Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
• • 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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• • 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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
• • 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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/38—Esters containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/56—Ring systems containing bridged rings
  • C07C2603/58—Ring systems containing bridged rings containing three rings
  • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
  • C07C2603/74—Adamantanes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
  • Y10S430/1055—Radiation sensitive composition or product or process of making
  • Y10S430/106—Binder containing
  • Y10S430/111—Polymer of unsaturated acid or ester

Definitions

• the present invention relates to a positive resist composition and a resist pattern forming method.
• Such a resist for a short wavelength light source is required to have high resolution capable of reproducing a pattern with a fine dimension and high sensitivity to such a short wavelength light source.
• a chemically amplified resist containing a base resin and an acid generator (hereinafter referred to as PAG) that generates an acid upon exposure is known.
• Chemically amplified resists are classified into a positive type in which the alkali solubility in the exposed area increases and a negative type in which the alkali solubility in the exposed area decreases.
• the base resin of the resist currently used in ArF excimer laser lithography, etc. it has excellent transparency at around 193 nm, so the structural unit derived from (meth) acrylate ester chain is the main chain.
• the resin (acrylic resin) possessed by is used (see Patent Document 1, for example).
• Such resists are required to have various lithography characteristics such as a depth of focus (DOF) characteristic and a resist pattern shape in addition to sensitivity and resolution.
• DOE depth of focus
• the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a positive resist composition and a resist pattern forming method which have a small diffetat and excellent lithographic characteristics.
• the present invention employs the following configuration.
• the first aspect of the present invention is a resin composition having a structural unit derived from an ( ⁇ lower alkyl) acrylate ester whose main chain is increased in alkali solubility by the action of an acid.
• a positive resist composition comprising a component (A) and an acid generator component (B) that generates acid upon irradiation with radiation,
• the resin component (A) is a copolymer having at least two structural units obtained by allowing an acid to be present when polymerizing at least one monomer. This is a positive resist composition.
• the second aspect of the present invention includes a step of forming a resist film on a substrate using the positive resist composition of the first aspect, a step of exposing the resist film, and the resist film. Developing a resist pattern to form a resist pattern.
• ( ⁇ lower alkyl) acrylate ester means one or both of ⁇ lower alkyl acrylate ester such as methacrylate ester and acrylate ester. .
• a lower alkyl acrylate ester means one in which the hydrogen atom bonded to the ⁇ carbon atom of the acrylate ester is substituted with a lower alkyl group.
• (a-lower alkyl) acrylic ester force-derived structural unit means a structural unit having a structure in which the ethylenic double bond of (a-lower alkyl) acrylic ester is cleaved.
• “Structural unit” means a monomer unit constituting a polymer (a resin component).
• Consing a structural unit derived from (OC lower alkyl) acrylate ester in the main chain means two carbon atoms derived from an ethylenic double bond of the structural unit derived from lower alkyl) acrylate Means the main chain of the polymer.
• alkyl group includes linear, branched and cyclic monovalent saturated hydrocarbon groups.
• the “lower alkyl group” is an alkyl group having 1 to 5 carbon atoms.
• Exposure is a concept that includes general irradiation of radiation.
• a positive type resister having a small differential and excellent lithography characteristics. And a resist pattern forming method.
• the positive resist composition of the present invention has a resin component ( ⁇ ) having a constitutional unit derived from ( ⁇ lower alkyl) acrylate ester in the main chain, whose alkali solubility is increased by the action of an acid (hereinafter, ( ⁇ ⁇ ⁇ ) component) and an acid generator component ( ⁇ ) (hereinafter referred to as ( ⁇ ) component) that generates an acid upon exposure.
• ⁇ resin component having a constitutional unit derived from ( ⁇ lower alkyl) acrylate ester in the main chain, whose alkali solubility is increased by the action of an acid (hereinafter, ( ⁇ ⁇ ⁇ ) component) and an acid generator component ( ⁇ ) (hereinafter referred to as ( ⁇ ) component) that generates an acid upon exposure.
• an acid generated from the component ( ⁇ ) by exposure is obtained by containing the component ( ⁇ ) and the component () whose alkali solubility is increased by the action of an acid.
• the alkali solubility of the component (v) is increased, so that it is changed from alkali-insoluble to alkali-soluble. Therefore, in the formation of the resist pattern, if the resist film obtained by using the positive resist composition is selectively exposed, or if post-exposure heating ( ⁇ ) is performed in addition to the exposure, the exposed portion becomes alkaline.
• ⁇ post-exposure heating
• the component (ii) is a copolymer having at least two structural units obtained by polymerizing at least one monomer to produce the copolymer, and allowing an acid to be present.
• the component ( ⁇ ) is a resin having a structural unit (al) derived from a lower alkyl) acrylate ester in the main chain. Therefore, it is necessary to contain at least one (a-lower alkyl) acrylate ester.
• the acid dissociates the ester terminal part of the ( ⁇ lower alkyl) acrylate ester before polymerization or the ester terminal part of the structural unit (al)
• the structural unit (a2) derived from the acid is formed, and as a result, a copolymer having the structural unit (a2) derived from the structural unit (al) and the lower alkyl) acrylic acid is obtained.
• the structural unit (al) is represented as a structural unit in which R is a hydrogen atom or a lower alkyl group and X is a monovalent organic group in the following general formula (a-1). it can.
• the “ester terminal portion” means X in the following general formula (a-1). That is, the “ester terminal portion” means a group bonded to an oxygen atom adjacent to the carbo group in the lower alkyl) acrylate ester.
• the lower alkyl group of R is an alkyl group having 1 to 5 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an nbutyl group, an isobutyl group, tert-Butyl group, pentyl group, isopentyl group, neopentyl group and the like include lower straight chain or branched alkyl groups. It is preferable that a hydrogen atom or a methyl group is bonded to the ⁇ -position in terms of industrial availability.
• an “organic group” is a group containing a carbon atom, and an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (fluorine atom, chlorine atom, etc.), etc.) You may have.
• the monovalent organic group in X is not particularly limited, and examples thereof include lower end alkyl (explained later in the structural units (all) to (al4)) and the ester terminal portion of an acrylate ester (an acid dissociable, dissolution inhibiting group, Rataton-containing monocyclic or polycyclic group, polar group-containing aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group and the like.
• the structural unit (a2) means a structural unit in which R is a hydrogen atom or a lower alkyl group and X is a hydrogen atom in the general formula (a-1).
• a structural unit represented by the following general formula (4) is particularly preferable.
• R represents a hydrogen atom or a methyl group.
• the structural unit (a2) during polymerization, only the structural unit formed by the cleavage of the ethylenic double bond of (a lower alkyl) acrylic acid (after polymerization) ( A structural unit formed by dissociating the ester terminal portion of the structural unit derived from the ( ⁇ -lower alkyl) acrylate ester in component A) by the action of an acid is also included.
• the structural unit (a2) is derived from (oc lower alkyl) attalic acid produced by dissociating the ester terminal portion of ( ⁇ lower alkyl) acrylate ester by the action of the acid.
• Structural unit (a2 "1) and (lower alkyl) acrylic acid ester The structural unit (a2 "2) force generated by dissociation of the ester terminal portion of the structural unit derived from Telka et al.
• the action of the acid is preferably at least one kind selected.
• the component (A) has a structural unit (al 1) derived from a (a lower alkyl) acrylate ester having an acid dissociable, dissolution inhibiting group described later, that is, (A) Component Force
• the component (A) is composed of the structural unit (a2) in consideration of the effect of the present invention, the ease of synthesis, etc.
• “Structural unit (a2 ,, — 1—1)” The lower alkyl group that leads to the structural unit (al 1))
• the acid dissociable, dissolution-inhibiting group of the allylic acid ester contains the acid (when the copolymer is produced).
• “Structural unit ( a 2” 2-1) ” a structural unit formed by dissociation of the acid dissociable, dissolution inhibiting group of the structural unit (all) by the action of the acid.
• an acid capable of dissociating a part of the ( ⁇ lower alkyl) acrylate ester regardless of the structure of the ester terminal portion is used at the time of polymerization. However, it is used for an ordinary chemical amplification resist composition.
