WO2007013471A1 - Compounds, process for production thereof, low-molecular compounds, positive resist compositions and process for formation of resist patterns - Google Patents

Compounds, process for production thereof, low-molecular compounds, positive resist compositions and process for formation of resist patterns Download PDF

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Publication number
WO2007013471A1
WO2007013471A1 PCT/JP2006/314696 JP2006314696W WO2007013471A1 WO 2007013471 A1 WO2007013471 A1 WO 2007013471A1 JP 2006314696 W JP2006314696 W JP 2006314696W WO 2007013471 A1 WO2007013471 A1 WO 2007013471A1
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Prior art keywords
integer
group
compound
alkyl group
general formula
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PCT/JP2006/314696
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French (fr)
Japanese (ja)
Inventor
Daiju Shiono
Taku Hirayama
Hideo Hada
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Tokyo Ohka Kogyo Co., Ltd.
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Publication date
Priority claimed from JP2005294531A external-priority patent/JP2007099727A/en
Priority claimed from JP2005298711A external-priority patent/JP4846332B2/en
Application filed by Tokyo Ohka Kogyo Co., Ltd. filed Critical Tokyo Ohka Kogyo Co., Ltd.
Publication of WO2007013471A1 publication Critical patent/WO2007013471A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
    • C07C65/105—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups polycyclic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/06—Hydroxy derivatives of triarylmethanes in which at least one OH group is bound to an aryl nucleus and their ethers or esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/103—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a diaryl- or triarylmethane dye

Definitions

  • the present invention relates to a compound that can be suitably used for the production of a low-molecular compound that can be used as a resist composition, a method for producing the compound, a low-molecular compound obtained by using the compound, and the low-molecular compound.
  • the present invention relates to a positive resist composition containing a molecular compound and a resist pattern forming method using the positive resist composition.
  • the wavelength of an exposure light source is generally shortened.
  • the power used in the past typically ultraviolet rays such as g-line and i-line
  • KrF excimer laser and ArF excimer laser have now begun mass production of semiconductor devices using KrF excimer laser and ArF excimer laser.
  • these excimer lasers have shorter wavelength excimer lasers, electron beams, EUV (
  • a chemically amplified resist containing a base material component capable of forming a film and an acid generator component that generates an acid upon exposure is known. It has been. Chemically amplified resists are classified into a negative type in which alkali solubility is reduced by exposure and a positive type in which alkali solubility is increased by exposure.
  • polymers have been used as the base component of such chemically amplified resists.
  • PHS polyhydroxystyrene
  • a part of its hydroxyl group protected with an acid dissociable, dissolution inhibiting group for example, polyhydroxystyrene (PHS) or a part of its hydroxyl group protected with an acid dissociable, dissolution inhibiting group.
  • Copolymers derived from PHS resin such as (meth) acrylate ester
  • rosin or the like in which a part of the body or its carboxy group is protected with an acid dissociable, dissolution inhibiting group is used.
  • polymers generally used as a base component have a large molecular size (average square radius per molecule) of around several nanometers.
  • the dissolution behavior of the resist in the current image solution is usually performed in units of one molecular component of the base material. Therefore, as long as a polymer is used as the base material component, further reduction in roughness is extremely difficult.
  • Non-Patent Documents 1 and 2 propose low molecular weight materials having an alkali-soluble group such as a hydroxyl group or a forceful alkoxy group, and a part or all of which is protected with an acid dissociable, dissolution inhibiting group.
  • Non-Patent Document 1 T. Hirayama, D. Shiono, H. Hada and J. Onodera: J. Photo polym. Sci. Technol. 17 (2004), p435
  • Non-Patent Document 2 Jim— Baek Kim, Hyo-Jin Yun, Young— Gil Kwon: Chemis try Letters (2002), pl064-1065
  • Such a low molecular weight material is expected to be able to reduce roughness due to a small molecular size because of its low molecular weight. Therefore, when a resist composition is used, there is an increasing demand for a low molecular material capable of forming a resist pattern at a level that can be actually used.
  • the present invention has been made in view of the above circumstances, and is useful for resist compositions.
  • An object of the present invention is to provide a method for forming a resist pattern using a mold resist composition.
  • a first aspect of the present invention that solves the above problems is a compound represented by the following general formula (1-0).
  • R U to R 13 are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is 1 to S + t + u is an integer of 3 to 5; q is an integer of 0 to 2; Q is an oxygen atom or a single bond; r is an integer of 0 to 3 P is 1 or 2.
  • the second aspect of the present invention is a low molecular compound represented by the following general formula (A-1-0) or (A-2-0).
  • R 5 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group or a halogenated alkyl group; R 3 "to R 4 R 9-to R 1C) -are each independently And 1, m, ⁇ 'and m are each independently an integer of 1 to 3; n, n and 1 to 3 are the groups represented by the following general formula (1-11-0).
  • Y is an (n + 1) valent organic group;
  • Z is an (n, +1) valent organic group.
  • the third aspect of the present invention is a positive electrode containing a base component (A-0) whose alkali solubility is increased by the action of an acid, and an acid generator component (B) which generates an acid upon irradiation with radiation.
  • Type resist composition comprising: A positive resist composition in which the base component (A-0) contains a low molecular compound (A1-0) represented by the following general formula (A-1-0) or (A-2-0) is there.
  • R 5 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group or a halogenated alkyl group; R 3 "to R 4 R 9-to R 1C) -are each independently And 1, m, ⁇ 'and m are each independently an integer of 1 to 3; n, n and 1 to 3 are the groups represented by the following general formula (1-11-0).
  • Y is an (n + 1) valent organic group;
  • Z is an (n, +1) valent organic group.
  • R U to R 13 are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3] S + t + u is an integer of 3-5; q is an integer of 0-2; Q is an oxygen atom or a single bond; r is an integer of 0-3.
  • the compound of the first aspect is preferably a compound represented by the following general formula (I)
  • R to R are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3] S + t + u is an integer from 3 to 5; q is an integer from 0 to 2; r is an integer from 1 to 3; p is 1 or 2. ]
  • R is an alkyl group having 1 to 10 carbon atoms; q is an integer of 0 2; p is 1 or 2; X is a halogen atom; r is an integer of 1 3; R Is a protecting group.
  • RR is an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 2; t is an integer of 1 3; u is an integer of 1 3; s + t + u Is an integer of 35; q is an integer of 0 2; r is an integer of 1 3; p is 1 or 2; R is a protecting group.
  • the low molecular compound of the second aspect of the present invention is preferably a low molecular compound represented by the following general formula (A-1) or (A-2). [0020] [Chemical 9]
  • ⁇ , R 5 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group or Harogeni spoon alkyl group;
  • R 3 ⁇ R 4, R 9 ⁇ R 1C) are each independently the following A group represented by the general formula (I 11); 1, m, ⁇ ′ and m are each independently an integer of 1 to 3; n, n are an integer of 1 to 3; Y Is an (n + 1) -valent organic group; Z is an (n, +1) -valent organic group.
  • R to R are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3] S + t + u is an integer of 3-5; q is an integer of 0-2; r is an integer of 1-3. ]
  • the fifth aspect of the present invention is a positive resist comprising a base component (A) whose alkali solubility is increased by the action of an acid, and an acid generator component (B) which generates an acid upon irradiation with radiation.
  • a strike composition comprising:
  • the base material component (A) is a positive resist composition containing a low molecular weight compound (A1) represented by the following general formula (A-1) or (A-2).
  • R 5 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group or a halogenoalkyl group
  • R 3 to R 4 and R 9 to R 1G are each independently Is a group represented by the formula (I 11); 1, m, ⁇ ′ and m are each independently an integer of 1 to 3; n, n are an integer of 1 to 3; Y is (N + 1) -valent organic group; Z is an (n, + 1) -valent organic group.
  • R to R are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3] S + t + u is an integer of 3-5; q is an integer of 0-2; r is an integer of 1-3.
  • a resist pattern forming method including a step of forming a resist pattern.
  • the compound of the first aspect is preferably a compound represented by the following general formula (I) '.
  • RU to R are each independently an alkyl group having 1 to C carbon atoms; s is 1
  • a compound (1) 'represented by the following general formula (1)' and a compound (2) 'represented by the following general formula (2)' This is a method for producing a compound having a step of obtaining a compound represented by the following general formula (I) ′ by reacting under acidic conditions.
  • R ′′ to R 13 are each independently an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is 1 to 3] S + t + u is an integer from 3 to 5; q is an integer from 0 to 2; p is 1 or 2.]
  • alkyl group in the claims and the specification includes linear, branched, and cyclic monovalent saturated hydrocarbon groups.
  • a compound that can be suitably used for the production of a low-molecular compound that can be used as a resist composition a method for producing the compound, a low-molecular compound obtained by using the compound, and the low-molecular compound
  • a positive resist composition containing a compound and a resist pattern forming method using the positive resist composition are provided.
  • FIG. 1 An EB exposure residual film curve showing a change in residual film ratio due to a change in EB irradiation amount of a positive resist composition containing a low molecular weight compound obtained by using the compound of the present invention.
  • the compound of the present invention is represented by the above general formula (I 0) (hereinafter represented by the general formula (I 0))
  • the compound is referred to as compound (I 0).
  • a hydroxyl group and R 11 and R 12 are bonded to two of the phenyl groups of the triphenylmethane skeleton, and a carboxyalkyloxy group (—O— (CH ) — CO—OH) or a carboxy group (—COOH), and optionally R 13
  • R "to R 13 , s, t, u, q, and p are 1 to! ⁇ 3, s, t, u, q, It is the same as p.Q in the above formula (I 0) is an oxygen atom or a single bond, and r is an integer of 0 to 3. The case where r is 0 means a single bond.
  • the compound (I 0) of the present invention can be suitably used for the production of a low molecular weight compound that can be used as a resist composition.
  • a low molecular weight compound that can be used as a resist composition.
  • Formula (A- 1-0) or (A- 2-0) in, ⁇ , R 5 to R 8 are each independently water atom, a halogen atom, an alkyl group or a halogenated alkyl group
  • R 3 " ⁇ R 4", R 9 - ⁇ R 1G " are each independently a group represented by the general formula (1-11- 0)
  • 1, m , 1 ', m, is independently N and n ′ are integers of 1 to 3
  • Y is an (n + 1) -valent organic group
  • Z is an ( ⁇ ′ + 1) -valent organic group.
  • R U to R 13 are each an alkyl group having 1 to L carbon atoms, s is an integer of 1 to 2, and t is an integer of 1 to 3. , U is an integer of 1 to 3, s + t + u is an integer of 3 to 5, q is an integer of 0 to 2, Q is an oxygen atom or a single bond, r is 0 to 3 Is an integer. The case where r is 0 means a single bond.
  • the positive resist composition of the present invention comprises a base component (A-0) (hereinafter referred to as (A-0) component) whose alkali solubility is increased by the action of an acid, and an acid upon irradiation with an acid.
  • the substrate component (A-0) contains a low molecular compound (A1-0) represented by the general formula (A-1-0) or (A-2-0).
  • This positive resist composition contains a base component (A—0) force and a low molecular compound (A1—0) represented by the above general formula (A—1—0) or (A—2—0) Except for this, it is the same as the positive resist composition of the fourth or ninth embodiment described later.
