of the solubility, boiling point, and viscosity of the specific acid-decomposable resin, so that unevenness in the thickness of the resist film and the generation of deposits during spin coating are more likely to be suppressed. It is speculated that Details of component (M1) and component (M2) are described in paragraphs [0218] to [0226] of WO2020/004306, the contents of which are incorporated herein.
• the solvent may further contain a solvent other than the solvent selected from (M1) and the solvent selected from (M2) (hereinafter also referred to as "other solvent").
• the content of the other solvent is preferably 5.0 to 30.0% by mass based on the total amount of the solvent.
• the resist composition may further contain an acid diffusion control agent.
• the acid diffusion control agent traps the acid generated from the photoacid generator or the like during exposure, and acts as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid.
• a known acid diffusion control agent can be appropriately used in the resist composition used in the pattern forming method of the present invention.
• an onium salt (hereinafter also referred to as “compound (CQ1)”), which is relatively weakly acidic with respect to the photoacid-generating component, can also be used as the acid diffusion control agent.
• CQ1 an onium salt
• the photoacid is produced by actinic rays or radiation irradiation.
• the weak acid is released by salt exchange to yield an onium salt having a strong acid anion.
• the strong acid is exchanged for a weak acid with lower catalytic activity, so that the acid is apparently deactivated and the acid diffusion can be controlled.
• Compounds (CQ1) are preferably compounds represented by the following formulas (d1-1) to (d1-3).
• R 51 is an organic group.
• the number of carbon atoms is preferably 1-30.
• Z 2c is an organic group.
• the number of carbon atoms in the organic group is preferably 1-30.
• this carbon atom when a carbon atom is adjacent to SO 3- specified in the formula, this carbon atom ( ⁇ carbon atom) is a fluorine atom and/or perfluoro Does not have an alkyl group.
• the ⁇ carbon atom is other than a ring member atom of a cyclic structure, and is preferably a methylene group.
• the ⁇ -position atom with respect to SO 3 — in Z 2c is a carbon atom ( ⁇ -carbon atom)
• the ⁇ -carbon atom also does not have a fluorine atom and/or a perfluoroalkyl group as a substituent.
• R 52 is an organic group (such as an alkyl group)
• Y 3 is —SO 2 —, a linear, branched or cyclic alkylene group, or an arylene group
• Y 4 is —CO— or — SO 2 —
• Rf is a hydrocarbon group having a fluorine atom (such as a fluoroalkyl group).
• Each M + is independently an ammonium cation, a sulfonium cation, or an iodonium cation.
• M 2 + in formulas (d1-1) to (d1-3) for example, cations in compounds represented by formula (ZI) and cations in compounds represented by formula (ZII) can be used.
• a basic compound (hereinafter referred to as "compound (CQ2)") having a nitrogen atom and whose basicity is reduced or lost by irradiation with actinic rays or radiation. ) can also be used.
• the compound (CQ2) is a compound that has a proton acceptor functional group and is decomposed by irradiation with actinic rays or radiation to reduce or eliminate the proton acceptor property, or change the proton acceptor property to acidic. be.
• the proton-accepting 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 cyclic polyether, It means a functional group having a nitrogen atom with a non-contributing lone pair of electrons.
• a nitrogen atom having a lone pair of electrons 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 proton acceptor functional groups include, for example, crown ether, azacrown ether, primary to tertiary amine, pyridine, imidazole, and pyrazine structures.
• the compound (CQ2) is decomposed by exposure to actinic rays or radiation to reduce or eliminate its proton acceptor property, or to generate a compound whose proton acceptor property has changed to an acidic state.
• the reduction or disappearance of proton acceptor property, or the change from proton acceptor property to acidity is a change in proton acceptor property due to the addition of protons to the proton acceptor functional group, specifically
• a proton adduct is produced from a compound (CQ2) having a proton acceptor functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.
• the proton acceptor property can be confirmed by measuring pH.
• the pKa of the compound generated by decomposition of the compound (CQ2) by irradiation with actinic rays or radiation is preferably pKa ⁇ -1, more preferably -13 ⁇ pKa ⁇ -1, and still more preferably -13 ⁇ pKa ⁇ -3. .
• Compounds thus generated may undergo intramolecular neutralization to a pKa of -1 or higher.
• Compound (CQ2) is preferably a compound represented by formula (c-1).
• W 1 and W 2 each independently represent -SO 2 - or -CO-.