• the acid dissociable, dissolution inhibiting group that is dissociated even with an acid having a lower strength.
• the component ( ⁇ ) contains the structural unit (al l), the structural unit (a2 ′′ —l ⁇ 1) and Z or the structural unit (a2 ′′ ⁇ 2-1) are easily formed.
• the structural unit (a2 "-1-1) and Z or the structural unit (a2" —2-1) in particular, the structural unit (al l) is represented by the general formula (al—0-2) described later.
• X in the above general formula (a-1) such as the structural unit represented by formula (al-1-01) or (al-1-03), inhibits acid dissociable dissolution. It is easy to form when it is the group itself.
• the total amount of the structural unit (al) and the structural unit (a2) in the component (A) is , Based on the combined total of all structural units constituting the component (A), 50 to: LOO mol% and it is Sig 80 preferred: preferred than LOO mol 0/0 power.
• the proportion of the structural unit (a2) is excellent in the effect of the present invention, so that it is 1 to 20 mol% with respect to the total of all the structural units constituting the component (A). 2 to 15 mol% is more preferred 2 to 10 mol% is particularly preferred 2 to 6 mol% is most preferred.
• the proportion of the structural unit (a2) is 1 mol% or more, the effect of reducing the diffetat is high.
• it is 20 mol% or less, the lithography properties are good.
• the component (A) has a structural unit (al 1) derived from an (ex lower alkyl) acrylate ester group having an acid dissociable, dissolution inhibiting group as the structural unit (al). It is preferable. That is, the component (A) is preferably a copolymer having the structural unit (al) and the structural unit (a2).
• Examples of the lower alkyl group as a substituent at the a-position of the (a-lower alkyl) acrylic acid ester include the same as the lower alkyl group for R in the general formula (a-1).
• the acid dissociable, dissolution inhibiting group in the structural unit (all) is a group that can be dissociated from the component (A) by an acid generated from the component (B) described later at the time of exposure. So long as it has an alkali dissolution inhibiting property that makes the whole insoluble in alkali, and after dissociation, the entire component (A) can be changed to alkali soluble, the acid dissociation of the base resin for chemically amplified resists has been used so far. What is proposed as a soluble dissolution inhibiting group can be used.
• (Meth) acrylic acid ester means one or both of acrylic acid ester and methacrylic acid ester.
• the tertiary alkyl ester is an ester formed by substitution with a hydrogen atom of a carboxy group, an alkyl group or a cycloalkyl group, and the carbonyloxy group (—C (O) —0-), the alkyl group or cycloalkyl
• the tertiary carbon atom of the kill group is bonded to the structure.
• this tertiary alkyl ester when an acid acts, the bond is broken between the oxygen atom and the tertiary carbon atom.
• the alkyl group or cycloalkyl group may have a substituent.
• a group that becomes acid dissociable by constituting a carboxy group and a tertiary alkyl ester will be referred to as a “tertiary alkyl ester type acid dissociable, dissolution inhibiting group” for convenience.
• a cyclic or chain alkoxyalkyl ester forms an ester by replacing a hydrogen atom of a carboxy group with an alkoxyalkyl group, and the carbonyloxy group (C (O) —O—)
• C (O) —O— A structure in which the alkoxyalkyl group is bonded to the terminal oxygen atom is shown. In this alkoxyalkyl ester, when an acid acts, the bond is broken between the oxygen atom and the alkoxyalkyl group.
• R represents a hydrogen atom or a lower alkyl group
• X 1 represents an acid dissociable, dissolution inhibiting group.
• R represents a hydrogen atom or a lower alkyl group
• X 2 represents an acid dissociable, dissolution inhibiting group
• Y 2 represents an aliphatic cyclic group.
• X 1 is not particularly limited as long as it is an acid dissociable, dissolution inhibiting group, and examples thereof include an alkoxyalkyl group, a tertiary alkyl ester type acid dissociable, dissolution inhibiting group, and the like.
• a dissociable, dissolution inhibiting group is preferred.
• tertiary alkyl ester type acid dissociable, dissolution inhibiting group examples include aliphatic branched acid dissociable, dissolution inhibiting groups, and acid dissociable, dissolution inhibiting groups containing aliphatic cyclic groups.
• aliphatic in the claims and the specification is a relative concept with respect to aromatics, and is defined to mean a group, a compound, or the like that does not have aromaticity.
• the “aliphatic cyclic group” means a monocyclic group or polycyclic group having no aromaticity.
• the basic ring structure is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but is not limited to a hydrocarbon group (alicyclic group). Hydrocarbon group).
• the “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated. A polycyclic group is preferred.
• an aliphatic cyclic group examples include, for example, a lower alkyl group, a fluorine atom or a fluorinated alkyl group, which may or may not be substituted, a monocycloalkane, a bicyclo Polycycles such as alkane, tricycloalkane, tetracycloalkane, etc. Examples include a group obtained by removing one or more hydrogen atoms from a loalkane.
• monocycloalkanes such as cyclopentane and cyclohexane
• groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
• the structural unit derived from (oc lower alkyl) acrylate having a tertiary alkyl ester-type acid dissociable, dissolution inhibiting group is represented by the following general formula (1).
• the structural unit can be illustrated.
• R is a hydrogen atom or a methyl group
• R is an alkyl group having 1 to 4 carbon atoms
• R and R are each independently a linear or branched alkyl having 1 to 12 carbon atoms.
• Specific examples of the aliphatic branched acid dissociable, dissolution inhibiting group include a tert butyl group and a t ert -amyl group.
• examples of the acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group include a group having a tertiary carbon atom on the ring skeleton of the cycloalkyl group, specifically, 2-methyl- Examples thereof include a 2-adamantyl group and a 2-ethyl-2-adamantyl group.
• an aliphatic cyclic group such as an adamantyl group and a branched alkylene having a tertiary carbon atom bonded thereto.
• a structural unit represented by the following general formula (al—104) is particularly preferable.
• R is a hydrogen atom or a lower alkyl group, and R 2 and R 3 are each independently a lower alkyl group.
• R is the same as described above, and R 1 and R lb each represent a lower alkyl group (either linear or branched, preferably 1 to 5 carbon atoms). ]
• R 2 In general formula (al-1-03) and general formula (al-1 04),! / And R are the same as above.
• the lower alkyl group for R 2, R 3 , R 15 and R 16 may be either linear or branched, and is preferably an alkyl group having 1 to 5 carbon atoms.
• alkoxyalkyl group is preferably a group represented by the following general formula (5).
• R 17 and R 18 are each independently an alkyl group or a hydrogen atom, and R 19 is an alkyl group or a cycloalkyl group. Alternatively, the ends of R 17 and R 19 are bonded to form a ring. It may be formed.
• the alkyl group preferably has 1 to 15 carbon atoms, and most preferably a straight chain or branched chain ethyl group or a methyl group with a methyl group being preferred.
• one of R 17 and R 18 is preferably a hydrogen atom and the other is a force methyl group.
• R 19 is an alkyl group or a cycloalkyl group, preferably having 1 to 15 carbon atoms, and may be linear, branched or cyclic. When R 19 is linear or branched, it preferably has 1 to 5 carbon atoms, more preferably a methyl group, and most preferably an ethyl group.
• R 19 is cyclic, it is preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and more preferably 5 to LO: LO is most preferable.
• one or more polycycloalkanes such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group. And the like, in which a hydrogen atom is removed.
• Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. It is done. Among them, a group in which one or more hydrogen atoms are removed from adamantane is preferable.
• R 17 and R 19 are each independently an alkylene group having 1 to 5 carbon atoms, and the end of R 19 and the end of R 17 may be bonded together.
• a cyclic group is formed by R 17 , R 19 , the oxygen atom to which R 19 is bonded, and the carbon atom to which the oxygen atom and R 17 are bonded.
• the cyclic group a 4- to 7-membered ring is preferable, and a 4- to 6-membered ring is more preferable.
• Specific examples of the cyclic group include a tetrahydrobiranyl group, Examples thereof include a tetrahydrofuranyl group.
• R is the same as described above.
• X 2 is the same as X 1 in the formula (a 1-0-1).