  • the content of the component (A-0) in the positive resist composition may be adjusted according to the resist film thickness to be formed.
  • the component (A-0) contains an optional oil component (component (A 2)) described later! ,.
  • the positive resist composition having the above structure can be used in a resist pattern forming method as in the fifth or tenth embodiment described later.
  • the compound of the first embodiment of the present invention (hereinafter referred to as compound (I)) has a hydroxyl group and R 11 as two phenyl groups of the triphenylmethane skeleton, as represented by the above general formula (I). And R 12 combine, and the remaining one phenol group is a carboxyalkyloxy group (O— (CH) — C
  • R U to R 13 are linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms.
  • alkyl group a linear or branched lower alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 5 to 6 carbon atoms is preferable.
  • the lower alkyl group include linear or branched alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an nbutyl group, an isobutyl group, a tertbutyl group, a pentyl group, an isopentyl group, and a neopentyl group.
  • a methyl group is preferable.
  • cyclic alkyl group examples include a cyclohexyl group and a cyclopentyl group.
  • P is 1 or 2.
  • p is 1 because a compound produced using the compound is suitable for a resist composition. That is, the compound (I) is preferably a compound represented by the following general formula (I 1).
  • q is an integer of 0 to 2, preferably 0 or 1, and most preferably 0.
  • r is an integer of 1 to 3, preferably 1 or 2, and most preferably 1.
  • the bonding position of the carboxyalkyloxy group [O— (CH) — CO— OH] is particularly limited.
  • the compound produced using the resulting compound is suitable for use as a resist composition, is easy to synthesize, and is bonded to at least the para position (position 4) of the phenyl group. Preferably it is.
  • the bonding position of R 13 is not particularly limited, but it is bonded to at least one of the carbon atoms adjacent to the carbon atom to which the carboxyalkyloxy group is bonded in view of synthesis. It is preferable.
  • s is an integer of 1 to 2, preferably 1.
  • t is an integer of 1 to 3, preferably 1 or 2, and most preferably 1.
  • u is an integer of 1 to 3, preferably 1 or 2, and most preferably 1.
  • s + t + u is an integer of 3 to 5, preferably 3 or 4, and most preferably 3.
  • the bonding position of the hydroxyl group is not particularly limited, but at least the para position of the phenol group is preferable in that the compound produced using the resulting compound is suitable for a resist composition and easy to synthesize. It is preferable that it is bonded to (position 4).
  • R U to R 12 is not particularly limited, but R 11 or R 12 is bonded to at least one of the carbon atoms adjacent to the carbon atom to which the hydroxyl group is bonded, in terms of synthesis and the like. It is particularly preferred instrument, hydroxyl bonded R 11 or R 12 is to both of the carbon atoms adjacent to the carbon atom attached, is preferably Rukoto! /,.
  • a compound represented by the following general formula (IV) is particularly preferable because a compound produced using the compound is suitable for a resist composition.
  • Ru R is an alkyl group having 1 to 10 carbon atoms; r is an integer of 1 to 3; p is 1 or 2. ]
  • R U ⁇ R 12 , r and p are the same as R U ⁇ R 12, r and p in formula (I).
  • R to R are each an alkyl group having 1 to 10 carbon atoms, and r is an integer of 1 to 3. ]
  • the compound represented by 2) or ( ⁇ -3) is preferred.
  • R to R are each an alkyl group having 1 to 10 carbon atoms, and r is an integer of 1 to 3] P is 1 or 2. ]
  • Compound (I) can be produced by a conventionally known method.
  • compound (I) is obtained by acidifying an optionally substituted alkoxy carboalkyloxybenzaldehyde and a phenol compound having a substituent.
  • a hydroxyl group of the tris (hydroxyphenyl) methane is reacted with a halogenated carboxylic acid such as a bromoacetate derivative to produce a carboxyalkyloxy group.
  • a halogenated carboxylic acid such as a bromoacetate derivative
  • the compound (I) is preferably produced by the following production method of the present invention.
  • the method for producing the compound (I) of the second embodiment of the present invention comprises reacting the compound (1) represented by the general formula (1) with the compound (2) represented by the general formula (2).
  • a step of obtaining a compound (3) represented by the above general formula (3) (hereinafter referred to as compound (3) formation step and ⁇ ⁇ ),
  • a step of obtaining the compound (I) of the present invention by reacting the compound (3) with the compound (4) represented by the general formula (4) under acidic conditions (hereinafter referred to as the compound (I) formation step) Ii).
  • the compound (I) formation step) Ii A step of obtaining the compound (I) of the present invention by reacting the compound (3) with the compound (4) represented by the general formula (4) under acidic conditions
  • R 13, q, p, r are, R 13, q in the general formula (I), p, in the formula is the same as r (2), the X
  • the halogen atom include a bromine atom, a chlorine atom, and a fluorine atom. A bromine atom is preferable because of excellent reactivity.
  • the protecting group for R does not react when the compound (1) is reacted with the compound (2), and it is acidic when the compound (3) is reacted in the next step of forming the compound (I).
  • the group is not particularly limited as long as it is a group capable of dissociating under conditions, and can be arbitrarily selected from those generally proposed as protecting groups.
  • the compounds that have been proposed include tertiary alkyl groups, tertiary alkyloxycarbon groups, alkoxycarboalkyl groups, alkoxyalkyl groups, and cyclic ether groups.
  • the tertiary alkyl group preferably has 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms.
  • an aliphatic polycyclic group such as a chain-like tertiary alkyl group such as tert-butyl group or tert-amyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, etc.
  • tertiary alkyl group containing a chain-like tertiary alkyl group such as tert-butyl group or tert-amyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, etc.
  • 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.
  • Examples of the tertiary alkyl group in the tertiary alkyloxycarbonyl group include the same groups as described above.
  • tertiary alkyloxycarbonyl group examples include a tert-butyloxycarbonyl group and a tert-amyloxycarbonyl group.
  • alkoxycarboalkyl group examples include a group represented by the following general formula (pi).
  • R 21 is a linear, branched or cyclic alkyl group, and may contain a hetero atom in its structure. That is, in the alkyl group as R 21 , part or all of the hydrogen atoms may be substituted with a group containing a hetero atom (including a hetero atom itself), and one of the carbon atoms of the alkyl group may be substituted. Part may be substituted with a heteroatom.
  • Hetero atoms include oxygen atoms, sulfur atoms, nitrogen atoms, fluorine atoms, etc.
  • the group containing hetero atoms may be a hetero atom itself, or a hetero atom, a carbon atom, and a Z or hydrogen atom. It may be a group consisting of, for example, an alkoxy group.
  • alkyl groups in which some or all of the hydrogen atoms are substituted with groups containing heteroatoms For example, a fluorinated lower alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced with fluorine atoms, or two hydrogen atoms bonded to the same carbon atom are replaced with one oxygen atom.
  • Examples of the group in which a part of the carbon atoms of the alkyl group is substituted with a group containing a hetero atom include, for example, an example in which the carbon atom is substituted with a nitrogen atom (for example, branched or In a cyclic alkyl group, the CH— is replaced by —NH
  • the linear alkyl group as R 21 preferably has 1 to 5 carbon atoms. Specifically, a methyl group, an ethyl group, an n propyl group, an n butyl group, an isobutyl group, and an n pentyl group may be used. And preferred are a methyl group or an ethyl group.
  • the branched alkyl group as R 21 preferably has 4 to 8 carbon atoms, more preferably 4 to 8 carbon atoms. Specific examples include an isobutyl group, a tert butyl group, an isopentyl group, a neopentyl group, a tert pentyl group, and the like, preferably a tert butyl group.
  • the cyclic alkyl group as R 21 preferably has 3 to 20 carbon atoms, more preferably 4 to 14 carbon atoms, and most preferably 5 to 12 carbon atoms.
  • the structure of the basic ring in the cyclic alkyl group may be monocyclic or polycyclic.
  • the basic ring may be a hydrocarbon ring composed of carbon and hydrogen, or may be a heterocycle in which a part of carbon atoms constituting the hydrocarbon ring is substituted with a heteroatom.
  • the basic ring is particularly preferably a hydrocarbon ring.
  • Specific examples of the hydrocarbon ring include monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane.
  • monocycloalkanes such as cyclopentane and cyclohexane, adamantane, norbornane, isobornane, tricyclo
  • polycycloalkanes such as decane and tetracyclododecane.
  • adamantane, norbornane, tricyclodecane, and tetracyclododecane are preferable, and adamantane is particularly preferable.
  • Examples of the lower alkyl group include linear or branched alkyl groups having 1 to 5 carbon atoms such as a methyl group and an ethyl group.
  • the fluorinated lower alkyl group is a group in which part or all of the hydrogen atoms of the lower alkyl group are substituted with fluorine atoms.
  • the number of substituents is preferably 1 to 3, and more preferably 1.
  • “having a substituent” means that a hydrogen atom bonded to a carbon atom constituting the basic ring is substituted with a substituent.
  • Examples of the cyclic alkyl group represented by R 21 include groups obtained by removing one hydrogen atom from these basic rings.
  • the carbon atom to which the oxygen atom adjacent to R 21 is bonded is one of the carbon atoms constituting the basic ring as described above, in particular, the oxygen atom adjacent to R 21
  • the carbon atom bonded to is preferably a tertiary carbon atom bonded to a substituent such as a lower alkyl group.
  • alkoxyalkyl group examples include a group represented by the following general formula (p2).
  • R 22 is a linear, branched or cyclic alkyl group, and R 22 which may contain a hetero atom in the structure thereof is the same as R 21 above Can be mentioned.
  • R 23 is a hydrogen atom or a lower alkyl group.
  • the lower alkyl group for R 23 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, a ⁇ butyl group, an isobutyl group, a tert butyl group, and a pentyl group. And a lower linear or branched alkyl group such as an isopentyl group and a neopentyl group.
  • R 23 is more preferably a hydrogen atom or a hydrogen atom which is preferably a hydrogen atom or a methyl group in terms of industrial availability.
  • the group represented by the formula ( P2 ) is preferably a group in which R 22 is a linear alkyl group.
  • R 22 is a linear alkyl group.
  • R 22 is a linear alkyl group.
  • examples include til group, 1-methoxypropyl group, 1 ethoxypropyl group, l-n-butoxetyl group, 1 pentafluoroethoxyethyl group, 1 trifluoromethoxyethyl group, 1 trifluoromethoxymethyl group, etc. It is done.
  • cyclic ether group examples include a tetrahydrovinyl group and a tetrahydrofuranyl group.
  • the protecting group for R is preferably a tertiary alkyl group or an alkoxyalkyl group in view of ease of dissociation by an acid, availability, and the like.
  • Jo ones chain-like tertiary alkyl group; in the formula (p2), a R 22 a linear or branched alkyl group, Yogu R 23 may include a hetero atom in its structure hydrogen
  • the compound (1) and the compound (2) can be reacted by a known method.
  • the compound (1) is dissolved in an organic solvent such as tetrahydrofuran (THF)
  • the reaction can be carried out by adding a base such as potassium carbonate to the solution and adding the compound (2) to the solution while stirring.