• R f represents an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or an optionally substituted aryl group.
• A represents a single bond or a divalent linking group.
• X represents a single bond, —SO 2 —, or —CO—.
• B represents a single bond, an oxygen atom, or -N(R x )R y -.
• R x represents a hydrogen atom or an organic group.
• R y represents a single bond or a divalent organic group.
• R represents a monovalent organic group having a proton acceptor functional group.
• R x may combine with R y to form a ring, or may combine with R to form a ring.
• [C + ] represents a counter cation.
• At least one of W 1 and W 2 is preferably —SO 2 —, more preferably both are —SO 2 —.
• Rf is preferably an alkyl group optionally having a fluorine atom having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and a perfluoroalkyl group having 1 to 3 carbon atoms. More preferably, it is an alkyl group.
• the divalent linking group for A is preferably a divalent linking group having 2 to 12 carbon atoms, such as an alkylene group and a phenylene group.
• an alkylene group having at least one fluorine atom is preferable, and the number of carbon atoms is preferably 2-6, more preferably 2-4.
• a linking group such as an oxygen atom or a sulfur atom may be present in the alkylene chain.
• the alkylene group is preferably an alkylene group in which 30 to 100% of the hydrogen atoms are substituted with fluorine atoms, and more preferably the carbon atoms bonded to the Q site have fluorine atoms.
• the divalent linking group for A is preferably a perfluoroalkylene group, more preferably a perfluoroethylene group, a perfluoropropylene group, or a perfluorobutylene group.
• the monovalent organic group for Rx preferably has 2 to 30 carbon atoms, such as an alkyl group, a cycloalkyl group optionally having an oxygen atom in the ring, an aryl group, an aralkyl group, and an alkenyl group. mentioned.
• the alkyl group for Rx may have a substituent, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom and/or a nitrogen atom in the alkyl chain. may have.
• Examples of the substituted alkyl group include groups in which a linear or branched alkyl group is substituted with a cycloalkyl group (eg, adamantylmethyl group, adamantylethyl group, cyclohexylethyl group, etc.).
• the cycloalkyl group for Rx may have a substituent, and is preferably a cycloalkyl group having 3 to 20 carbon atoms.
• the cycloalkyl group may have an oxygen atom in the ring.
• the aryl group for Rx may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.
• the aralkyl group for Rx may have a substituent, preferably an aralkyl group having 7 to 20 carbon atoms.
• the alkenyl group for Rx may have a substituent, and examples thereof include groups having a double bond at any position of the alkyl group exemplified for Rx.
• the divalent organic group for Ry is preferably an alkylene group.
• the ring that can be formed by combining Rx and Ry includes, for example, a 5- to 8-membered ring containing a nitrogen atom, particularly preferably a 6-membered ring.
• the nitrogen atom contained in the ring may be a nitrogen atom other than the nitrogen atom directly bonded to X in -N(Rx)Ry-.
• R and Rx are bonded to each other to form a ring.
• the formation of a ring improves the stability and the storage stability of the composition using it.
• the ring preferably has 4 to 20 carbon atoms, may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom and/or a nitrogen atom in the ring.
• the nitrogen atom contained in the ring may be a nitrogen atom other than the nitrogen atom directly bonded to X in -N(Rx)Ry-.
• the monocyclic ring includes a 4-, 5-, 6-, 7-, and 8-membered ring containing a nitrogen atom.
• Such ring structures include, for example, a piperazine ring and a piperidine ring.
• Polycyclic rings include structures consisting of combinations of two or more monocyclic structures.
• Each of the monocyclic and polycyclic rings may have a substituent, such as a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group.
• alkoxy groups preferably 1 to 10 carbon atoms
• acyl groups preferably 2 to 15 carbon atoms
• acyloxy groups preferably 2 to 15 carbon atoms
• alkoxycarbonyl groups preferably 2 to 15 carbon atoms
• aminoacyl group preferably 2 to 20 carbon atoms.
• substituents may have further substituents if possible.
• Examples of aryl groups and cycloalkyl groups further having substituents include alkyl groups (preferably having 1 to 15 carbon atoms).
• substituents further possessed by the aminoacyl group include alkyl groups (preferably having 1 to 15 carbon atoms).
• the proton-accepting functional group in R is as described above, and has a partial structure such as crown ether, primary to tertiary amine, and nitrogen-containing heterocycle (pyridine, imidazole, pyrazine, etc.) structure. is preferred.