• Y 2 is a divalent aliphatic cyclic group.
• Y 2 is a divalent aliphatic cyclic group, the same as described in the above “aliphatic cyclic group” can be used except that a group in which two or more hydrogen atoms are removed is used. .
• examples of the structural unit (al 1) include structural units represented by the following general formulas (al-1) to (al-4).
• X ′ represents a tertiary alkyl ester type acid dissociable, dissolution inhibiting group
• Y represents a lower alkyl group having 1 to 5 carbon atoms, or an aliphatic cyclic group
• n represents 0 or 1 to Represents an integer of 3
• m represents 0 or 1
• R is the same as defined above
• R 1 ′ and R 2 ′ each independently represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms;
• At least one of R 1 'and R 2 ' is preferably a hydrogen atom, more preferably a hydrogen atom.
• n is preferably 0 or 1.
• X ' is the same as the tertiary alkyl ester-type acid dissociable, dissolution inhibiting group exemplified in X 1 above. It is something like.
• Examples of the aliphatic cyclic group for Y include the same as those exemplified in the description of the “aliphatic cyclic group” above.
• the structural unit (all) one type may be used alone, or two or more types may be used in combination.
• the structural unit represented by the general formula (al-1) is specifically preferred ( al 1 1 1 to ( al 1 1 1 6 ) or (ai 1 1 1 35) to (al 1 It is more preferable to use at least one selected from the structural unit forces represented by —41).
• the structural unit (al) in particular, the structural units of the formula (al— 1— 1) to the formula (al-1 1 4) are used.
• the following general formula (al-02) is also preferable.
• R represents a hydrogen atom or a lower alkyl group
• R 11 represents a lower alkyl group
• R represents a hydrogen atom or a lower alkyl group
• R ′′ represents a lower alkyl group
• h represents an integer of 1 to 3
• R is the same as described above.
• the lower alkyl group for R 11 is the same as the lower alkyl group for R, and is preferably a methyl group or an ethyl group! /.
• R is the same as described above.
• the lower alkyl group for R 12 is the same as the lower alkyl group for R, and a methyl group or an ethyl group is preferred, and an ethyl group is most preferred.
• h is preferably 1 or 2, and most preferably 2.
• the structural unit (al l) is selected as a group force that is a structural unit force represented by the general formula (al-1-01) or (a 1-1 -03). It is preferable that at least one of them is excellent in the effect of the present invention.
• the amount of the structural unit (al l) based on the combined total of all structural units constituting the component (A), 1 0-80 Monore 0/0 force S Preferably, 20-70 Monore 0 / more preferably 0 force S, and most preferably 25 to 50 Monore 0/0 force S further favorable Mashigu 30-40 mol%.
• Component (A) is derived from (OC lower alkyl) acrylate ester having a latathone-containing monocyclic or polycyclic group in addition to the structural unit (al) as the structural unit (al). Preferred to have units (al 2).
• the latonone-containing monocyclic or polycyclic group of the structural unit (al2) can be used to enhance the adhesion of the resist film to the substrate or to develop water-containing development when component (A) is used to form the resist film. It is effective in increasing the affinity with the liquid.
• the ratatone-containing monocyclic or polycyclic group refers to a cyclic group containing one ring (lataton ring) containing an O C (O) structure.
• the rataton ring is counted as the first ring, and when only the rataton ring is present, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure.
• any structure can be used without particular limitation as long as it has such a structure (-0— C (O) —) and a cyclic group. It is.
• the latathone-containing monocyclic or polycyclic latonic ring is a 5-membered ring.
• a structural unit derived from an (a-lower alkyl) acrylic acid ester having a cyclic group is preferable because it is excellent in the effects of the present invention.
• Examples of the structural unit that can be used include the structural unit represented by the following general formula (2).
• L is represented by the following general formula ( 3) represents a rataton structure, and A and L are bonded by 1 to 2 linking groups.
• any one or two of R to R is a linking group with A in the general formula (2), and the remaining
• examples of the latatin-containing monocyclic group include groups in which one hydrogen atom has been removed from a petit latataton such as ⁇ -petit latataton.
• the effect of the present invention is particularly excellent when the structural unit (al 2) is at least one selected from the group force represented by the following general formula (a2-1). Therefore, it is preferable.
• R is a hydrogen atom or a lower alkyl group
• R ′ is independently a hydrogen atom, a lower alkyl group, or an alkoxy group having 1 to 5 carbon atoms.
• the lower alkyl group for R and R 'in the general formula (a2-1) is the same as the lower alkyl group for R in the structural unit (a11).
• R ′ is preferably a hydrogen atom in view of industrial availability.
• examples of the latathone-containing polycyclic group include groups in which a bicycloalkane, tricycloalkane, or tetracycloalkane having a latathone ring has one hydrogen atom removed.
• the group having the following structural formula except for one latathone-containing tricycloalkane-powered hydrogen atom is advantageous in terms of industrial availability and the like.
• R is a hydrogen atom or a lower alkyl group
• R ′ is a hydrogen atom, a lower alkyl group, or an alkoxy group having 1 to 5 carbon atoms
• m is an integer of 0 or 1.
• R and R ′ are the same as R and R ′ in general formula (a2-1).
• the structural units represented by the general formulas (a2-2) to (a2-5) are illustrated more specifically below.
• the structural unit from which (a lower alkyl) acrylate ester force having a latathone-containing polycyclic group is also represented by the general formula (a2-2) or (a2-3) It is preferable to use at least one selected from the group powers constituting unit force. Specifically, the formulas (a2 2-1), (a2 2-2), (a2 3-1), (a2 3-2), (a2 3-9) and (a2— It is preferable to use at least one selected from 3-10).
• component (A) as the structural unit (a l 2), one type may be used alone, or two or more types may be used in combination.
• a polar group-containing aliphatic hydrocarbon group is further added in the component (A), as a structural unit (al), in addition to the structural unit (all), or in addition to the structural units (all) and (al 2). It preferably has a structural unit (al 3) derived from (ex lower alkyl) acrylate ester.
• Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, and a hydroxyalkyl group substituted with a partial S hydrogen atom of an alkyl group, and a hydroxyl group is particularly preferred.
• Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) and an alicyclic hydrocarbon group.
• a polycyclic aliphatic hydrocarbon group (polycyclic group) is preferred.
• Examples of the polycyclic group include resins for resist compositions for ArF excimer lasers. ⁇ Many proposed V, medium powers can be selected and used as appropriate.
• Examples of the structural unit derived from (a lower alkyl) acrylate ester containing a hydroxyl group-containing aliphatic hydrocarbon group include a structural unit represented by the following general formula (11).
• R is a hydrogen atom or methyl group, A is a monocyclic or bridged ring having 6 to 12 carbon atoms
• a divalent to trivalent alicyclic hydrocarbon group k represents an integer of 1 to 2;
• the structural unit (al3) among these, a hydroxyl group, a cyano group, a carboxy group, or an aliphatic polyvalent group containing a hydroxyalkyl group in which part of hydrogen atoms of an alkyl group is substituted with a fluorine atom.
• a structural unit containing a cyclic group and derived from an ( ⁇ lower alkyl) acrylate ester is more preferable.
• the polycyclic group include groups obtained by removing two or more hydrogen atoms from bicycloalkane, tricycloalkane, tetracycloalkane and the like.
• groups in which two or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
• a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
• Such a polycyclic group can be used by appropriately selecting from among many proposed polymers (resin components) for resist compositions for ArF excimer lasers.
• groups in which two or more hydrogen atoms are removed from adamantane groups in which two or more hydrogen atoms are removed from norbornane, and two or more hydrogen atoms are removed from tetracyclododecane!
• the group is industrially preferred.
• the structural unit (al3) when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, ( ⁇ lower alkyl) acrylic
• the structural unit derived from the hydroxyethyl ester power of an acid is preferred, and when the hydrocarbon group is a polycyclic group, the structural unit represented by the following formula (a3-1) is represented by (a3-2): And a structural unit represented by (a3-3) is preferable.
• the structural unit (al3) is at least one selected from the group force that is the structural unit force represented by the following formula (a3-1), the effects of the present invention are excellent. preferable.