  • any organic solvent may be selected from general organic solvents that can dissolve the compounds (1) to (3).
  • Examples of common organic solvents include ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, and cyclohexanone; ethers such as THF, dioxane, glyme, and propylene glycol monomethyl ether; esters such as Echiru; ether esters such as propylene glycol methylation ether acetate; Y Rataton, etc. can be exemplified such Buchirorataton, can be used alone or in combination.
  • the reaction temperature is preferably 10-60 ° C, more preferably 20-60 ° C, usually at room temperature (20-2
  • the reaction time is preferably 1 to 24 hours, more preferably 4 to 15 hours.
  • reaction solution may be used in the next step as it is. However, it is preferable to add water Z ethyl acetate and the like, and concentrate the organic layer (ethyl acetate layer, etc.) under reduced pressure to obtain compound (3). U ⁇ .
  • the compound (3) is dissolved in an organic solvent such as methanol, and about 2 equivalents of the compound (4) is added to the compound (3).
  • the reaction can be carried out by adding an acid.
  • the acid used at this time is not particularly limited as long as the compound (3) reacts with the compound (4) and the protective base is dissociated.
  • Preferred examples include hydrochloric acid, sulfuric acid, sulfuric anhydride, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid and the like.
  • hydrochloric acid is preferably used. Any one of these acids may be used alone, or two or more of these acids may be used in combination.
  • the acid is added in an amount of 1 to 700 parts by weight, preferably 100 to 600 parts by weight per 100 parts by weight of the compound (3).
  • the reaction temperature is preferably 20 to 80 ° C, more preferably 30 to 65 ° C.
  • the reaction time is preferably 2 to 96 hours, more preferably 5 to 72 hours.
  • a well-known method can be used. Specifically, for example, it was obtained by neutralizing the remaining acid by adding a base such as sodium hydroxide to the reaction solution, and then performing extraction operation by adding water Z ethyl acetate or the like.
  • the compound (I) can be obtained by concentrating the organic layer (such as an ethyl acetate layer) under reduced pressure and performing column chromatography or the like.
  • the compound (I) of the present invention can be suitably used for the production of a low-molecular compound that can be used as a resist composition.
  • the compound represented by the general formula (I 1) can be suitably used for the production of the low molecular compound of the present invention described below.
  • the low molecular compound of the third embodiment of the present invention (hereinafter referred to as low molecular compound (A1)) is It is represented by the general formula (A-1) or (A-2).
  • R 5 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group or a halogenated alkyl group;
  • R 3 to R 4 , R 9 to R 1C are each independently A group represented by the general formula (I 11); 1, m, ⁇ ′ and m are each independently an integer of 1 to 3; n, n are an integer of 1 to 3; Y Is an (n + 1) -valent organic group; Z is an (n, +1) -valent organic group.
  • Low molecular weight compound (Al) Has a structure as described above, for example, when it is blended with a positive resist composition together with an acid generator component, R 3 to R 4 due to the action of an acid generated from the acid generator component upon exposure. And an oxygen atom bonded to a carbon atom of a carbo group adjacent to R 9 to R 1G and a carbon atom bonded to the oxygen atom (to, R 5 to R 8 etc. The bond between the bonded carbon atoms) is broken and decomposed.
  • R 1 ! ⁇ Each independently represents a hydrogen atom, a halogen atom, an alkyl group, or a halogenated alkyl group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
  • the alkyl group of I ⁇ to R 2 is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups having 1 to C: LO.
  • a linear or branched lower alkyl group having 1 to 5 or a cyclic alkyl group having 5 to 6 carbon atoms is preferable.
  • the linear or branched lower alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n -butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. It is done.
  • the cyclic alkyl group include a cyclohexyl group and a cyclopentyl group.
  • halogenated alkyl group examples include alkyl groups in which some or all of the hydrogen atoms of the alkyl groups listed above are substituted with halogen atoms.
  • the I ⁇ to R 2 a hydrogen atom is particularly preferable.
  • R 3 to R 4 are each independently a group represented by the general formula (1-11), and in the general formula (1-11)! ⁇ 11 to! ⁇ 13 , s, t, u, q, r are the same as 1 to! ⁇ 3 , s, t, u, q, r in the formula (I).
  • R 3 to R 4 may be the same or different from each other, but are preferably the same in terms of synthesis.
  • m are each independently an integer of 1 to 3, preferably 1 or 2, and most preferably 1.
  • n is an integer of 1 to 3, preferably 1 or 2, and most preferably 1.
  • n is an integer of 2 or more, that is, the compound (A1) force R 4 -COO- [C (R 2 ) H
  • Y is an (n + 1) -valent organic group.
  • the organic group is preferably a linear, branched or cyclic saturated hydrocarbon group.
  • a linear or branched saturated hydrocarbon group is more preferred.
  • the saturated hydrocarbon group preferably has 1 to 15 carbon atoms, and more preferably 1 to 6 carbon atoms in which L0 is more preferable.
  • the saturated hydrocarbon group may have a substituent.
  • the substituent is not particularly limited, and examples thereof include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, and linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms.
  • “having a substituent” means that part or all of the hydrogen atoms of the saturated hydrocarbon group are substituted with a substituent.
  • Examples of Y include a group in which a part of carbon atoms of the saturated hydrocarbon group as described above is substituted with a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • Y a divalent or trivalent saturated hydrocarbon group is particularly preferable, and a divalent saturated hydrocarbon group (alkylene group) is particularly preferable.
  • the saturated hydrocarbon group may be linear, branched or cyclic.
  • trivalent linear or branched saturated hydrocarbon group examples include groups in which three hydrogen atoms have been removed from methane, ethane, propane, butane, pentane, hexane, heptane, octane and the like.
  • trivalent cyclic saturated hydrocarbon group three hydrogen atoms were removed from a saturated hydrocarbon ring such as cyclopentane, cyclohexane, cycloheptane, norbornane, isobornane, adamantane, tricyclodecane, tetracyclododecane, etc.
  • a saturated hydrocarbon ring such as cyclopentane, cyclohexane, cycloheptane, norbornane, isobornane, adamantane, tricyclodecane, tetracyclododecane, etc.
  • examples thereof include a cyclic group and a group in which a linear or branched alkylene group is bonded to the cyclic group.
  • linear or branched alkylene group examples include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a tert-butylene group, a pentylene group, an isopentylene group, and a neopentylene group.
  • the cyclic alkylene group includes a cyclic group obtained by removing two hydrogen atoms from a saturated hydrocarbon ring such as cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, and tetracyclododecane. And a group in which a linear or branched alkylene group is bonded to the group.
  • Y is particularly preferably an ethylene group or a propylene group, more preferably a linear alkylene group, more preferably a linear or branched alkylene group.
  • R 9 to R 1G examples include the same as R 3 to R 4 in formula (A-1).
  • M ′, n ′, and Z are the same as 1, m, n, and Y in general formula (A-1), respectively.
  • the low molecular compound (A1) is a material that can form an amorphous film by spin coating.
  • the amorphous film means an optically transparent film that does not crystallize.
  • the spin coating method is one of the commonly used thin film forming methods, and whether or not the compound is a material capable of forming an amorphous film by the spin coating method is determined on an 8-inch silicon wafer. It can be discriminated by whether or not the coating film formed by the spin coating method is completely transparent. More specifically, for example, the determination can be made as follows.
  • a solvent generally used as a resist solvent for the compound for example, 100 parts by mass of a low molecular compound (A1) is dissolved in 1570 parts by mass of an organic solvent of propylene glycol monomethyl ether acetate.
  • Ultrasonic treatment (dissolution treatment) is performed using a sonic cleaner, and the solution is spin-coated on the wafer at 1500 rpm, and optionally a dry baking (PAB, Post Applied Bake) of 110 °. C, apply for 90 seconds, and in this state, visually check whether an amorphous film is formed depending on whether it is transparent or not. It should be noted that the transparent film is not a monolithic film.
  • the low molecular weight compound (A1) has good stability of the amorphous film formed as described above.
  • the low molecular compound (A1) is allowed to stand in a room temperature environment for 2 weeks. Even later, it is preferable to maintain an amorphous state.
  • the low molecular compound (A1) is, for example, one or more compounds (I) dissolved in a solvent such as tetrahydrofuran in the presence of a catalyst such as triethylamine and the following general formula (a — It can be synthesized by reacting with the bischloro compound represented by 1) or (a-2).
  • R 1 ⁇ ! T, R 5 to R 8 , Y, ⁇ , 1, m, 1, and m are R ⁇ R 2 , R 5 to R 8 , Y in the above general formulas (A-1) to ( ⁇ —2) , Z, 1, m, 1, m. ]
  • the low molecular weight compound (Al) is a positive type resin containing a base component (A) whose alkali solubility is increased by the action of an acid and an acid generator component (B) which generates an acid upon irradiation with radiation.
  • a base component (A) whose alkali solubility is increased by the action of an acid and an acid generator component (B) which generates an acid upon irradiation with radiation.
  • an acid generator component (B) which generates an acid upon irradiation with radiation.
  • it can be suitably used as the substrate component (A).
  • a positive resist composition containing the low molecular compound (A1) By using a positive resist composition containing the low molecular compound (A1), a high-resolution resist pattern can be formed. In addition, roughness can be reduced.
  • the low molecular weight compound (A1) of the present invention is a low molecular weight non-polymer, Inhibition of acid-dissociable dissolution of alkali-soluble groups, such as those used in chemically amplified positive resists and the conventional low-molecular compounds proposed in Non-Patent Documents 1 and 2 mentioned above Since it does not need to be protected by a group, the structure is clear and the molecular weight is less uneven. Therefore, properties such as alkali solubility and hydrophilicity / hydrophobicity are uniform, and therefore, a resist film having uniform properties can be formed.
  • the low molecular weight compound (A1) is decomposed by the action of the acid generated by exposure to produce 2 to 4 decomposition products, and the ability to increase alkali solubility. There is no large molecular weight protruding, and the difference in the individual molecular weights of the resulting degradation products becomes relatively small. For this reason, the decomposed products are evenly distributed in the resist film, and the difference in dissolution behavior of the decomposed products in the alkaline developer is small.
  • a resist film having a uniform property can be formed before and after exposure, thereby forming a resist pattern with high resolution and reducing roughness. Presumed to be possible.
  • the properties of the low molecular weight compound (A1) are uniform, it is considered that a resist film having uniform properties (such as strength, hydrophilicity, hydrophobicity, etc.) can be formed.
  • the diffetat can also be reduced.
  • diffetats are, for example, general defects detected when the resist pattern after development is also observed by the KLA Tencor surface defect observation device (trade name “KLA”). . This defect includes, for example, scum after development, bubbles, dust, bridges between resist patterns, uneven color, and precipitates.
  • the storage stability of the positive resist composition containing the low molecular compound (A1) is also improved. improves.
  • the positive resist composition of the fourth embodiment of the present invention comprises a base component (A) (hereinafter referred to as “component (A)”) whose alkali solubility is increased by the action of an acid, and an acid upon irradiation with an acid.