• a functional group having a nitrogen atom is preferable, and a group having a primary to tertiary amino group or a nitrogen-containing heterocyclic group is more preferable.
• all atoms adjacent to nitrogen atoms contained in the structures are preferably carbon atoms or hydrogen atoms.
• an electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly connected to the nitrogen atom.
• the monovalent organic group in such a monovalent organic group (group R) containing a proton-accepting functional group preferably has 2 to 30 carbon atoms, and is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group. and alkenyl groups, and each group may have a substituent.
• the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group in the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group containing a proton-accepting functional group in R are each Rx groups similar to the alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups mentioned above.
• substituents that each of the above groups may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a cycloalkyl group (preferably having 3 to 10 carbon atoms. may be substituted with a group having (such as an ester group)), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms), an acyl group (preferably having 2 to 20), acyloxy groups (preferably having 2 to 10 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 20 carbon atoms), and aminoacyl groups (preferably having 2 to 20 carbon atoms).
• substituents possessed by cyclic groups such as aryl groups and cycloalkyl groups include alkyl groups (preferably having 1 to 20 carbon atoms).
• substituents possessed by the aminoacyl group include, for example, 1 or 2 alkyl groups (preferably having 1 to 20 carbon atoms).
• [C + ] is preferably a sulfonium cation or an iodonium cation as a counter cation.
• sulfonium cations and iodonium cations cations in compounds represented by formula (ZI), cations in compounds represented by formula (ZII), etc. can also be used.
• a low-molecular-weight compound having a nitrogen atom and a group that is released by the action of an acid (hereinafter referred to as "compound (CQ3)").
• the compound (CQ3) is preferably an amine derivative having a group on the nitrogen atom that leaves under the action of an acid.
• the group that leaves 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, more preferably a carbamate group or a hemiaminal ether group.
• the molecular weight of the compound (CQ3) is preferably 100-1000, more preferably 100-700, even more preferably 100-500.
• Compound (CQ3) may have a carbamate group having a protecting group on the nitrogen atom.
• the protective group constituting the carbamate group is preferably a group represented by the following formula (d-1).
• Rb each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group ( preferably 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms).
• Rb's may be linked together to form a ring.
• the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are each independently a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, a functional group such as an oxo group, an alkoxy group, or It may be substituted with a halogen atom.
• Rb The same applies to the alkoxyalkyl group represented by Rb.
• Rb is preferably a linear or branched alkyl group, cycloalkyl group or aryl group, more preferably a linear or branched alkyl group or cycloalkyl group.
• Examples of the ring formed by connecting two Rb's to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
• Specific structures of the group represented by formula (d-1) include, but are not limited to, structures disclosed in paragraph [0466] of US Patent Publication No. US2012/0135348A1.
• the compound (CQ3) is preferably a compound having a structure represented by the following formula (6).
• l represents an integer of 0 to 2
• m represents an integer of 1 to 3
• Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
• the two Ra's may be the same or different, and the two Ra's may be linked together to form a heterocyclic ring together with the nitrogen atom in the formula.
• This hetero ring may contain a hetero atom other than the nitrogen atom in the formula.
• Rb has the same definition as Rb in formula (d-1) above, and preferred examples are also the same.
• the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra may be independently substituted with an alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb. It may be substituted with the same groups as the groups described above.
• alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above groups) for Ra include the same groups as the specific examples described above for Rb. be done.
• Zwitterions can also be used as acid diffusion control agents.
• the zwitterionic acid diffusion control agent preferably has a carboxylate anion and preferably also has a sulfonium or iodonium cation.
• a non-basic acid diffusion control agent is particularly preferable because the effects of the present invention are more excellent.
• the term "having no basicity" as used herein means a compound whose conjugate acid has a pKa of 4.5 or more.
• the non-basic acid diffusion control agent has an onium salt (compound (CQ1)) that is relatively weakly acidic with respect to the photoacid-generating component described above, and a nitrogen atom, A low-molecular-weight compound (compound (CQ3)) having a group that leaves under the action of an acid can be mentioned.
• the content of the acid diffusion control agent (the total when multiple types are present) is 0.1 to 10.0 mass with respect to the total solid content of the composition. %, more preferably 0.1 to 8.0% by mass, even more preferably 0.1 to 5.0% by mass.