• j is preferably 1 or 2, and more preferably 1.
• j is 2, it is preferable that the hydroxyl group is bonded to the 3rd and 5th positions of the adamantyl group.
• j is 1, a hydroxyl group is preferably bonded to the 3rd position of the adamantyl group.
• q is preferably 1.
• the cyan group is preferably bonded to the 5th or 6th position of the norbornyl group.
• t ′ is preferably 1. 1 is preferably 1. s is preferably 1. It is preferable that a 2-norbornyl group or a 3-norbornyl group is bonded to the end of the carboxy group of ( ⁇ lower alkyl) acrylic acid! /. Fluorine alkyl alcohol is preferably bonded to the 5th or 6th position of the norbornyl group! /.
• one type may be used alone, or two or more types may be used in combination.
• the proportion of the structural unit (al3) in the component (A) is 5 to 50 mol% with respect to all the structural units constituting the component (A).
• 15 ⁇ 45 mole 0/0 is the most favorable preferable more preferably fixture 15 to 35 mole 0/0 more preferably tool 15-25 mol 0/0.
• the component (A) includes other structural units (al4) other than the structural units (al) to (al3) as the structural unit (al) within the range not impairing the effects of the present invention! Moyo! /
• the structural unit (al4) is not classified into the above structural units (al 1) to (al3), and is not particularly limited as long as it is another structural unit.
• ArF excimer lasers for ArF excimer lasers, for KrF excimer lasers (preferably Can be used for resists such as ArF excimer laser), which have been known for their strength.
• the structural unit (al4) for example, a structural unit containing an acid non-dissociable aliphatic polycyclic group and derived from a (lower alkyl) acrylate ester is preferable.
• the polycyclic group are the same as those exemplified in the case of the structural unit (all), for ArF excimer laser, for KrF excimer laser (preferably Ar F excimer).
• a number of conventionally known strengths can be used as the resin component of resist compositions such as for lasers.
• At least one kind selected from tricyclodecanyl group, adamantyl group, tetracyclododecyl group, isobornyl group and norbornyl group is preferable in terms of industrial availability.
• These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.
• structural unit (al4) include those having the structures of the following general formulas (a4-l) to (a4-5).
• the powerful structural unit (al4) is not an essential component of the component (A), but when it is included in the component (A), it is added to the total of all structural units constituting the component (A). in contrast, the structural unit (AL4) 1 to 30 mole 0/0, and preferably to 5 to 20 mole 0/0 contained preferably.
• the component (A) contains at least the structural units (al 1), (al 2) and
• copolymer having all of (a2) (hereinafter referred to as copolymer (A1)) is preferred because of excellent effects of the present invention.
• copolymer (A1) in particular, the structural unit represented by the above general formula (1) as the structural unit (all), the structural unit represented by the above general formula (2) as the structural unit (al2), A copolymer containing the structural unit represented by the general formula (4) as the structural unit (a2) is preferred.
• composition of the copolymer (A1), the structural unit (al l) 10 to 60 mol%, the structural unit (al2) is from 5 to 60 mole 0/0, the structural unit (AL3) force to 40 mole 0/0, the structural unit (a2) is that particularly preferred instrument is within the limits of 1 to 30 mol 0/0, the structural unit (al l) is 20 to 50 mol%, the structural unit (al2) power 20-60 Monore 0 / 0, single stand (al3) force 5 to 35 Monore 0/0, single stand (a2) power 2 to 20 Monore It is preferable to be within the range of%.
• the component (A) is a structural unit (al l), (al2) and (a2) a terpolymer having a force, or a structural unit (al l), (al2) (Al3) and (a2) are preferred quaternary copolymers.
• the mass average molecular weight (Mw) of the component (A) is not particularly limited, but is preferably in the range of 2,000-40,000 ⁇ . It is particularly preferable that it is within the range of 3,000 to 30,000, and it is particularly preferable that it is within the range of 4,000 to 25,000. If it is smaller than the upper limit of this range, it has sufficient solubility in a resist solvent for use as a resist, and if it is larger than the lower limit of this range, the dry etching resistance and resist pattern cross-sectional shape are good.
• the degree of dispersion (Mw / Mn) i is preferably 1.0 to 5.0 force S, more preferably 1.0 to 3.0 force S, and most preferably 1.2 to 2.5.
• the component (A) is produced by a production method generally used for production of a polymer, for example, a known polymerization method such as radical polymerization, except that an acid is present during production. Can do. At this time, the acid addition may be performed at the same time as the polymerization of the monomer or after the polymerization reaction is completed.
• a production method generally used for production of a polymer for example, a known polymerization method such as radical polymerization, except that an acid is present during production. Can do.
• the acid addition may be performed at the same time as the polymerization of the monomer or after the polymerization reaction is completed.
• the polymerization method includes a solution polymerization method in which at least one monomer and a polymerization initiator are dissolved in a solvent, added to the polymerization solvent, and the monomer is radically polymerized at a predetermined polymerization temperature. It is preferable to use it.
• a chain transfer agent may be used in combination.
• a —C (CF 3) 1 OH group is introduced to the terminal of the copolymer (A).
• some of the hydrogen atoms in the alkyl group are fluorine atoms.
• a copolymer having a substituted hydroxyalkyl group introduced is effective in reducing diffetats and LER (Line Edge Roughness).
• the polymerization initiator is not particularly limited as long as it is generally used as a radical generator.
• 2,2'-azobisisobutyric-tolyl 2,2'-azobis (2- Methylbutyrate-tolyl), 2,2'-azobisisobutyrate dimethyl, 1,1'-azobis (cyclohexan-1-carbo-tolyl), 4,4'-azobis (4-cyananovaleric acid), etc.
• Azo compound decano Ylperoxide, lauroyl peroxide, benzoyl peroxide, bis (3,5,5-trimethylhexanoyl) peroxide, succinic acid peroxide, tert butyl peroxide 2-ethylhexanoate, tert butyl peroxypivalate, Organic peroxides such as 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate can be used alone or in combination.
• the amount of the polymerization initiator used can be selected according to the target Mw, monomer, polymerization initiator, chain transfer agent, type of solvent, composition, polymerization temperature, dropping rate and the like.
• chain transfer agent for example, known thiol compounds such as dodecanethiol, mercaptoethanol, mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid and the like can be used alone or in combination.
• the amount of chain transfer agent used can be selected according to the target Mw, monomer, polymerization initiator, chain transfer agent, type of solvent, composition, polymerization temperature, dropping rate, and the like.
• the polymerization solvent is preferably a solvent that dissolves a monomer, a polymerization initiator, a chain transfer agent, and a solvent that dissolves a copolymer obtained by polymerization.
• a solvent that dissolves a monomer e.g., acetone, methyl ethyl ketone, methyl amyl ketone, and cyclohexanone
• ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, and cyclohexanone
• ethers such as tetrahydrofuran, dioxane, glyme, and propylene glycol monomethyl ether
• esters such as ethyl acetate and lactate ethyl
• propylene glycol methyl ether acetate Ether esters such as y
• ratatones such as butyrolatatane, and the like, which can be used alone or in combination.
• the acid used for the production of the component (A) does not have polymerizability with respect to the monomer used for the production of the copolymer, and at least a part of the ( ⁇ lower alkyl) acrylate ester. It is defined as being capable of dissociating a ster end (X in the above general formula (a-1). For example, an acid dissociable, dissolution inhibiting group of the structural unit (all)).
• a strong acid having a pKa of 2.0 or less at 25 ° C. in water More preferred is 1.0 or less, and particularly preferred is 0.5 or less strong acid.
• strong acids include perfluorocarboxylic acids such as trifluoroacetic acid, trifluoromethanesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid and its hydrate, benzenesulfonic acid and its hydrate.
• Organic sulfonic acids such as sulfuric acid, hydrochloric acid, nitric acid, Examples thereof include perchloric acid and hydrobromic acid. Two or more of these strong acids may be used in combination. Of these, sulfuric acid is most preferred because of the excellent effects of the present invention.
• the acid addition method is not particularly limited.
• the amount of acid added during polymerization of the monomer depends on the ratio of the target structural unit (a2) and the amount used ( ⁇ lower alkyl). It can be set as appropriate depending on the structure of the ester end of the acrylic ester, the type of acid used, and the like.