  • the positive resist composition containing the component (A) and the component (B) when the acid generated from the component (B) by exposure acts on the component (A) by exposure, the whole component (A) However, it is changed to alkali-soluble from Al-insoluble silica. Therefore, in the formation of the resist pattern, when the resist film having the positive resist composition strength is selectively exposed or heated after exposure in addition to the exposure, the exposed portion turns to be soluble in the Al force while the unexposed portion is changed. Since it remains insoluble in alkali and does not change, a positive resist pattern can be formed by alkali development.
  • the component (A) contains the low molecular compound (A1).
  • the low molecular compound (A1) may be used alone or in combination of two or more.
  • the proportion of the low molecular weight compound (A1) is preferably more than 40% by mass, more preferably more than 50% by mass, and most preferably more than 80% by mass. Is 100% by mass.
  • the proportion of the low molecular compound (A1) in component (A) can be measured by means such as reverse phase chromatography.
  • the component (A) has been proposed as a base material component of a chemically amplified resist layer to the extent that the effect of using the low molecular compound (A1) is not impaired.
  • component (A2) examples include those proposed as base resins for conventional chemically amplified KrF positive resist compositions, ArF positive resist compositions, and the like. It can be suitably selected according to the type of exposure light source used sometimes.
  • the content of the component (A) in the positive resist composition may be adjusted according to the resist film thickness to be formed.
  • the component (B) is not particularly limited, and any component that has been proposed as an acid generator for chemical amplification resists can be used.
  • Such acid generators have so far been iodenium salts and sulfo-salt salts.
  • Various generators such as generators, iminosulfonate acid generators, disulfone acid generators are known.
  • form salt-based acid generators include acid generators represented by the following general formula (b-0).
  • R 51 represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group
  • R 52 represents a hydrogen atom, a hydroxyl group, a halogen atom, a straight chain, branched or cyclic alkyl group, a linear or branched halogenated alkyl group or a linear or branched alkoxy group
  • R 53 is substituted Moyoi Is an aryl group
  • u and are integers 1 to 3.
  • R 51 represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group.
  • the linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
  • the cyclic alkyl group preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and still more preferably 6 to carbon atoms: LO.
  • 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 fluorination rate of the alkyl group (the ratio of the number of substituted fluorine atoms to the total number of hydrogen atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%, particularly hydrogen atoms. This is preferable because the strength of the acid increases.
  • R 51 is most preferably a linear alkyl group or a linear fluorinated alkyl group.
  • R 52 is a hydrogen atom, a hydroxyl group, a halogen atom, a linear, branched or cyclic alkyl group, a linear or branched halogen-I human alkyl group or a linear or branched alkoxy group, It is.
  • examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and a fluorine atom is preferable.
  • the linear or branched alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably carbon number power ⁇ Most preferred is ⁇ 3.
  • R 52 the alkyl group of cyclic, number 4-10 force preferred instrument carbon 4-12 carbon atoms
  • S further preferred instrument carbon atoms 5: most preferably LO.
  • the halogenated alkyl group is a group in which part or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms.
  • the alkyl group herein are the same as the “linear or branched alkyl group” in R 52 .
  • Examples of the halogen atom to be substituted include the same as those described for the “halogen atom” in R 52 above.
  • halogenated alkyl group it is desirable that 50 to 100% of the total number of hydrogen atoms are substituted with halogen atoms, and it is more preferable that all are substituted! /.
  • the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.
  • R 52 is preferably a hydrogen atom.
  • R 53 may have a substituent, but may be an aryl group, and the structure of the basic ring (matrix ring) may be a naphthyl group, a phenyl group, an anthracene group. From the viewpoint of the effect of the present invention and the absorption of exposure light such as ArF excimer laser, the phenyl group is desirable.
  • substituents examples include a hydroxyl group and a lower alkyl group (straight or branched chain, preferably having 5 or less carbon atoms, particularly preferably a methyl group).
  • aryl group for R 53 those having no substituent are more preferable.
  • u ′ ′ is an integer of 1 to 3, 2 or 3 is preferred, and 3 is particularly desirable.
  • Preferable examples of the acid generator represented by the general formula (b-O) include those represented by the following chemical formula.
  • the acid generators represented by the general formula (b—O) can be used alone or in combination.
  • 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, Decanyl group, etc., excellent resolution, A methyl group is preferable because it can be synthesized at a low cost.
  • R 4 represents a linear, branched or cyclic alkyl group or fluorinated alkyl group.
  • 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 most preferably 1 to 4 carbon atoms. Also.
  • the fluorination rate (ratio of fluorine atoms in the alkyl group) of the fluorinated alkyl group is preferably 10 to: LOO%, 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. Of R 5, ⁇ ⁇ R 6 , at least one represents an aryl group. All of R 5 ′′ to R 6 , are preferably 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.
  • the onion salt-based acid generator represented by the above general formula (b-1) or (b-2) include trifluoromethanesulfonate, nonafluorobutanesulfonate, bis (4 — Tert-Butylphenol) Jodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, triphenylsulfur trifluoride Fluorosulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tri (4 methylphenol) sulfo-trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorolob Tan sulfonate, dimethyl (4-hydroxynaphthyl) sulfone trifluoromethane sulfonate, its heptafluoropropane sulfonate or
  • ohmic salt in which the cation part of these ohmic salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate.
  • the anion part is replaced with a caron part represented by the following general formula (b-3) or (b-4).
  • a -um salt-based acid generator can also be used (the cation moiety is the same as (b-1) or (b-2)).
  • 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 linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 3 carbon atoms. 5 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 LOO%. Most preferably, it is a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
  • the oxime sulfonate 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 31 and R 32 each independently represents an organic group.
  • the organic group of R 31 and R 32 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.).
  • a linear, branched or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent.
  • the substituent is not particularly limited, and examples thereof include a fluorine atom and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.
  • “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 31 is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms.
  • organic group for R 32 a linear, branched or cyclic alkyl group, aryl group or cyan group is preferable.
  • alkyl group and aryl group for R 32 include the same alkyl groups and aryl groups as those described above for R 31 .
  • R 32 in particular, 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 is preferred.
  • More preferable examples of the oxime sulfonate acid generator include compounds represented by the following general formula (B-2) or (B-3).
  • R 33 represents a cyano group, an alkyl group having no substituent, or a halogenalkyl group.
  • R 34 is an aryl group.
  • R 35 represents an alkyl group having no substituent or a halogenated alkyl group.
  • R 36 represents a cyano group, an alkyl group having no substituent, or a halogenalkyl group.
  • R 37 is a divalent or trivalent aromatic hydrocarbon group.
  • R 38 is an alkyl group having no substituent or a halogenated alkyl group.
  • ⁇ ' is 2 or 3.
  • the alkyl group or halogenated alkyl group having no substituent of R 33 preferably has 1 to 8 carbon atoms: 1 to 8 carbon atoms. Is more preferred. Carbon number 1 to 6 is most preferred.
  • R 33 is more preferably a fluorinated alkyl group, preferably a halogenated alkyl group.
  • the fluorinated alkyl group in R 33 is preferably fluorinated with 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, and even more preferably 90% or more. I like it! /
  • the aryl group of R 3 includes an aromatic group such as a phenol group, a biphenyl group, a fluoro group, a naphthyl group, an anthracyl group, a phenanthryl group, and the like.
  • a roaryl group is preferable.
  • the aryl group of R 34 may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group.
  • the alkyl group or halogenated alkyl group in the substituent preferably has 1 to 4 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the halogenated alkyl group is preferably a fluorinated alkyl group.
  • the alkyl group or halogenated alkyl group having no substituent of R 35 preferably has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. Most preferred.
  • R 35 is preferably a partially or fully fluorinated alkyl group, preferably a halogenated alkyl group.
  • the fluorinated alkyl group in R 35 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.
  • the alkyl group or halogenated alkyl group having no substituent of R 36 is an alkyl group or halogenalkyl having no substituent of the above R 33. The same thing as a group is mentioned.
  • Examples of the divalent or trivalent aromatic hydrocarbon group for R 37 include groups in which the aryl group strength of R 34 is one or two hydrogen atoms removed.
  • P ′ ′ is preferably 2.
  • oxime sulfonate-based acid generators include ⁇ - (p-toluenesulfo-oxyximino) monobenzyl cyanide, ⁇ - ( ⁇ chlorobenzene-sulfo-oxyoximino) -benzyl cyanide, ⁇ - ( 4-Nitrobenzenesulfo-ruximino) —Benzyl cyanide, Hiichi (4-troo 2 trifluoromethylbenzenesulfo-ruximino) Benzyl cyanide, ⁇ - (Benzenesulfo-Luximinomino) -4-chlorobenzoyl cyanide, ⁇ (Benzenesulfo-Luximinomino) -2, 4 Dichlorobenzil cyanide, ⁇ — (Benzenesulfo-Luximinomino) -2 6 Dichlorobenzil cyanide, ⁇ (Benzenesulf
  • 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.
  • diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552 and JP-A-11-035573 can also be suitably used.
  • poly (bissulfol) diazomethanes include 1,3 bis (phenylsulfol diazomethylsulfol) pronone, 1, 4 disclosed in JP-A-11 322707.
  • 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 is preferably 1 to 15 parts by mass, more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the component (A). Pattern formation is sufficiently performed when the amount falls within the above range. Further, it is preferable because a uniform solution can be obtained and the storage stability becomes good. [0119] [Optional components]
  • the positive resist composition of the present invention is further optional in order to improve the resist pattern shape, post exposure stability of the latent image formed oy the pattern-wise exposure of the resist layer, and the like.
  • component (D) nitrogen-containing organic compound (hereinafter referred to as component (D)) can be blended.
  • 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).
  • component (E) an organic carboxylic acid or phosphorus oxo acid or a derivative thereof (hereinafter referred to as component (E)) can be contained.
  • component (D) and the component (E) can be used in combination, or one 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 diphenol ester and other phosphoric acid or derivatives such as those esters, phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid Phosphonic acid such as n-butyl ester, phenol phosphonic acid, diphosphoric phosphonic acid ester, dibenzyl phosphonic acid ester and derivatives thereof, phosphinic acid such as phosphinic acid, phenol phosphinic acid and the like And derivatives such as esters, of which phosphonic acid is particularly preferred.
  • 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 can be produced by dissolving the material in an organic solvent (hereinafter sometimes referred to as "component (S)").
  • each component to be used it is sufficient if each component to be used can be dissolved into a uniform solution. Any one of conventionally known solvents for chemically amplified resists can be used. Two or more kinds can be appropriately selected and used.
  • ⁇ -latatones such as butyrolatatatone
  • ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone
  • polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and their derivatives Cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate , It may be mentioned Echiru pyruvate, methyl methoxypropane
  • 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 (PGME A) and a polar solvent is also 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. Preferably within the range.
  • the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. ,.
  • a mixed solvent of at least one selected from among PGMEA and EL and ⁇ -petit-mouth rataton is also preferable.
  • the mixing ratio of the former and the latter is preferably 70: 30-95: 5.
  • the amount of component (S) used is not particularly limited, but it is a concentration that can be applied to a substrate, etc., and can be appropriately set according to the coating film thickness.
  • the solid content concentration of the resist composition is 2 to 2. It is used so as to be in the range of 0% by mass, preferably 5 to 15% by mass.