• the acid diffusion controller may be used singly or in combination of two or more.
• the resist composition may contain a surfactant.
• a surfactant is contained, the adhesion is better and a pattern with fewer development defects can be formed.
• the surfactant is preferably a fluorine-based and/or silicon-based surfactant.
• the fluorine-based and/or silicon-based surfactants used herein do not include the specific polarity conversion compound, which is the component (C) described above.
• Fluorinated and/or silicon-based surfactants include surfactants disclosed in paragraphs [0218] and [0219] of WO2018/19395.
• One type of these surfactants may be used alone, or two or more types may be used.
• the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition.
• the resist composition contains a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, or a carboxylic acid alicyclic or aliphatic compounds containing groups).
• the resist composition may further contain a dissolution inhibiting compound.
• dissolution inhibiting compound as used herein means a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.
• the solid content in the resist composition is 10.0% by mass or more. That is, the resist composition has a solid content of 10.0% by mass or more relative to the total mass of the composition.
• the solid content in the resist composition is preferably 11.0% by mass or more, more preferably 12.0% by mass or more. Although the upper limit is not particularly limited, for example, 15.0% by mass or less is preferable.
• the pattern forming method of the present invention has the following steps.
• Step 1 A step of forming a resist film having a thickness of 500 nm or more using a resist composition
• Step 2 A step of subjecting the resist film to immersion exposure with radiation or actinic rays having a wavelength of 200 nm or less and performing heat treatment
• Step 3 A step of developing the exposed resist film with an alkali developer to form a pattern.
• Step 1 is a step of forming a resist film on a substrate using a resist composition.
• the resist composition is as described above.
• a method of forming a resist film on a substrate using a resist composition includes, for example, a method of coating the substrate with the resist composition.
• the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
• the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
• the resist composition can be applied onto substrates such as those used in the manufacture of integrated circuit devices (eg, silicon, silicon dioxide coatings) by a suitable coating method such as a spinner or coater.
• the coating method is preferably spin coating using a spinner.
• the rotation speed for spin coating using a spinner is preferably 1000 to 3000 rpm.
• the substrate may be dried to form a resist film. If necessary, various base films (inorganic film, organic film, antireflection film) may be formed under the resist film.
• a drying treatment may be performed on the coating film applied on the substrate.
• the drying method include a method of drying by heating. Heating can be carried out by a means provided in a normal exposure machine and/or a developing machine, and may be carried out using a hot plate or the like.
• the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
• the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, even more preferably 60 to 600 seconds.
• the film thickness of the resist film is 500 nm or more, more preferably 550 nm or more.
• the upper limit is preferably 700 nm or less, more preferably 600 nm or less.
• a topcoat composition may be used to form a topcoat on the upper layer of the resist film. It is preferable that the topcoat composition does not mix with the resist film and can be uniformly coated on the upper layer of the resist film.
• the topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. can be formed. For example, it is preferable to form a top coat containing a basic compound as described in JP-A-2013-61648 on the resist film. Specific examples of basic compounds that the topcoat may contain include basic compounds that the resist composition may contain.
• the topcoat preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.
• Step 2 is a step of subjecting the resist film to liquid immersion exposure with a predetermined wavelength and then heat-treating it.
• the exposure step includes a step of subjecting the resist film formed through step 1 to immersion exposure with radiation having a wavelength of 200 nm or less or actinic rays through a predetermined mask.
• Radiation or actinic rays with a wavelength of 200 nm or less include far-ultraviolet light with a wavelength of 1 to 200 nm, specifically ArF excimer laser (193 nm).
• step 2 after the exposure treatment, the resist film after exposure is subjected to heat treatment (post-exposure baking) before being subjected to the alkali development treatment in step 3.
• the heat treatment accelerates the reaction of the exposed area, resulting in better sensitivity and pattern shape.
• the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
• the heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, even more preferably 30 to 120 seconds.
• the heat treatment can be carried out by a means provided in a normal exposing machine and/or developing machine, and may be carried out using a hot plate or the like.
• Step 3 is a step of developing the exposed resist film with an alkaline developer to form a pattern.
• Examples of the development method include a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), and a method in which the developer is piled up on the surface of the substrate by surface tension and remains stationary for a certain period of time for development (paddle method). ), a method of spraying the developer onto the surface of the substrate (spray method), and a method of continuously ejecting the developer while scanning the developer ejection nozzle at a constant speed onto the substrate rotating at a constant speed (dynamic dispensing method). is mentioned. Further, after the step of developing, a step of stopping development may be performed while replacing the solvent with another solvent.