• an acid be present in the solution at a concentration of 0.1 to LOOOppm. It is more preferred to be present at 1 to 500 ppm. It is particularly preferred that acid is present at a concentration of 5 to 300 ppm. Most preferred is 5 to 50 ppm.
• the component (A) can be obtained through the following step (P) and at least one of the step (Q-1) and the step (Q-2) (hereinafter referred to as the step (Q-1). ) And step (Q 2) may be combined with step (Q) t).
• Step (Q-1) A step of generating (-lower alkyl) acrylic acid by dissociating the ester terminal of (a lower alkyl) acrylic acid ester by the action of an acid.
• X @ (P) can be carried out by radical polymerization (solution polymerization) in a polymerization solvent, and a known method force can be selected without limitation.
• a method for example, (1) a monomer is dissolved in a solvent together with a polymerization initiator, and the mixture is heated and polymerized as it is.
• the so-called dropping method in which the monomer and the polymerization initiator are separately dissolved in the solvent, if necessary, and dissolved in the heated solvent.
• So-called independent droplets that are dropped and polymerized separately Examples thereof include (4) an initiator dropping method in which the above monomer is dissolved in a solvent and heated, and a polymerization initiator dissolved in a solvent is separately dropped to polymerize.
• the independent dropping method (3) is preferred.
• a chain transfer agent may be used as described above.
• the dropping method of (2) to (4) it may be mixed with a monomer and dropped with a polymerization initiator which may be dropped or further dissolved in a preheated solvent. May be.
• the composition of the dropped monomer, the composition ratio of the monomer, the polymerization initiator, and the chain transfer agent may be changed with the dropping time.
• the polymerization temperature can be appropriately selected depending on the boiling point of the solvent, monomer, chain transfer agent, etc., the half-life temperature of the polymerization initiator, and the like. Since polymerization is difficult to proceed at low temperatures, there is a problem in productivity, and when it is higher than necessary, there is a problem in terms of stability of the monomer and the resulting copolymer. Therefore, it is preferably selected in the range of 40 to 120 ° C, particularly preferably 60 to 100 ° C.
• the dropping time in the dropping method is short, the molecular weight distribution tends to be widened, and a large amount of solution is dripped at a time.
• Heat hysteresis force S is not preferable because productivity is reduced. Therefore, a range force of 30 minutes to 24 hours, preferably 1 hour to 12 hours, particularly preferably 2 hours to 8 hours is selected.
• the temperature After completion of the dropping in the dropping method and after raising the temperature to the polymerization temperature in the batch method, it is preferable to maintain the temperature for a certain period of time or to mature by raising the temperature to react the remaining unreacted monomer. If the aging time is too long, the production efficiency per hour is lowered, and an unnecessarily high heat history is applied to the copolymer, which is not preferable. Therefore, it is usually selected within the range of 12 hours, preferably within 6 hours, particularly preferably within the range of 1 to 4 hours.
• X @ (P) in particular, at least an ( ⁇ -lower alkyl) acrylate ester having an acid dissociable, dissolution inhibiting group and a ratatone-containing monocyclic or polycyclic group (a lower alkyl group) It is preferable to copolymerize two or more monomers including an acrylate ester, and in particular, a (lower alkyl) acrylate ester having an acid dissociable, dissolution inhibiting group, and a ratatone-containing monocyclic or polycyclic monomer. (A lower alkyl) acrylate ester with a cyclic group It is preferable to copolymerize a (lower alkyl) acrylate ester containing a polar group-containing aliphatic hydrocarbon group.
• the step (Q) may be performed at the same time as the step (i) or after the step (i).
• step (concurrently) means that the polymerization of the monomer is performed in the presence of an acid
• step (ii) means that the acid is added after stopping the polymerization reaction. Means that.
• step (Q) and step (i) are performed simultaneously, step (ii), step (Q-1) and step (Q2) can proceed in parallel.
• step (ii) by adding an acid during the polymerization reaction of the ( ⁇ -lower alkyl) acrylate ester contained as a monomer, —lower alkyl) dissociation of the ester end of the acrylate ester and in the polymer produced
• the dissociation of the ester terminal portion of the structural unit (al) of the compound proceeds simultaneously with the polymerization of the monomer.
• the acid may be allowed to coexist with the solvent, monomer, polymerization initiator or chain transfer agent before the polymerization alone or during the polymerization, or the solvent, monomer, polymerization initiator, chain transfer agent. May be supplied together.
• the acid supply timing may be before / after the dropping, during the ripening, after the completion of the ripening and until the reaction is stopped!
• step (Q) when the step (Q) is performed after the step (P), only the step (Q-2) is performed as the step (Q).
• step (Q) is performed after step (P)
• the presence of acid continues after step (P) or after a purification step for removing impurities such as unreacted monomers after step (P). This can be done by heating down.
• step (Q) the type of acid used and the concentration of the acid are as described above.
• reaction temperature and time can be appropriately set depending on the proportion of the target structural unit (a2), the type of acid used, the type of ester terminal of ( ⁇ -lower alkyl) acrylic acid, —lower alkyl) acrylic acid ester, and the like.
• the reaction temperature is usually 40 ° C or higher, and the reaction time preferably performed at the polymerization temperature described in X @ (P) is preferably 30 minutes or longer, preferably 1 hour or longer. ! /
• the copolymer obtained through the step (P), or the step (P) and the step (Q) is an unreacted monomer, a low molecular weight component such as an oligomer, a polymerization initiator, a chain transfer agent, and the like. Reaction residue In order to include unnecessary substances such as acid used in step (Q), the step (P) or the step (R) for purifying the copolymer obtained through the step (P) and the step (Q) should be performed. Is preferred ⁇ .
• Examples of the purification method include the following (R-1), (R-la) (R-lb) (R-2), (R-2a) and the like.
• R-la A method in which a poor solvent is added following (R-1), the copolymer is washed, and then the solvent phase is separated.
• R-lb A method in which a good solvent is added following (R-1), the copolymer is redissolved, a poor solvent is further added to reprecipitate the copolymer, and then the solvent phase is separated.
• R-2 A method in which a poor solvent is added to form a poor solvent phase and a good solvent phase to separate the poor solvent phase.
• R-2a A method of adding a poor solvent following (R-2), washing the good solvent phase, and then separating the poor solvent phase.
• the poor solvent is not particularly limited as long as it is a solvent in which the copolymer is difficult to dissolve.
• water alcohols such as methanol and isopropanol, saturated hydrocarbons such as hexane and heptane, and the like can be used. it can.
• the good solvent is not particularly limited as long as it is a solvent in which the copolymer is easily dissolved, but the same solvent as the polymerization solvent is preferable in terms of management of the production process.
• step (R) when the step (R) is performed after the step (Q), the acid used in the step (Q) is removed by performing the following methods (R-3) and (R-4). Also good.
• step (Q) When the acid used in step (Q) is removed in (R-1) or (R-2), water, methanol, It is preferable to use alcohols such as propanol.
• the purified copolymer contains the solvent used at the time of purification, it is dried under reduced pressure and then dissolved in an organic solvent (resist solvent) as described later, or the resist solvent or polymer is mixed. After being dissolved in a good solvent such as a solvent, the resist solution can be finished by, for example, distilling off low-boiling substances other than the resist solvent under reduced pressure and replacing the solvent while supplying the resist solvent as necessary.
• an organic solvent resist solvent
• the resist solution can be finished by, for example, distilling off low-boiling substances other than the resist solvent under reduced pressure and replacing the solvent while supplying the resist solvent as necessary.
• the temperature of drying under reduced pressure and solvent replacement is not particularly limited as long as the temperature does not change the copolymer, but it is usually 100 ° C or less, preferably 80 ° C or less, more preferably 70 ° C or less. Is particularly preferred.
• the amount of the resist solvent used for solvent substitution is too small, the low boiling point compound cannot be removed sufficiently, and if it is too much, it takes time for solvent substitution and undesirably gives the copolymer more heat history.
• it can be selected from the range of 1.05 to 10 times, preferably 1.1 to 5 times, particularly preferably 1.2 to 3 times the amount of solvent in the finished solution.