  • the positive resist composition of the fourth embodiment includes a step of forming a resist film on a substrate using the positive resist composition of the fourth embodiment, a step of exposing the resist film, and the step of It can be used for a resist pattern forming method (resist pattern forming method of the fifth embodiment) including a step of developing a resist film to form a resist pattern.
  • the resist pattern forming method can be performed, for example, as follows.
  • the positive resist composition of the fourth embodiment is applied onto a substrate such as a silicon wafer with a spinner or the like, and optionally subjected to pre-beta ( ⁇ ) to form a resist film.
  • the formed resist film is exposed through a mask pattern using an exposure apparatus such as an ArF exposure apparatus, an electron beam drawing apparatus, or an EUV exposure apparatus, or drawn by direct irradiation of an electron beam without using a mask pattern.
  • PEB post-exposure heating
  • rinsing is performed, and the developer on the substrate and the resist composition dissolved by the developer are washed away and dried to obtain a resist pattern.
  • the operating conditions and the like are preferably set as appropriate according to the composition and characteristics of the positive resist composition to be used.
  • the exposure light source is not particularly limited. ArF excimer laser, KrF excimer laser, F
  • the positive resist composition is effective for ArF excimer laser, electron beam or EUV, particularly ArF excimer laser or electron beam.
  • a post-beta step after the alkali development may be included, and an organic or inorganic antireflection film may be provided between the substrate and the resist film.
  • the low molecular compound (A1) can also be suitably used as a dissolution inhibitor for a positive resist composition.
  • a dissolution inhibitor that also has the low molecular compound (A1) power By using a dissolution inhibitor that also has the low molecular compound (A1) power, the alkali solubility of the resist film (before exposure) obtained using the positive resist composition containing the dissolution inhibitor is suppressed. Therefore, when the resist film is selectively exposed, the difference in alkali solubility (dissolution contrast) between the exposed portion and the unexposed portion is increased, and a resist pattern with good resolution and shape can be formed.
  • Such a dissolution inhibitor can be used by being added to a two-component chemically amplified resist composition containing a resin component having an acid dissociable dissolution inhibiting group and an acid generator component. It can also be used as a V-type three-component chemically amplified resist composition using a resin component, an acid generator component and a dissolution inhibitor that do not have a dissolution inhibitor group.
  • the compound of the sixth embodiment of the present invention (hereinafter referred to as compound (I) ′) has a hydroxyl group in two of the phenyl groups of the trimethane skeleton, as represented by the general formula (I) ′.
  • This is a tris (hydroxyphenyl) methane derivative having a structure in which R 11 and R 12 are bonded, and the remaining one group is bonded to a carboxy group (—COOH) and optionally R 13 .
  • R U to R 13 are the same as R U to R 13 in general formula (I) of the first embodiment.
  • p is 1 or 2.
  • the compound (I) ′ is preferably a compound represented by the following general formula (I 1) ′.
  • q is an integer of 0 to 2, preferably 0 or 1, and most preferably 0.
  • the bonding position of the carboxy group is not particularly limited, but at least one of the strengths of the compound produced using the obtained compound is suitable for the resist composition and the ease of synthesis. It is preferably bonded to the para position (position 4) of the ru group.
  • the bonding position of R 13 is not particularly limited, but is preferably bonded to at least one of the carbon atoms adjacent to the carbon atom to which the carboxyalkyloxy group is bonded, from the viewpoint of synthesis.
  • s is an integer of 1 to 2, preferably 1.
  • t is an integer of 1 to 3, preferably 1 or 2, and most preferably 1.
  • u is an integer of 1 to 3, preferably 1 or 2, and most preferably 1.
  • s + t + u is an integer of 3 to 5, preferably 3 or 4, and most preferably 3.
  • the bonding position of the hydroxyl group is not particularly limited, but the compound produced using the obtained compound is suitable for a resist composition and has at least one force group in view of ease of synthesis. It is preferably bonded to the para position (position 4).
  • R U to R 12 is not particularly limited, but R 11 or R 12 is bonded to at least one of the carbon atoms adjacent to the carbon atom to which the hydroxyl group is bonded, in terms of synthesis and the like.
  • R 11 or R 12 is preferably bonded to both carbon atoms adjacent to the carbon atom to which the hydroxyl group is bonded! /.
  • the compound (I) 'of the present invention in particular, a compound represented by the following general formula ( ⁇ )', and a compound produced by using the compound are suitable for resist compositions. Therefore, it is preferable.
  • R "to R” are each independently an alkyl group having 1 to C: LO; p is 1 or 2. ]
  • a compound having p of 1 is preferable, and a compound represented by the following general formula (II-1) ′ in which a carboxy group is bonded to the para position of the phenyl group is preferable.
  • R ′′ to R are each independently an alkyl group having 1 to carbon atoms: LO.
  • Compound (I) is, by selecting the type of the substituents R n to R 13, various characteristics, it is possible to adjust the alkali solubility and the like, for example.
  • the compound in which the substituent R 11 bonded to the ortho position of the phenolic hydroxyl group in the above formula ( ⁇ ) ′ is a bulky group such as a cyclohexyl group has the same structure, and R 11 Compared with a compound in which is a non-bulky group such as a methyl group, the alkali solubility is small.
  • the alkali solubility of the low molecular weight compound (A1) ′ obtained by using the compound (I) ′ as described later, for example, can be increased.
  • Compound (I) ' can be produced by applying a conventionally known method. Further, as shown in the following production method of the compound (I) ′ of the present invention, a carboxybenzaldehyde having a substituent and a phenol compound having a substituent may be subjected to acidic conditions. It can be produced from coconut paste by reaction (dehydration condensation) below.
  • the production method of the compound (I) ′ according to the seventh embodiment of the present invention includes the compound (1) ′ represented by the general formula (1) ′ and the compound (2) ′ represented by the general formula (2) ′. ) And reacting under acidic conditions to obtain compound (I) ′ of the present invention (hereinafter referred to as compound (I) ′ forming step).
  • reaction between compound (1) ′ and compound (2) ′ is carried out under acidic conditions.
  • the formyl group (one CHO) of compound (1) ′ reacts with compound (2) ′ to form compound (I) ′.
  • compound (1) ′ is dissolved in an organic solvent such as methanol, and about 2 equivalents of compound (2) ′ is added to compound (1) ′.
  • an acid such as hydrochloric acid, the reaction can be carried out.
  • the organic solvent used at this time may be any organic solvent that can dissolve the compounds (1) 'to (2)'. Any organic solvent may be selected. For example, methanol, ethano C1-C4 alcohol such as alcohol, tetrahydrofuran (THF) and the like. this Any of these organic solvents may be used alone or in admixture of two or more.
  • the acid used at this time is not particularly limited as long as it causes a reaction between compound (1) ′ and compound (2) ′.
  • Preferred are hydrochloric acid (aqueous salt hydrogen chloride solution), sulfuric acid, sulfuric anhydride, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid, etc. Specific examples can be given.
  • hydrochloric acid is preferably used. Any one of these acids may be used alone, or two or more of these acids may be used in combination.
  • the acid may be added in an amount that causes a reaction between compound (1) ′ and compound (2) ′.
  • compound (1) ′ is added to 100 parts by mass.
  • the amount is preferably 1 to 700 parts by mass, more preferably 100 to 600 parts by mass.
  • the reaction temperature is preferably 20 to 80 ° C, more preferably 30 to 65 ° C.
  • the reaction time is preferably 2 to 96 hours, more preferably 5 to 72 hours.
  • a base such as sodium hydroxide or sodium hydroxide is added to the reaction solution to neutralize the acid in the reaction solution.
  • a base such as sodium hydroxide or sodium hydroxide
  • the carboxy group may be slightly esterified by the alcohol. Therefore, in order to hydrolyze the ester, it is preferable to remove an excess base.
  • compound (I) ′ is dissolved as a salt.
  • reaction solution is transferred to a separatory funnel and washed with water Z-jetyl ether to remove the raw materials (compounds used in the reaction, etc.), and then the aqueous layer is taken out and washed with an aqueous hydrochloric acid solution. When neutralized, precipitation occurs. By collecting this precipitate by filtration or the like, compound (I) ′ can be obtained.
  • the compound (I) ′ thus obtained may be further subjected to purification treatment such as washing with water and reprecipitation.
  • the compound (I) ′ of the present invention can be suitably used for the production of a low molecular weight compound that can be used for a resist composition.
  • a compound represented by the above general formula (I 1) ′ (hereinafter referred to as compound (I 1) ′) is a low compound represented by the following general formula (A—1) ′ or (A—2) ′. It can be suitably used for the production of molecular compound (A1) '.
  • ⁇ , R 5 ⁇ R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group or a halogenoalkyl group
  • R 3 , ⁇ R 4 ′, R 9 , ⁇ R 10 are each independently
  • I 11 In the following general formula (I 11) ′, 1, m, ⁇ ′ and m are each independently an integer of 1 to 3; n, n and 1 to 3 Y is an (n + 1) valent organic group; Z is an (n, +1) valent organic group.
  • the low molecular weight compound (A1) has the structure as described above. For example, when it is blended with the acid generator component in a positive resist composition, it is generated from the acid generator component by exposure. Carbon group carbon adjacent to R 3 , ⁇ R 4 , and R 9 , ⁇ R 1G The bond between the oxygen atom bonded to the elementary atom and the carbon atom bonded to the oxygen atom ( ⁇ , R 5 to R 8 etc. bonded) is broken and decomposed.
  • the degradation product for example 'the case of the compound represented by the results distal portion is decomposed (n + 1) number of carboxylic acid (1 R 3' the general formula (A-1) - COOH And n R 4 '—COOH) and one compound derived from the central part (the part including Y, etc.). Also, 'if the compound represented by the results terminal portion with decomposition (n, + 1) number of carboxylic acid (1 R 9' the general formula (A- 2) - COOH and n, pieces R 1G , —CO OH) and one compound derived from the central part (the part including Z, etc.)
  • R 3 'to R 4 are each independently a group represented by general formula (1-11), and 1 to! ⁇ 13 , s, in general formula (1-11-1) t, u, q are the same as in formula (I), 1 to! ⁇ 13 , s, t, u, q.
  • R 3 to R 4 may be the same or different from each other, but are preferably the same in terms of synthesis.
  • m are each independently an integer of 1 to 3, preferably 1 or 2, and most preferably 1.
  • n is an integer of 1 to 3, preferably 1 or 2, and most preferably 1.
  • n is an integer of 2 or more, that is, the compound (A1), R 4 '-COO- [C (R 2
  • Y is an (n + 1) -valent organic group, and includes the same (n + 1) -valent organic group as Y in the general formula (A-1).
  • the alkyl group and halogenated alkyl group of R 5 to R 8 are represented by general formula (A-1) or general formula (A-1)! Examples include the same alkyl groups and halogenated alkyl groups as ⁇ 1 to! ⁇ 2 .
  • Examples of R 9 to R 1g include the same as R 3 to R 4 in the general formula (A-1).
  • M, n, and Z are the same as those in general formula (A-1), 1, m, n, and Y, respectively.
  • Low molecular weight compound (A1) has a chain structure between, and R 4 'or between R 9 ' and R 1G
  • Tg glass transition point
  • the low molecular compound (A1) ' is a material capable of forming an amorphous film by the spin coat method, as with the low molecular compound (A1) of the third embodiment.