• the development time is not particularly limited as long as the resin in the unexposed areas is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
• the temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.
• an alkaline aqueous solution containing alkali is preferably used as the alkaline developer.
• the type of alkaline aqueous solution is not particularly limited, for example, quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. and an alkaline aqueous solution containing Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Suitable amounts of alcohols, surfactants and the like may be added to the alkaline developer.
• the alkali concentration of the alkali developer is usually 0.1 to 20 mass %. Further, the pH of the alkaline developer is usually 10.0 to 15.0.
• the pattern forming method preferably includes a step of washing with a rinse after step 3.
• Pure water is an example of the rinse solution used in the rinse step after the step of developing with an alkaline developer.
• An appropriate amount of surfactant may be added to pure water.
• An appropriate amount of surfactant may be added to the rinse solution.
• the method of the rinsing step is not particularly limited. For example, a method of continuously discharging the rinsing liquid onto the substrate rotating at a constant speed (rotation coating method), or a method of immersing the substrate in a tank filled with the rinsing liquid for a certain period of time. method (dip method), and method of spraying a rinse liquid onto the substrate surface (spray method).
• the pattern forming method of the present invention may include a heating step (post-baking) after the rinsing step. Post-baking removes the developer and rinse liquid remaining between and inside the patterns. In addition, the post-baking smoothes the resist pattern and improves the surface roughness of the pattern. Post-baking is usually performed at 40 to 250° C. (preferably 90 to 200° C.) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
• the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and substrate) to form a pattern on the substrate.
• the method for processing the substrate (or the underlying film and the substrate) is not particularly limited, but the substrate (or the underlying film and the substrate) is dry-etched using the pattern formed in step 3 as a mask.
• a method of forming a pattern is preferred. Dry etching is preferably oxygen plasma etching.
• Various materials used in the pattern forming method of the present invention contain impurities such as metals. preferably not included.
• the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less.
• examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, Zn, and the like.
• a method of reducing impurities such as metals contained in various materials for example, a method of selecting a raw material with a low metal content as a raw material constituting various materials, a method of filtering the raw materials constituting various materials with a filter. and a method of performing distillation under conditions in which contamination is suppressed as much as possible by, for example, lining the inside of the apparatus with Teflon (registered trademark).
• impurities may be removed with an adsorbent, or filter filtration and adsorbent may be used in combination.
• adsorbent known adsorbents can be used.
• inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
• Whether the metal impurities are sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing equipment.
• the content of the metal component contained in the cleaning liquid after use is preferably 100 mass ppt (parts per trillion) or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less.
• Conductive compounds are added to organic treatment liquids such as rinsing liquids in order to prevent damage to chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge.
• the conductive compound is not particularly limited, and examples thereof include methanol.
• the amount to be added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable developing properties or rinsing properties.
• Examples of chemical pipes include SUS (stainless steel), or antistatic polyethylene, polypropylene, or various pipes coated with fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.). can be used.
• Antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can also be used for filters and O-rings.
• the present invention also relates to an electronic device manufacturing method including the pattern forming method described above, and an electronic device manufactured by this manufacturing method.
• the electronic device of the present invention is preferably mounted in electric/electronic equipment (household appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.).
• the present invention also relates to an actinic ray-sensitive or radiation-sensitive resin composition (resist composition).
• the resist composition of the present invention is It contains the following components (A) to (D) and has a solid content of 10.0% by mass or more.
• Solvent
• the resist composition is the same as the resist composition used in the pattern forming method of the present invention, and the preferred embodiments are also the same.
• [Acid-decomposable resin] The structures of the acid-decomposable resins (Polymer-A to Polymer-G, Polymer-A', and Polymer-B') shown in Table 4 are shown below.
• the weight average molecular weight (Mw) and the degree of dispersion (“Pd” (Mw/Mn)) of the acid-decomposable resin were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene).
• the composition ratio (mol %) of the acid-decomposable resin was measured by 13 C-NMR (nuclear magnetic resonance).
• the acid-decomposable resins shown below were all synthesized according to a known synthesis method.
• Table 1 below shows the composition ratios (mol%), weight average molecular weights, and dispersities of Polymer-A to Polymer-G, Polymer-A', and Polymer-B'.