• the component (B) is not particularly limited, and those that have been proposed as acid generators for chemical amplification resists can be used.
• acid generators include onium salt-based acid generators such as ododonium salts and sulfo-um salts, oxime sulfonate-based acid generators, bisalkyl or bisarylsulfonyldiazomethanes.
• diazomethane acid generators such as poly (bissulfol) diazomethanes, nitrobenzilsulfonate acid generators, iminosulfonate acid generators, and disulfone acid generators are known.
• Examples of the onium salt-based acid generator include compounds represented by the following general formula (b-1) or (b-2).
• R 1 " ⁇ 3 ", R 5 "to R 6 " each independently represents an aryl group or an alkyl group;
• R 4 " represents a linear, branched or cyclic alkyl group or a fluorinated alkyl. Represents at least one of,, ⁇ "represents an aryl group, and at least one of R 5 " to R 6 "represents an aryl group.
• the aryl group of R lw to R 3 is not particularly limited, for example, an aryl group having 6 to 20 carbon atoms, in which part or all of the hydrogen atoms are alkyl groups, alkoxy groups. It may not be substituted with a group, a halogen atom, etc.
• the aryl group is preferably an aryl group having 6 to 7 carbon atoms because it can be synthesized at low cost. For example, a phenol group and a naphthyl group can be mentioned.
• alkyl group on which the hydrogen atom of the aryl group may be substituted are a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group, which are preferably alkyl groups having 1 to 5 carbon atoms. It is most preferred.
• alkoxy group that may be substituted with a hydrogen atom of the aryl group, a methoxy group and an ethoxy group are preferred, with an alkoxy group having 1 to 5 carbon atoms being preferred.
• the halogen atom that may be substituted for the hydrogen atom of the aryl group is preferably a fluorine atom.
• the “ ⁇ ” alkyl group is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. From the viewpoint of excellent resolution, the number of carbon atoms is preferably 1 to 5. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, A decanyl group and the like can be mentioned, and a methyl group can be mentioned as a preferable one because it is excellent in resolution and can be synthesized at low cost.
• R lw to R 3 ′′ are a phenol group.
• R 4 represents a linear, branched or cyclic alkyl group or fluorinated alkyl group. Most preferably, the linear or branched alkyl group has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms.
• the cyclic alkyl group is a cyclic group as shown by the above R 1 ′′, preferably a carbon number of 4 to 15 carbon atoms, more preferably a carbon number of 4 to 10 carbon atoms. Most preferably, the number is from 6 to 10.
• the fluorinated alkyl group is most preferably 1 to 4 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Also.
• the degree of fluorination of the alkyl group is preferably 10 to: LO 0%, more preferably 50 to 100%, and in particular, all hydrogen atoms are fluorine atoms. The substituted one is preferable because the strength of the acid is increased.
• R 4 ′′ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.
• R 5 ′′ to R 6 ′′ each independently represents an aryl group or an alkyl group. It is preferable that at least one of R 5 ′′ to R 6 , represents an aryl group, and all of R 5 , to R 6 , are aryl groups.
• Examples of the aryl group of R 5 “to R 6 " include the same as the aryl group of,, ⁇ "
• Examples of the alkyl group for R 5 "to R 6 " include the same alkyl groups as for,, to ".
• R 5 ′′ to R 6 ′′ are phenol groups.
• Those similar to - "(1 b) R 4 in the formula is as" the like R 4 of formula (b-2) in.
• acid salt-based acid generator examples include trifluoromethane sulfonate or nonafluorobutane sulfonate of diphenylodium, trifluoromethanesulfonate or nona of bis (4-tertbutylbutyl) ododonium.
• ohmic salts in which the ionic part of these ohmic salts is replaced with methane sulfonate, n propane sulfonate, n butane sulfonate, or n octane sulfonate can also be used.
• X represents a C 2-6 alkylene group in which at least one hydrogen atom is replaced by a fluorine atom; ⁇ ", ⁇ "each independently represents at least one hydrogen atom is fluorine. Represents an alkyl group having 1 to 10 carbon atoms substituted with an atom.
• X is a straight or branched chain in which at least one hydrogen atom is replaced by a fluorine atom
• An alkylene group having 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and most preferably 3 carbon atoms.
• ⁇ "and ⁇ " are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably It is C1-C7, More preferably, it is C1-C3.
• the carbon number of the alkylene group of X "or the carbon number of the alkyl group of ⁇ " and ⁇ " is preferably as small as possible because it has good solubility in the resist solvent within the above carbon number range. ⁇ .
• U is preferred because of its improved transparency to electron beams, and the proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to L00%. Most preferably, it is a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
• the oxime sulfonate-based acid generator is a compound having at least one group represented by the following general formula (B-1), and generates an acid upon irradiation with radiation. It is what has.
• Such oxime sulfonate acid generators are widely used for chemically amplified resist compositions, and can be arbitrarily selected and used.
• R 29 and R 3 ° each independently represents an organic group.
• the organic group is a group containing a carbon atom, and an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.)) Etc.).
• an atom other than a carbon atom for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.)
• the organic group for R 29 is preferably a linear, branched or cyclic alkyl group or aryl group. These alkyl groups and aryl groups may have a substituent. As the substituent Examples thereof include, for example, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms and the like. Here, “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
• alkyl group 1 to 20 carbon atoms are preferable. 1 to 10 carbon atoms are more preferable. 1 to 8 carbon atoms are more preferable. 1 to 6 carbon atoms are particularly preferable. 1-4 carbon atoms are particularly preferable. Most preferred.
• a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable.
• the partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the completely halogenated alkyl group means that all of the hydrogen atoms are halogen atoms. It means an alkyl group substituted by.
• halogen atom examples include a fluorine atom, a chlorine atom, an fluorine atom, and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group! /.
• the aryl group is preferably 4 to 20 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, more preferably LO.
• a partially or completely halogenated aryl group is particularly preferable.
• a partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and a fully halogenated aryl group means that all hydrogen atoms are halogenated.
• R 29 is particularly preferably an unsubstituted alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms.
• organic group for R 3G a linear, branched or cyclic alkyl group, aryl group or cyan group is preferable.
• alkyl group and aryl group for R 3 include the same alkyl groups and aryl groups as those described above for R 29 .
• R 3 is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.
• Examples thereof include compounds represented by B-2) or (B-3).
• R 31 represents a cyano group, an alkyl group having no substituent, or a halogenalkyl group.
• R 32 is an aryl group.
• R 33 is an alkyl group having no substituent or a halogenated alkyl group.
• R d4 represents a cyano group, an alkyl group having no substituent, or a halogen alkyl group.
• R 35 is a divalent or trivalent aromatic hydrocarbon group.
• R 36 is an alkyl group having no substituent or a halogenated alkyl group.
• p is 2 or 3.
• the alkyl group or halogenated alkyl group having no substituent of R 31 preferably has 1 to carbon atoms: L0, preferably 1 to carbon atoms. 8 is more preferred. Most preferred is 1 to 6 carbon atoms.
• R 31 is preferably a fluorinated alkyl group, preferably a halogenated alkyl group.
• the fluorinated alkyl group in which a hydrogen atom of the alkyl group is 50% or more fluorinated is more preferable. 70% or more, more preferably 90% or more fluorinated! /, Preferably!
• R 32 aryl groups include aromatic hydrocarbon rings such as phenol, biphenylyl, fluorenyl, naphthyl, anthracyl, and phenanthryl groups. Examples include a group in which one hydrogen atom is removed, and a heteroaryl group in which a part of the carbon atoms constituting the ring of these groups is substituted with a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Among these, a fluorenyl group is preferable.
• the aryl group of R 1 may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group.
• Alkyl group or halogen in the substituent The alkyl group is more preferably 1 to 4 carbon atoms, more preferably 1 to 8 carbon atoms.
• the halogenated alkyl group is preferably a fluorinated alkyl group.
• the alkyl group or halogenated alkyl group having no substituent for R 33 preferably has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. Most preferred.
• R 33 is preferably a fluorinated alkyl group, preferably a halogenated alkyl group, and more preferably a partially fluorinated alkyl group.