  • the low molecular weight compound (A1) ′ has good stability of the amorphous film formed as described above.
  • PAB Post Applied Bake
  • a room temperature environment is used. It is preferable that the amorphous state is maintained even after being left for 2 weeks.
  • the low molecular compound (A1) ' is, for example, one or more compounds (I)' (more specifically, one or more compounds (1-1) '), tetrahydrofuran, And can be synthesized by reacting with a bischloro compound represented by the above general formula (a-1) or (a-2) in the presence of a catalyst such as triethylamine.
  • the low molecular weight compound (A1) ' is a base component whose alkali solubility is increased by the action of an acid.
  • a positive resist composition containing (A) ′ and an acid generator component (B) that generates an acid upon irradiation with radiation, it can be suitably used as the substrate component (A) ′.
  • a positive resist composition containing the low molecular compound (A1) ′ By using a positive resist composition containing the low molecular compound (A1) ′, a high resolution resist pattern can be formed. In addition, roughness can be reduced.
  • the low molecular weight compound (A1) ′ of the present invention is a low molecular weight non-polymer, and also has been used in conventional chemically amplified positive resists and the above-mentioned non-patent documents 1 and 2 etc.
  • the alkali-soluble groups do not need to be protected by the acid-dissociable, dissolution-inhibiting groups, so the structure is clear and the molecular weight is less uneven. Therefore, properties such as alkali solubility and hydrophilicity / hydrophobicity are uniform, and therefore a resist film with uniform properties can be formed.
  • the low molecular compound (A1) ′ of the present invention is decomposed by the action of the acid generated by exposure to produce 2 to 4 decomposition products, and the alkali solubility is increased. Later, no large molecular weight remains, and the difference in the individual molecular weights of the resulting degradation products becomes relatively small. For this reason, the decomposed products are evenly distributed in the resist film, and the difference in dissolution behavior in the alkaline developer between the decomposed products is small.
  • the low molecular weight compound (A1) has uniform properties, and it is thought that resist films with uniform properties (alkali and hydrophilic' hydrophobic, etc.) can be formed.
  • diffetats can be reduced.
  • diffetats are, for example, general defects detected when the resist pattern after development is also observed by the KLA Tencor surface defect observation device (trade name “KLA”). .
  • KLA KLA Tencor surface defect observation device
  • the storage stability of the positive resist composition containing the low molecular compound (A1)' is also considered. Will also improve.
  • the positive resist composition of the ninth embodiment generates a base component (A) ′ (hereinafter referred to as (A) ′ component) whose alkali solubility is increased by the action of an acid, and an acid upon irradiation with radiation.
  • a positive resist composition containing an acid generator component (B) (hereinafter referred to as component (B)), wherein the component (A) is represented by the general formula (A-1) 'or (A-2) Contains a low molecular weight compound (A1) represented by '.
  • the entire component (A)' It changes from alkali-insoluble to alkali-soluble. Therefore, in the formation of the resist pattern, when the resist film having the positive resist composition strength is selectively exposed or heated after exposure in addition to the exposure, the exposed portion turns into alkali-soluble while the unexposed portion becomes Since it remains insoluble in alkali and does not change, a positive resist pattern can be formed by alkali development.
  • the component contains the low molecular compound (A1)'.
  • the low molecular compound (A1) ′ may be used alone or in combination of two or more.
  • the proportion of 'low molecular weight compound (A1)' in the component is preferably more than 40% by mass 5
  • the ratio of the “low molecular compound (A1)” in the component can be measured by means such as reverse phase chromatography.
  • (A) 'Component has been proposed as a base material component of a chemically amplified resist layer so far as it does not impair the effect of using low molecular weight compound (A1)'! Containing a coconut oil component (hereinafter sometimes referred to as component (A2))! /, May! /.
  • Examples of the component (A2) include those proposed as base resins for conventional chemically amplified KrF positive resist compositions, ArF positive resist compositions, and the like. It can be suitably selected according to the type of exposure light source used sometimes. [0160] The content of the component (A) 'in the positive resist composition of the ninth embodiment may be adjusted according to the resist film thickness to be formed.
  • the component (B) is the same as the component (B) mentioned in the positive resist composition of the fourth embodiment.
  • R lw to R 3 ′′ are most preferably a phenyl group or a naphthyl group, respectively.
  • one type of acid generator may be used alone, or two or more types may be used in combination.
  • the content of the component (B) is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the (A) ′ component, and more preferably 1 to 15 parts by mass preferable. Pattern formation is sufficiently performed by setting the above range. In addition, it is preferable because a uniform solution is obtained and storage stability is good.
  • a nitrogen-containing organic compound (D) (hereinafter referred to as (D) is further added as an optional component in order to improve the resist pattern shape, the stability over time, and the like. Component)).
  • aliphatic amines particularly secondary aliphatic amines and tertiary aliphatic amines, can be used arbitrarily from known ones. Is preferred.
  • “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.
  • An ⁇ aliphatic cyclic group '' means a monocyclic group or a polycyclic group having no aromaticity.
  • an aliphatic amine at least one hydrogen atom of ammonia NH must have at least 12 carbon atoms.
  • Examples include amines substituted with alkyl groups or hydroxyalkyl groups below (alkylamines or alkylalcoholamines) or cyclic amines.
  • alkylamines and alkyl alcoholamines include the fourth embodiment.
  • the thing similar to a state is mentioned.
  • trialkylamines having 5 to 10 carbon atoms are more preferable, and tri-n-octylamine is most preferable.
  • Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom.
  • the heterocyclic compound may be monocyclic (aliphatic monocyclic ammine) or polycyclic (aliphatic polycyclic ammine).
  • aliphatic monocyclic amine examples include piperidine and piperazine.
  • aliphatic polycyclic amines those having 6 to 10 carbon atoms are preferred.
  • 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 fourth component is further added as an optional component.
  • the same organic carboxylic acid or phosphorous oxoacid or 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 of them can be used.
  • 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 ninth embodiment further has a miscible additive, for example, an additional resin for improving the performance of the resist film, in order to improve coatability.
  • a miscible additive for example, an additional resin for improving the performance of the resist film, in order to improve coatability.
  • surfactants, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes and the like can be added and contained as appropriate.
  • the positive resist composition of the ninth embodiment can be produced by dissolving the material in an organic solvent (hereinafter, sometimes referred to as "(S), component").
  • each component to be used it is sufficient if each component to be used can be dissolved into a uniform solution. Any one of conventionally known solvents for chemically amplified resists can be used. Alternatively, two or more types can be appropriately selected and used.
  • latones such as ⁇ -butyrolatatane; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl- ⁇ -amyl ketone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol, dipropylene Polyhydric alcohols such as glycol and derivatives thereof; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; the above polyhydric alcohols or the above Monomethyl ether, monoethylenoatenore, monopropinoreatenore, monobutenoleatenore, etc.
  • Hue - polyvalent derivatives of alcohol such as compounds having an ether bond such as ether, cyclic ethers and like Jiokisan, methyl lactate Echiru
  • esters such as methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and the like.
  • organic solvents can be used alone or as a mixed solvent of two or more.
  • PGMEA propylene glycol monomethyl ether acetate
  • PGME propylene glycol monomethyl ether
  • EL EL
  • a mixed solvent in which PGMEA and a polar solvent are mixed is preferable.
  • the mixing 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. Preferably within range! /.
  • the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2.
  • the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: Three.
  • a mixed solvent of at least one selected from among PGMEA and EL and ⁇ -petit-mouthed ratatones is also preferable.
  • the mixing ratio of the former and the latter is preferably 70:30 to 95: 5.
  • the amount of the component 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. 2 -20% by mass, preferably 5-15% by mass.
  • the positive resist composition of the ninth embodiment includes a step of forming a resist film on a substrate using the positive resist composition of the ninth embodiment, a step of exposing the resist film, and the It can be used for a resist pattern forming method (resist pattern forming method of the tenth embodiment) including a step of developing a resist film to form a resist pattern.
  • the resist pattern forming method can be carried out in the same manner as the resist pattern forming method of the fifth embodiment except that the positive resist composition of the ninth embodiment is used as the positive resist composition.
  • the low molecular compound (A1) ′ can also be suitably used as a dissolution inhibitor for positive resist compositions.
  • a dissolution inhibitor composed of the low molecular compound (A1) ′ By using a dissolution inhibitor composed of the low molecular compound (A1) ′, the alkali solubility of a resist film (before exposure) obtained using a positive resist composition containing the dissolution inhibitor is suppressed. The Therefore, when the resist film is selectively exposed, the difference in alkali solubility (dissolution contrast) between the exposed portion and the unexposed portion is increased, and a resist pattern with good resolution and shape can be formed. .
  • Such a dissolution inhibitor can be used by being added to a two-component chemically amplified resist composition containing a resin component having an acid dissociable dissolution inhibiting group and an acid generator component. It can also be used as a V-type three-component chemically amplified resist composition using a resin component, an acid generator component and a dissolution inhibitor that do not have a dissolution inhibitor group.
  • THF tetrahydrofuran
  • 4-hydroxybenzaldehyde (1) 200 g was dissolved in 20 g of 4-hydroxybenzaldehyde (1) and dissolved.
  • K 2 CO 3 potassium carbonate
  • the positive resist composition is uniformly applied on an 8-inch silicon substrate subjected to hexamethyldisilazane treatment using a spinner, and subjected to beta treatment (PAB) at 110 ° C. for 90 seconds to form a resist film. (Film thickness 150 nm) was formed.
  • the resist film is drawn on a large area (1 / zm square) at an acceleration voltage of 70 kV using an electron beam lithography machine HL-800D (manufactured by Hitachi), and beta treatment (PEB) at 110 ° C for 90 seconds. ) performed, tetramethylammonium - Umuhidorokishido developed for 60 seconds using a (0.5 mass 0/0 aqueous solution of TMAH) (23 ° C) was carried out. At that time, find the change in the remaining film ratio (resist film thickness after development, Z film thickness (before exposure) resist film thickness) due to the change in the electron beam (EB) exposure dose (EB irradiation dose, / cm 2 ). A residual film curve was created (Fig. 1).
  • the positive resist composition containing the low molecular weight compound obtained by using the compound of the present invention can obtain a good contrast.
  • reaction solution was returned to room temperature, and then an aqueous potassium hydroxide solution was added to make the reaction solution alkaline, followed by stirring for 10 hours.
  • reaction solution was neutralized with a saline-hydrogen aqueous solution (neutrality was confirmed with a pH test paper) to obtain a precipitate.
  • This precipitate was filtered, washed with water, and dried to obtain 31 g of compound (3).
  • reaction solution was returned to room temperature, and then an aqueous potassium hydroxide solution was added to make the reaction solution alkaline, followed by stirring for 10 hours.
  • reaction solution was neutralized with a saline-hydrogen aqueous solution (neutrality was confirmed with a pH test paper) to obtain a precipitate.
  • the precipitate was filtered, washed with water, and dried to obtain 15 g of compound (5).
  • IR data 3357, 2926, 2852, 1692 , 1609, 1416, 1283cm _1.