• the composition ratio (mol %) is shown in order from the left repeating unit of the acid-decomposable resin described above.
• Photoacid generator The structures of the photoacid generators (PAG-A to PAG-P) shown in Table 4 are shown below.
• Table 2 shows the structure and pKa of the acid generated by each photoacid generator during exposure.
• Acid diffusion control agent The structures of the acid diffusion control agents (Quencher-A to Quencher-G) shown in Table 4 are shown below. In the following description, Quencher-A and Quencher-D to Quencher-F correspond to non-basic acid diffusion control agents.
• the structures of the polarity conversion compounds (Surfactant-A to D, Surfactant-A' and Surfactant-B') shown in Table 4 are shown below.
• the repeating unit at the left end of Surfactant-A corresponds to a repeating unit having an alkali-decomposable group, and also corresponds to the repeating unit represented by the above formula (III).
• the repeating unit at the right end of Surfactant-B corresponds to a repeating unit having an acid-decomposable group, and also corresponds to the repeating unit represented by formula (II) above.
• the repeating unit at the right end of Surfactant-C corresponds to a repeating unit having an acid-decomposable group, and also corresponds to the repeating unit represented by formula (II) above.
• the repeating unit on the right end of Surfactant-D corresponds to a repeating unit having an acid-decomposable group, and also corresponds to the repeating unit represented by formula (II) above.
• Table 3 below shows the composition ratios (mol%), weight average molecular weights, and dispersities of Surfactants-A to D and Surfactant-A'.
• the composition ratio (mol %) is shown in order from the repeating unit on the left side of the polarity conversion compound (resin) described above.
• step 3 ⁇ Water contact angle of Surfactant-A>
• the film (single film) made of Surfactant-A is brought into contact with the alkaline developer used in step 3
• the surface of the film (single film) made of Surfactant-A that is brought into contact with the alkaline developer is brought into contact with water. It was confirmed that the difference between the angle and the water contact angle of the surface of the surface of the Surfactant-A film (single film) after contact with the alkaline developer was 10° or more.
• the step 3 refers to "for the resist film after post-exposure bake, Developing for 30 seconds with a tetramethylammonium hydroxide (TMAH) aqueous solution (2.38% by mass) as a developer”.
• TMAH tetramethylammonium hydroxide
• the wafer used for measurement was developed with a tetramethylammonium hydroxide (TMAH) aqueous solution (2.38% by mass) as a developer for 30 seconds using a spin coater "ACT-8" manufactured by Tokyo Electron Co., Ltd., followed by pure water. for 30 seconds. It was then spun dry. Then, the contact angle was measured in the same manner as described above at a point other than the measurement point for the contact angle measurement before the alkali development treatment (in other words, the measurement point was changed), and the difference in the contact angle was obtained. .
• TMAH tetramethylammonium hydroxide
• step 2 is the following part of [ArF exposure pattern formation and evaluation] ⁇ Pattern formation (1): Formation of positive pattern by ArF-wet exposure (Examples and comparative examples)> pattern exposure under predetermined conditions, and bake the resist film after exposure at 120° C. for 60 seconds”.
• the entire surface of the single film was exposed using an ArF excimer laser scanner (manufactured by ASML; PAS5500/1500, NA 0.75, Conventional, Sigma 0.500). Ultrapure water was used as the immersion liquid. Then, the single film after the overall exposure was baked at 120° C. for 60 seconds. After that, contact angle measurement is performed in the same manner as the above procedure at a point different from the measurement point for contact angle measurement before exposure and heat treatment (in other words, changing the measurement point), and the difference in contact angle is obtained. rice field.
• Surfactant-A' corresponds to a compound that does not have a group that generates a polar group by the action of an acid or a group that generates a polar group by the action of an alkali.
• the water contact angle of Surfactant-A′ before and after alkali development was confirmed in the same manner as Surfactant-A, and the difference was less than 10°.
• the water contact angle of Surfactant-A′ before and after heat treatment was confirmed in the same manner as Surfactant-B, and the difference was less than 10°.
• Surfactant-B' corresponds to a compound that does not have a group that generates a polar group by the action of an acid or a group that generates a polar group by the action of an alkali.
• the water contact angle of Surfactant-B′ before and after alkali development was confirmed in the same manner as for Surfactant-A, and the difference was less than 10°.