• the fluorinated alkyl group in R 33 preferably has 50% or more of the hydrogen atoms of the alkyl group fluorinated, more preferably 70% or more, and even more preferably 90% or more. This is preferable because the strength of the acid is increased. Most preferably, it is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted.
• Examples of the divalent or trivalent aromatic hydrocarbon group for R 35 include groups in which the aryl group strength of R 32 is one or two hydrogen atoms.
• p is preferably 2.
• oxime sulfonate-based acid generator examples include ⁇ - ( ⁇ -toluenesulfo-luoximino) -benzyl cyanide, ⁇ - ( ⁇ -chlorobenzenesulfo-roximino) -benzil cyanide, ⁇ - (4-Nitrobenzenesulfo-luoximino) -benzyl cyanide, ⁇ - (4-Nitro-2-trifluoromethylbenzenesulfo-luoximino) -benzyl cyanide, a- (benzenesulfo-ruximino) -4 -Clorobenzyl cyanide, a-(Benzenesulfo-ruximino)-2, 4-dichlorobenzil cyanide, ⁇ -(Benzenesulfo-ruxinomino) -2, 6-dichlorobenzil cyanide, ⁇ -( Benz
• CH 3 -C N-OS02- (CH 2 ) 3CH3
• bisalkyl or bisarylsulfol diazomethanes include bis (isopropylsulfol) diazomethane, bis (p-toluenesulfol) diazomethane, bis ( 1,1-dimethylethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, bis (2,4-dimethylphenylsulfol) diazomethane and the like.
• an onium salt having a fluorinated alkyl sulfonate ion as an ion.
• one type of these acid generators may be used alone, or two or more types may be used in combination.
• the content of the component (B) in the positive resist composition of the present invention is 0.5 to 30 parts by mass, preferably 1 to: LO parts by mass with respect to 100 parts by mass of the component (A). By making it in the above range, pattern formation is sufficiently performed. Further, it is preferable because a uniform solution can be obtained and storage stability is improved.
• the positive resist composition of the present invention is further optional in order to improve the resist pattern shape, post exposure stability or the latent image formed by the pattern-wise exposure of the resist layer, etc.
• component (D) nitrogen-containing organic compound (hereinafter referred to as component (D)) can be blended.
• aliphatic amines particularly secondary aliphatic amines and tertiary aliphatic amines are preferred.
• the aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic groups preferably have from 12 to 12 carbon atoms.
• Aliphatic amines contain at least one hydrogen atom of ammonia NH and have 12 or more carbon atoms.
• Examples include amines substituted with the lower alkyl group or hydroxyalkyl group (alkylamines or alkylalcoholamines). Specific examples thereof include mono- such as n-hexylamine, n-ptylamine, n-octylamine, n-noramine, n-decylamine and the like.
• Alkylalkylamines such as jetylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri- n -propylamine, tri-n-butylamine, tri — Trialkylamines such as n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-no-lamine, tri-n-de-lamine, tri-n-dodecylamine
• Alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di- n -octanolamine, tri-n-octanolamine, and the like. Of these, alkyl alcoholamines are preferred, with alkyl alcoholamines
• Component (D) is usually used in the range of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).
• the positive resist composition of the present invention includes, as an optional component, for the purpose of preventing sensitivity deterioration due to the blending of the component (D), and improving the resist pattern shape and stability with time, etc.
• An organic carboxylic acid or phosphorus oxo acid or a derivative thereof (E) (hereinafter referred to as component (E)) can be contained.
• the component (D) and the component (E) can be used together, or one kind of force can be used.
• organic carboxylic acid for example, malonic acid, citrate, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
• Phosphoric acid or its derivatives include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester, etc., phosphoric acid or derivatives thereof such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid Phosphonic acid such as n-butyl ester, phenol phosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives thereof; phosphinic acid such as phosphinic acid, phenylphosphinic acid and Examples thereof include derivatives such as esters, and phosphonic acid is particularly preferable among these.
• Component (E) is used in a proportion of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).
• the positive resist composition of the present invention there are further additives that are miscible as desired, for example, an additional grease for improving the performance of the resist film, and a surfactant for improving the coating property.
• an additional grease for improving the performance of the resist film for example, a surfactant for improving the coating property.
• a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, and the like can be appropriately added and contained.
• the positive resist composition of the present invention can be produced by dissolving the material in an organic solvent.
• each component to be used can be dissolved into a uniform solution.
• any one or two of the known solvents for chemically amplified resists can be used. These can be appropriately selected and used.
• latones such as ⁇ -butyrolatatane; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol
• Polyhydric alcohols such as monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of dipropylene glycol monoacetate and derivatives thereof; Cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, pyrbi Acid Echiru, methyl methoxypropionate, and the like esters such as ethoxy
• organic solvents can be used alone or as a mixed solvent of two or more.
• a mixed solvent obtained by mixing propylene glycol monomethyl ether acetate (PGMEA) and a polar solvent is preferable.
• the mixing ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is preferable to be within the range.
• the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. ,.
• an organic solvent at least one selected from among PGMEA and EL.
• a mixed solvent of seeds and ⁇ -petit-mouthed rataton is also preferred.
• the mixing ratio of the former and the latter is preferably 70: 30-95: 5.
• the amount of the organic solvent used is not particularly limited, but it is a concentration that can be applied to a substrate and the like, and is appropriately set according to the coating film thickness. %, Preferably 5-15% by mass.
• the resist pattern forming method of the present invention can be performed, for example, as follows. That is, first, the positive resist composition is applied onto a substrate such as silicon wafer with a spinner or the like, and the pre-beta is applied at a temperature of 80 to 150 ° C. for 40 to 120 seconds, preferably 60 to Apply for 90 seconds to form a resist film.
• the resist film is selectively exposed to a single ArF excimer laser beam through a desired mask pattern using, for example, an ArF exposure apparatus, and then subjected to PEB (post-exposure heating under a temperature condition of 80 to 150 ° C. ) For 40 to 120 seconds, preferably 60 to 90 seconds.
• PEB post-exposure heating under a temperature condition of 80 to 150 ° C.
• alkali developing solution for example 0.1 to 10 mass 0/0 tetramethylammonium - developing is conducted using an Umuhido port Kishido solution.
• Post-beta may be applied after development if necessary.
• An organic or inorganic antireflection film can be provided between the substrate and the coating layer of the resist composition.
• the wavelength used for the exposure (irradiation) is not particularly limited, ArF excimer laser,
• the present invention is particularly effective for ArF excimer lasers.
• the positive resist composition and the resist pattern forming method of the present invention can form a resist pattern with reduced diffetivity and excellent lithography properties.
• hydroxyl and carbo Methods such as introducing a polar group such as a xyl group to increase the hydrophilicity and increasing the affinity between the resist and the developing solution can be considered.
• increasing the hydrophilicity of the base resin usually involves a decrease in lithography properties, it is difficult to achieve both a reduction in diffetats and excellent lithospheric properties.
• the cause may be a difference in polarity and polymerization rate between ( ⁇ -lower alkyl) acrylic acid ester and ( ⁇ -lower alkyl) acrylic acid. That is, when ( ⁇ -lower alkyl) acrylic acid ester and ( ⁇ -lower alkyl) acrylic acid are compared, (a-lower alkyl) acrylic acid has a higher polymerization rate. For this reason, the distribution of each structural unit becomes uneven in the resin used in conventional resists, resulting in high, low, and low hydrophobicity in the molecule. However, it is presumed that the lithography characteristics deteriorated.
• a resist using a copolymer obtained by polymerizing (a lower alkyl) acrylic acid ester in the presence of an acid, and ( ⁇ lower alkyl) acrylic acid Compared to resists using copolymers obtained by polymerizing esters and lower alkyl) acrylic acid in the absence of acid, the latter has poor lithographic properties such as DOF, but the former It is clear that the characteristics are good and the diffetat is reduced. From this, it is clear that the fine structure is different between the former and the latter.
• G a structural unit derived from ⁇ -petit-mouth rataton metatalylate.
• “Monomer G” ⁇ -butyrolatatone metatalylate. “Ga”: ⁇ —a structural unit derived from a small-mouthed rataton atelate.