  • the present invention relates to a compound that can be suitably used for the production of a low-molecular compound that can be used as a resist composition, a method for producing the compound, a low-molecular compound obtained using the compound, and the low-molecular compound.
  • a positive resist composition can be provided, and a resist pattern forming method using the positive resist composition can be provided.

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Abstract

Compounds represented by the general formula (I) or (I’) wherein R11 to R13 are each alkyl having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3; the sum of s, t and u is an integer of 3 to 5; q is an integer of 0 to 2; r is an integer of 1 to 3; and p is 1 or 2.

Description

明 細 書  Specification
化合物およびその製造方法、低分子化合物、ポジ型レジスト組成物およ びレジストパターン形成方法  Compound and method for producing the same, low molecular weight compound, positive resist composition, and resist pattern forming method
技術分野  Technical field
[0001] 本発明は、レジスト組成物用としての利用が可能な低分子化合物の製造に好適に 使用できる化合物、および該化合物の製造方法、前記化合物を用いて得られる低分 子化合物、該低分子化合物を含有するポジ型レジスト組成物、該ポジ型レジスト組成 物を用いるレジストパターン形成方法に関する。  [0001] The present invention relates to a compound that can be suitably used for the production of a low-molecular compound that can be used as a resist composition, a method for producing the compound, a low-molecular compound obtained by using the compound, and the low-molecular compound. The present invention relates to a positive resist composition containing a molecular compound and a resist pattern forming method using the positive resist composition.
本願は、 2005年 07月 25曰に曰本国に出願された特願 2005— 214219号と、 20 05年 10月 13曰に曰本国に出願された特願 2005— 298711号と、 2005年 10月 07 日に日本国に出願された特願 2005— 294531号に基づく優先権を主張し、その内 容をここに援用する。  This application consists of Japanese Patent Application No. 2005-214219, filed in Japan on July 25, 2005, and Japanese Patent Application No. 2005-298711, filed in Japan on October 13, 2005, October 2005 Claiming priority based on Japanese Patent Application No. 2005-294531 filed in Japan on 07th, the contents of which are incorporated herein by reference.
背景技術  Background art
[0002] 近年、半導体素子や液晶表示素子の製造においては、リソグラフィー技術の進歩 により急速にパターンの微細化が進んで 、る。  In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has rapidly progressed due to advances in lithography technology.
微細化の手法としては、一般に、露光光源の短波長化が行われている。具体的に は、従来は、 g線、 i線に代表される紫外線が用いられていた力 現在では、 KrFェキ シマレーザーや、 ArFエキシマレーザーを用いた半導体素子の量産が開始されてい る。また、これらエキシマレーザーより短波長の Fエキシマレーザー、電子線、 EUV (  As a technique for miniaturization, the wavelength of an exposure light source is generally shortened. Specifically, the power used in the past, typically ultraviolet rays such as g-line and i-line, has now begun mass production of semiconductor devices using KrF excimer laser and ArF excimer laser. In addition, these excimer lasers have shorter wavelength excimer lasers, electron beams, EUV (
2  2
極紫外線)や X線などにっ 、ても検討が行われて 、る。  Extreme ultraviolet rays) and X-rays are also being studied.
また、微細な寸法のパターンを形成可能なパターン形成材料の 1つとして、膜形成 能を有する基材成分と、露光により酸を発生する酸発生剤成分とを含有する化学増 幅型レジストが知られている。化学増幅型レジストには、露光によりアルカリ可溶性が 低下するネガ型と、露光によりアルカリ可溶性が増大するポジ型とがある。  As one of the pattern forming materials capable of forming a pattern with a fine dimension, a chemically amplified resist containing a base material component capable of forming a film and an acid generator component that generates an acid upon exposure is known. It has been. Chemically amplified resists are classified into a negative type in which alkali solubility is reduced by exposure and a positive type in which alkali solubility is increased by exposure.
[0003] 従来、このような化学増幅型レジストの基材成分としてはポリマーが用いられており 、例えばポリヒドロキシスチレン (PHS)やその水酸基の一部を酸解離性溶解抑制基 で保護した榭脂等の PHS系榭脂、（メタ)アクリル酸エステルカゝら誘導される共重合 体やそのカルボキシ基の一部を酸解離性溶解抑制基で保護した榭脂等が用いられ ている。 [0003] Conventionally, polymers have been used as the base component of such chemically amplified resists. For example, polyhydroxystyrene (PHS) or a part of its hydroxyl group protected with an acid dissociable, dissolution inhibiting group. Copolymers derived from PHS resin such as (meth) acrylate ester For example, rosin or the like in which a part of the body or its carboxy group is protected with an acid dissociable, dissolution inhibiting group is used.
しかし、このようなパターン形成材料を用いてパターンを形成した場合、パターンの 上面や側壁の表面に荒れ (ラフネス）が生じる問題がある。たとえばレジストパターン 側壁表面のラフネス、すなわちラインエッジラフネス（LER)は、ホールパターンにお けるホール周囲の歪みや、ラインアンドスペースパターンにおけるライン幅のばらつき 等の原因となるため、微細な半導体素子の形成等に悪影響を与えるおそれがある。 かかる問題は、パターン寸法が小さいほど重大となってくる。そのため、例えば電子 線や EUVによるリソグラフィーでは、数 lOnmの微細なパターン形成を目標として ヽ ること力ら、現状のパターンラフネスを越える極低ラフネスが求められて 、る。  However, when a pattern is formed using such a pattern forming material, there is a problem that roughness is generated on the upper surface of the pattern and the surface of the side wall. For example, the roughness of the resist pattern side wall surface, that is, the line edge roughness (LER), causes distortion around the hole in the hole pattern and variations in the line width in the line and space pattern. It may adversely affect Such a problem becomes more serious as the pattern size is smaller. For this reason, for example, in lithography using an electron beam or EUV, an extremely low roughness exceeding the current pattern roughness is required due to the ability to form a fine pattern of several lOnm.
しかし、一般的に基材成分として用いられているポリマーは、分子サイズ (一分子当 たりの平均自乗半径)が数 nm前後と大きい。パターン形成の現像工程において、現 像液に対するレジストの溶解挙動は通常、基材成分 1分子単位で行われるため、基 材成分としてポリマーを使う限り、さらなるラフネスの低減は極めて困難である。  However, polymers generally used as a base component have a large molecular size (average square radius per molecule) of around several nanometers. In the development process of pattern formation, the dissolution behavior of the resist in the current image solution is usually performed in units of one molecular component of the base material. Therefore, as long as a polymer is used as the base material component, further reduction in roughness is extremely difficult.
[0004] このような問題に対し、極低ラフネスを目指した材料として、基材成分として低分子 材料を用いるレジストが提案されている。たとえば非特許文献 1, 2には、水酸基、力 ルポキシ基等のアルカリ可溶性基を有し、その一部または全部が酸解離性溶解抑制 基で保護された低分子材料が提案されて 、る。 [0004] To solve such problems, a resist using a low-molecular material as a base component has been proposed as a material aiming for extremely low roughness. For example, Non-Patent Documents 1 and 2 propose low molecular weight materials having an alkali-soluble group such as a hydroxyl group or a forceful alkoxy group, and a part or all of which is protected with an acid dissociable, dissolution inhibiting group.
非特許文献 1 :T. Hirayama, D. Shiono, H. Hada and J. Onodera :J. Photo polym. Sci. Technol. 17 (2004)、 p435  Non-Patent Document 1: T. Hirayama, D. Shiono, H. Hada and J. Onodera: J. Photo polym. Sci. Technol. 17 (2004), p435
非特許文献 2 :Jim— Baek Kim, Hyo-Jin Yun, Young— Gil Kwon: Chemis try Letters (2002)、 pl064〜 1065  Non-Patent Document 2: Jim— Baek Kim, Hyo-Jin Yun, Young— Gil Kwon: Chemis try Letters (2002), pl064-1065
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0005] このような低分子材料は、低分子量であるが故に分子サイズが小さぐラフネスを低 減できると予想される。そのため、レジスト組成物とした際に、実際に使用できるレべ ルでレジストパターンを形成できる低分子材料に対する要求が高まっている。 [0005] Such a low molecular weight material is expected to be able to reduce roughness due to a small molecular size because of its low molecular weight. Therefore, when a resist composition is used, there is an increasing demand for a low molecular material capable of forming a resist pattern at a level that can be actually used.
本発明は、上記事情に鑑みてなされたものであって、レジスト組成物用としての利 用が可能な低分子化合物の製造に好適に使用できる化合物、および該化合物の製 造方法、前記化合物を用いて得られる低分子化合物、該低分子化合物を含有する ポジ型レジスト組成物、該ポジ型レジスト組成物を用いるレジストパターン形成方法を 提供することを目的とする。 The present invention has been made in view of the above circumstances, and is useful for resist compositions. A compound that can be suitably used for producing a low-molecular compound that can be used, a method for producing the compound, a low-molecular compound obtained by using the compound, a positive resist composition containing the low-molecular compound, the positive An object of the present invention is to provide a method for forming a resist pattern using a mold resist composition.
課題を解決するための手段  Means for solving the problem
[0006] 上記課題を解決する本発明の第一の態様 (aspect)は、下記一般式 (1— 0)で表さ れる化合物である。  [0006] A first aspect of the present invention that solves the above problems is a compound represented by the following general formula (1-0).
[0007] [化 1]  [0007] [Chemical 1]
Figure imgf000005_0001
Figure imgf000005_0001
[式（I 0)中、 RU〜R13はそれぞれ炭素数 1〜10のアルキル基であり； sは 1〜2の 整数であり； tは 1〜3の整数であり； uは 1〜3の整数であり； s+t+uは 3〜5の整数で あり； qは 0〜2の整数であり； Qは酸素原子又は単結合であり、； rは 0〜3の整数であ り； pは 1又は 2である。 ] [In the formula (I 0), R U to R 13 are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is 1 to S + t + u is an integer of 3 to 5; q is an integer of 0 to 2; Q is an oxygen atom or a single bond; r is an integer of 0 to 3 P is 1 or 2. ]
[0008] また、本発明の第二の態様は、下記一般式 (A— 1— 0)または (A— 2— 0)で表され る低分子化合物である。  [0008] The second aspect of the present invention is a low molecular compound represented by the following general formula (A-1-0) or (A-2-0).
[0009] [化 2]
Figure imgf000006_0001
[0009] [Chemical 2]
Figure imgf000006_0001
O R5 0 OR 5 0
R9—— C—— O- c- -z- c- -0—— C— R1 R 9 —— C—— O- c- -z- c- -0—— C— R 1
R6 R8 m R 6 R 8 m
( A - 2— 0 )  (A-2— 0)
[式中、 〜 ， R5〜R8はそれぞれ独立して水素原子、ハロゲン原子、アルキル基 またはハロゲンィ匕アルキル基であり； R3"〜R4 R9 -〜 R1C)-はそれぞれ独立して下記 一般式 (1—11—0)で表される基であり； 1, m, Ι' , m，はそれぞれ独立して 1〜3の整 数であり； n, n，は 1〜3の整数であり； Yは（n+ 1)価の有機基であり； Zは（n， + 1)価 の有機基である。 ] [Wherein, R 5 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group or a halogenated alkyl group; R 3 "to R 4 R 9-to R 1C) -are each independently And 1, m, Ι 'and m are each independently an integer of 1 to 3; n, n and 1 to 3 are the groups represented by the following general formula (1-11-0). Y is an (n + 1) valent organic group; Z is an (n, +1) valent organic group.]