• the water contact angle of Surfactant-B′ before and after the heat treatment was confirmed in the same manner as Surfactant-B, and the difference was less than 10°.
• solid content means all components other than the solvent.
• content (% by mass) of each component other than the solvent shown in Table 4 means the content ratio with respect to the total solid content.
• content ratio in the “Component (D)/solvent” column shown in Table 4 means the content ratio (% by mass) of each solvent with respect to all solvents.
• solid content concentration means the solid content (% by mass) with respect to the total mass of the resist composition.
• an ArF excimer laser immersion scanner manufactured by ASML; XT1700i, NA 1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection
• ASML ArF excimer laser immersion scanner
• XT1700i NA 1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection
• Ultrapure water was used as the immersion liquid.
• the exposed resist film was baked at 120° C. for 60 seconds, developed with a tetramethylammonium hydroxide (TMAH) aqueous solution (2.38 mass %) as a developer for 30 seconds, and then rinsed with pure water for 30 seconds. Thereafter, this was spin-dried to obtain a line-and-space pattern (LS pattern) with a pitch of 140 nm and a space of 70 nm.
• TMAH tetramethylammonium hydroxide
• the pattern formation method of the present invention can form patterns with excellent defect suppression properties.
• the compound represented by the formula (ZI-3) was used as the photoacid generator, it was confirmed that the defect suppressing property of the formed pattern was more excellent (Examples 9 to 15, 24 to 26 See the results of Further, it was confirmed that when the acid-decomposable resin has two or more types of repeating units having a hydrophilic group, the defect-suppressing property of the formed pattern is more excellent (see the results of Examples 27 to 29, etc.).
• the resist composition of the comparative example was insufficient in these performances.
• pattern formation was performed in the same manner as in the pattern formation method of Comparative Example 1 except that the film thickness of the resist film was 100 nm (the solid content concentration of the resist composition: 4% by mass), and the same defect evaluation was performed. bottom. Although the number of defects in the formed pattern was reduced as compared with the pattern formation method of Comparative Example 1, the desired defect suppression performance was not achieved.
• pattern formation was performed in the same manner as the pattern formation method of Comparative Example 1 except that the pattern was formed by ⁇ Pattern formation (2): formation of positive pattern by ArF-dry exposure> shown below, and the same defect evaluation was performed. carried out. Although the number of defects in the formed pattern was reduced as compared with the pattern formation method of Comparative Example 1, the desired defect suppression performance was not achieved.
• ⁇ Pattern formation (2) Formation of positive pattern by ArF-dry exposure> Using a spin coater "ACT-12" manufactured by Tokyo Electron Co., Ltd., a silicon wafer (12 inch) is coated with an organic antireflection film forming composition ARC29A (manufactured by Brewer Science) and baked at 205 ° C. for 60 seconds. , an antireflection film having a film thickness of 82 nm was formed. Next, a resist composition was applied onto the obtained antireflection film using the same apparatus and baked at 120° C. for 60 seconds to obtain a film thickness corresponding to the resist composition (film thickness: see Table 4). A resist film was formed.
• ARC29A organic antireflection film forming composition manufactured by Brewer Science
• the obtained resist film was scanned with an ArF scanner PAS5500/1100 (NA 0.75, Annular, outer sigma 0.85, inner sigma 0.60) manufactured by ASML, with a pitch of 200 nm and a space of 100 nm. Pattern exposure was performed through a % halftone mask. The exposed resist film was baked at 120° C. for 60 seconds, developed with a tetramethylammonium hydroxide (TMAH) aqueous solution (2.38 mass %) as a developer for 30 seconds, and then rinsed with pure water for 30 seconds. Thereafter, this was spin-dried to obtain a line-and-space pattern (LS pattern) with a pitch of 200 nm and a space of 100 nm.
• TMAH tetramethylammonium hydroxide

Landscapes

• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• General Physics & Mathematics (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Materials For Photolithography (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=84919989

Family Applications (1)

Country Status (3)

Citations (4)

• 2022
  • 2022-06-28 JP JP2023535214A patent/JPWO2023286586A1/ja active Pending
  • 2022-06-28 WO PCT/JP2022/025662 patent/WO2023286586A1/ja not_active Ceased
  • 2022-07-06 TW TW111125323A patent/TW202307568A/zh unknown

Patent Citations (4)

Also Published As

Similar Documents

Legal Events