• MA a structural unit derived from methacrylate.
• AA A structural unit that also induces acrylic acid power.
• the copolymer Mw, Mw / Mn, and the ratio (molar ratio) of the structural units constituting the copolymer were determined by the following method.
• Detector Differential refractive index (RI) detector.
• each of all ( ⁇ -lower alkyl) acrylate esters in the copolymer forces each of the derived structural units (sum of G or Ga, M or Ma and O or Oa).
• the proportion (mol%) of the structural unit was measured under the following analytical conditions.
• copolymer (Q) The same as the copolymer obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 5 (hereinafter referred to as copolymer (Q) for convenience) except that sulfuric acid was not added in each example. 13 C-NMR was measured under the conditions of (2) above for the copolymer (hereinafter referred to as copolymer (P) t, for convenience) produced as described above. The area of was determined.
• the peak area of the total carbon carbon is PN
• the peak area of the quaternary carbon of M or Ma is the oxygen of the non-carbon in the Rataton bond of PA, G or Ga.
• the peak area of the carbon bonded to the carbon is not the carbon in the ester bond of PC, O or Oa, but the peak area of the carbon bonded to the other oxygen is PD
• the peak area of the carbonyl carbon derived from the polymerization initiator The ratio pi was determined according to the calculation formula (1).
• pl (PN— PA— PC— PD) Z ⁇ PA + (PC / 2) + PD ⁇
• the peak area of the total carbon carbon is QN
• the peak area of the quaternary carbon of M or Ma is the carbon that is not a carbon in the rataton bond of QA, G, or Ga.
• the peak area of the carbon bonded to oxygen in the copolymer (Q) is defined as QD, where the peak area of the carbon bonded to the other oxygen is not carbocycle in the ester bond of QC, O or Oa.
• the ratio of M or Ma, AA or MA, G or Ga, O or Oa to the sum of Ma, G or Ga, O or Oa is qA, qB, qC or qD, respectively. ).
• composition ratio of M or Ma, AA or MA, G or Ga, O or Oa in the copolymer (Q) is q * A, q * B, q * C, q * D, respectively. According to 6)-(9) Asked.
• MEK methyl ethyl ketone
• MAIB 2,2′-azobisisobutyrate
• the monomer solution and the initiator solution kept at room temperature were dropped into a reaction vessel kept at 79 to 81 ° C separately at a constant rate for 4 hours using a metering pump. After completion of the dropwise addition, the mixture was further aged for 2 hours while maintaining at 80 to 81 ° C., and then cooled to room temperature and the polymerization solution was taken out.
• a copolymer (A) -2 was obtained in the same manner as in Synthesis Example 1 except that the amount of sulfuric acid used was 34 mg.
• the acid species used in the production of the copolymer and the acid concentration (mass ppm) in the reaction system were obtained.
• the measurement results of Mw, MwZMn and constituent unit composition of the copolymer are summarized in Table 1.
• a copolymer (A) -3 was obtained in the same manner as in Synthesis Example 1 except that the amount of sulfuric acid used was 39 mg.
• Table 1 summarizes the measurement results of the acid species used in the production of the copolymer, the acid concentration (mass ppm) in the reaction system, and the Mw, MwZMn, and constituent unit composition of the obtained copolymer.
• Monomer M384g, monomer Ga250g, monomer 0179g, and sulfuric acid 31mg were used as the monomer solution in the monomer solution, and copolymer (A) -4 was obtained in the same manner as in Synthesis Example 1, except that the initiator solution was MEK64g and MAIB32g.
• Table 1 summarizes the measurement results of the acid species used in the production of the copolymer, the acid concentration in the reaction system (mass ppm), the Mw, MwZMn, and constitutional unit composition of the resulting copolymer.
• Copolymer (A) -5 was obtained in the same manner as in Synthesis Example 1 except that 390 mg of trifluoroacetic acid (TFA) was used instead of sulfuric acid.
• Table 1 summarizes the measurement results of the acid species used in the production of the copolymer, the acid concentration in the reaction system (mass ppm), and the Mw, MwZMn, and constituent unit composition of the resulting copolymer.
• a copolymer (A) -6 was obtained in the same manner as in Synthesis Example 1 except that no sulfuric acid was added. Table 1 summarizes the measurement results of Mw, MwZMn and constituent unit composition of the obtained copolymer.
• a copolymer (A) -7 was obtained in the same manner as in Synthesis Example 1, except that 11.5 g of acrylic acid was added as a monomer without adding sulfuric acid and the amount of monomer Ma used was 317 g.
• Table 1 summarizes the measurement results of Mw, MwZMn and constituent unit composition of the obtained copolymer.
• a copolymer (A) -8 was obtained in the same manner as in Comparative Synthesis Example 2, except that the amount of addition of acrylic acid was 17.3 g and the amount of monomer Ma used was 299 g.
• Table 1 summarizes the measurement results of Mw, Mw / Mn and constituent unit composition of the obtained copolymer.
• Comparative Synthesis Example 4 A copolymer (A) -9 was obtained in the same manner as in Synthesis Example 4 except that no sulfuric acid was added. Table 1 summarizes the measurement results of Mw MwZMn and constituent unit composition of the obtained copolymer.
• a copolymer (A) -10 was obtained in the same manner as in Synthesis Example 4 except that 13.8 g of methacrylic acid was added as a monomer without addition of sulfuric acid and the amount of monomer M used was 347 g.
• Table 1 summarizes the measurement results of Mw MwZMn and constitutional unit composition of the obtained copolymer.
• component, component, (D) component, (ii) component and organic agent were mixed and dissolved in the compositions and blending amounts shown in Table 2 to prepare a positive resist composition solution.
• An organic anti-reflection coating composition “ARC-29A” (trade name, manufactured by Plue Science) was applied onto an 8-inch silicon plate using a spinner and baked on a hot plate at 205 ° C. for 60 seconds. By drying, an organic antireflection film having a thickness of 77 nm was formed.
• a positive resist composition solution is applied onto the antireflection film using a spinner, pre-beta (PAB) at 105 ° C. for 90 seconds, and dried to form a resist film having a thickness of 220 ⁇ m. Formed.
• the positive resist composition solution was applied directly onto a hexamethyldisilazane (HMDS) -treated 8-inch silicon wafer using a spinner, and pre-beta (PAB) at 105 ° C for 90 seconds on a hot plate. And dried to form a resist film having a thickness of 220 nm.
• HMDS hexamethyldisilazane
• PAB pre-beta
• PEB treatment was performed for 90 seconds at 110 ° C, followed by paddle development for 60 seconds with an aqueous solution of 2.38 mass% tetramethylamine hydroxide at 23 ° C, 1 second at 1000 rpm, then 15 seconds at 500 rpm.
• a rinsing solution was dropped under the conditions (forced conditions such that diffracting is more likely to occur) and dried to form a resist pattern.
• a dense hole pattern with a hole diameter of 300 nm (a pattern in which hole patterns with a diameter of 300 nm are arranged at intervals of 300 nm) was formed.
• the surface defect observation device KLA2351 (product name) manufactured by KLA Tencor was used to measure the number of defects in the wafer.
• Example 1 110 100 23.5 4.0 1698
• Example 3 110 100 21.5 4.0 376
• Example 4 100 105 23.0 4.0 150
• Example 5 110 100 22.0 4.0 400
• Comparative Example 5 100 105 270 3.5 47351 As described above, Examples 1 to 5 using a copolymer produced in the presence of sulfuric acid or trifluorosuccinic acid all had good lithography characteristics such as a large DOF. It was. In addition, the diffout was reduced.
• Comparative Examples 1 to 5 using a copolymer produced without adding sulfuric acid had a bad lithographic property, particularly DOF.
• Comparative Examples 1 and 2 had a large number of defects, so it was impossible to evaluate other items.
• Comparative Example 3 using a copolymer containing 4.9 mol% of soot obtained using acrylic acid although the defect was reduced, the DOF was small.
• Comparative Example 5 using a copolymer containing 4 mol% of soot obtained using methacrylic acid had poor lithography properties and a large number of defects, such as small DOF.

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