[化 3] [Chemical 3]
Figure imgf000006_0002
Figure imgf000006_0002
[式中、 R 〜R はそれぞれ炭素数 1〜10のアルキル基であり； sは 1〜2の整数であ り； tは 1〜3の整数であり； uは 1〜3の整数であり； s + t + uは 3〜5の整数であり； qは 0〜2の整数であり； Qは酸素原子又は単結合であり； rは 0〜3の整数である。 ] また、本発明の第三の態様は、酸の作用によりアルカリ可溶性が増大する基材成分 ( A— 0)、および放射線の照射により酸を発生する酸発生剤成分 (B)を含有するポジ 型レジスト組成物であって、 前記基材成分 (A— 0)が、下記一般式 (A— 1— 0)または (A— 2— 0)で表される 低分子化合物 (A1—0)を含有するポジ型レジスト組成物である。 [Wherein R to R are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3] S + t + u is an integer of 3-5; q is an integer of 0-2; Q is an oxygen atom or a single bond; r is an integer of 0-3. The third aspect of the present invention is a positive electrode containing a base component (A-0) whose alkali solubility is increased by the action of an acid, and an acid generator component (B) which generates an acid upon irradiation with radiation. Type resist composition comprising: A positive resist composition in which the base component (A-0) contains a low molecular compound (A1-0) represented by the following general formula (A-1-0) or (A-2-0) is there.
[0012] [化 4] [0012] [Chemical 4]
(Λ— 1 - 0： (Λ— 1-0:
Figure imgf000007_0001
Figure imgf000007_0001
[式中、 〜 ， R5〜R8はそれぞれ独立して水素原子、ハロゲン原子、アルキル基 またはハロゲンィ匕アルキル基であり； R3"〜R4 R9 -〜 R1C)-はそれぞれ独立して下記 一般式 (1—11—0)で表される基であり； 1, m, Ι' , m，はそれぞれ独立して 1〜3の整 数であり； n, n，は 1〜3の整数であり； Yは（n+ 1)価の有機基であり； Zは（n， + 1)価 の有機基である。 ] [Wherein, R 5 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group or a halogenated alkyl group; R 3 "to R 4 R 9-to R 1C) -are each independently And 1, m, Ι 'and m are each independently an integer of 1 to 3; n, n and 1 to 3 are the groups represented by the following general formula (1-11-0). Y is an (n + 1) valent organic group; Z is an (n, +1) valent organic group.]
[0013] [化 5] [0013] [Chemical 5]
Figure imgf000007_0002
1— 1 1 0 )
Figure imgf000007_0002
1— 1 1 0)
[式中、 RU〜R13はそれぞれ炭素数 1〜10のアルキル基であり； sは 1〜2の整数であ り； tは 1〜3の整数であり； uは 1〜3の整数であり； s + t + uは 3〜5の整数であり； qは 0〜2の整数であり； Qは酸素原子又は単結合であり； rは 0〜3の整数である。 ] [0014] 上記第一の態様の化合物は、下記一般式 (I)で表される化合物であることが好ましい [Wherein R U to R 13 are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3] S + t + u is an integer of 3-5; q is an integer of 0-2; Q is an oxygen atom or a single bond; r is an integer of 0-3. ] [0014] The compound of the first aspect is preferably a compound represented by the following general formula (I)
[0015] [化 6] [0015] [Chemical 6]
Figure imgf000008_0001
Figure imgf000008_0001
[式 (I)中、 R 〜R はそれぞれ炭素数 1〜10のアルキル基であり； sは 1〜2の整数 であり； tは 1〜3の整数であり； uは 1〜3の整数であり； s+t+uは 3〜5の整数であり； qは 0〜2の整数であり； rは 1〜3の整数であり； pは 1又は 2である。 ] [In the formula (I), R to R are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3] S + t + u is an integer from 3 to 5; q is an integer from 0 to 2; r is an integer from 1 to 3; p is 1 or 2. ]
[0016] また、本発明の第四の態様は、下記一般式（1)で表される化合物（1)と下記一般 式 (2)で表される化合物（2)とを反応させて下記一般式 (3)で表される化合物（3)を 得る工程と、 [0016] Further, in the fourth aspect of the present invention, the following general formula (1) is reacted with the compound (2) represented by the following general formula (2). Obtaining a compound (3) represented by the formula (3);
前記化合物 (3)と下記一般式 (4)で表される化合物 (4)とを酸性条件下で反応させ て下記一般式 (I)で表される化合物 (I)を得る工程とを有する、下記一般式 (I)で表さ れる化合物 (I)の製造方法である。  Reacting the compound (3) with a compound (4) represented by the following general formula (4) under acidic conditions to obtain a compound (I) represented by the following general formula (I). This is a method for producing compound (I) represented by the following general formula (I).
[0017] [化 7] [0017] [Chemical 7]
Figure imgf000009_0001
Figure imgf000009_0001
[式中、 R は炭素数 1 10のアルキル基であり； qは 0 2の整数であり； pは 1又は 2 であり；Xはハロゲン原子であり； rは 1 3の整数であり； Rは保護基である。 ] [Wherein R is an alkyl group having 1 to 10 carbon atoms; q is an integer of 0 2; p is 1 or 2; X is a halogen atom; r is an integer of 1 3; R Is a protecting group. ]
[化 8] [Chemical 8]
Figure imgf000009_0002
Figure imgf000009_0002
(I)  (I)
[式中、 R R はそれぞれ炭素数 1 10のアルキル基であり； sは 1 2の整数であ り； tは 1 3の整数であり； uは 1 3の整数であり； s + t + uは 3 5の整数であり； qは 0 2の整数であり； rは 1 3の整数であり； pは 1又は 2であり； Rは保護基である。 ] 本発明の第二の態様の低分子化合物は、下記一般式 (A— 1)または (A— 2)で表 される低分子化合物であることが好まし 、。 [0020] [化 9] [Wherein RR is an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 2; t is an integer of 1 3; u is an integer of 1 3; s + t + u Is an integer of 35; q is an integer of 0 2; r is an integer of 1 3; p is 1 or 2; R is a protecting group. The low molecular compound of the second aspect of the present invention is preferably a low molecular compound represented by the following general formula (A-1) or (A-2). [0020] [Chemical 9]
Figure imgf000010_0001
Figure imgf000010_0001
[式中、 〜 ， R5〜R8はそれぞれ独立して水素原子、ハロゲン原子、アルキル基 またはハロゲンィ匕アルキル基であり； R3〜R4, R9〜R1C)はそれぞれ独立して下記一般 式 (I 11)で表される基であり； 1, m, Ι' , m，はそれぞれ独立して 1〜3の整数であり ； n, n，は 1〜3の整数であり； Yは（n+ 1)価の有機基であり； Zは（n， + 1)価の有機 基である。 ] Wherein, ~, R 5 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group or Harogeni spoon alkyl group; R 3 ~R 4, R 9 ~R 1C) are each independently the following A group represented by the general formula (I 11); 1, m, Ι ′ and m are each independently an integer of 1 to 3; n, n are an integer of 1 to 3; Y Is an (n + 1) -valent organic group; Z is an (n, +1) -valent organic group. ]
[0021] [化 10] [0021] [Chemical 10]
Figure imgf000010_0002
Figure imgf000010_0002
[式中、 R 〜R はそれぞれ炭素数 1〜10のアルキル基であり； sは 1〜2の整数であ り； tは 1〜3の整数であり； uは 1〜3の整数であり； s + t + uは 3〜5の整数であり； qは 0〜2の整数であり； rは 1〜3の整数である。 ] [Wherein R to R are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3] S + t + u is an integer of 3-5; q is an integer of 0-2; r is an integer of 1-3. ]
[0022] 本発明の第五の態様は、酸の作用によりアルカリ可溶性が増大する基材成分 (A) 、および放射線の照射により酸を発生する酸発生剤成分 (B)を含有するポジ型レジ スト組成物であって、 前記基材成分 (A)が、下記一般式 (A— 1)または (A— 2)で表される低分子化合 物 (A1)を含有するポジ型レジスト組成物である。 [0022] The fifth aspect of the present invention is a positive resist comprising a base component (A) whose alkali solubility is increased by the action of an acid, and an acid generator component (B) which generates an acid upon irradiation with radiation. A strike composition comprising: The base material component (A) is a positive resist composition containing a low molecular weight compound (A1) represented by the following general formula (A-1) or (A-2).
[0023] [化 11] [0023] [Chemical 11]
Figure imgf000011_0001
Figure imgf000011_0001
[式中、 〜 ， R5〜R8はそれぞれ独立して水素原子、ハロゲン原子、アルキル基 またはハロゲンィ匕アルキル基であり； R3〜R4, R9〜R1Gはそれぞれ独立して下記一般 式 (I 11)で表される基であり； 1, m, Ι' , m，はそれぞれ独立して 1〜3の整数であり ； n, n，は 1〜3の整数であり； Yは（n+ 1)価の有機基であり； Zは（n， + 1)価の有機 基である。 ] [Wherein, R 5 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group or a halogenoalkyl group; R 3 to R 4 and R 9 to R 1G are each independently Is a group represented by the formula (I 11); 1, m, Ι ′ and m are each independently an integer of 1 to 3; n, n are an integer of 1 to 3; Y is (N + 1) -valent organic group; Z is an (n, + 1) -valent organic group. ]
[0024] [化 12] [0024] [Chemical 12]
Figure imgf000011_0002
Figure imgf000011_0002
[式中、 R 〜R はそれぞれ炭素数 1〜10のアルキル基であり； sは 1〜2の整数であ り； tは 1〜3の整数であり； uは 1〜3の整数であり； s + t + uは 3〜5の整数であり； qは 0〜2の整数であり； rは 1〜3の整数である。 ] [0025] 本発明の第六の態様は、前記第五の態様のポジ型レジスト組成物を用いて基板上 にレジスト膜を形成する工程、前記レジスト膜を露光する工程、および前記レジスト膜 を現像してレジストパターンを形成する工程を含むレジストパターン形成方法である。 [Wherein R to R are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3] S + t + u is an integer of 3-5; q is an integer of 0-2; r is an integer of 1-3. ] [0025] In a sixth aspect of the present invention, a step of forming a resist film on a substrate using the positive resist composition of the fifth aspect, a step of exposing the resist film, and developing the resist film And a resist pattern forming method including a step of forming a resist pattern.
[0026] 上記第一の態様の化合物は、下記一般式 (I) 'で表される化合物であることが好ま しい。  [0026] The compound of the first aspect is preferably a compound represented by the following general formula (I) '.
[0027] [化 13]  [0027] [Chemical 13]
Figure imgf000012_0001
Figure imgf000012_0001
[式 (I)，中、 RU〜R "はそれぞれ独立して炭素数 1〜： L0のアルキル基であり； sは 1[In the formula (I), RU to R "are each independently an alkyl group having 1 to C carbon atoms; s is 1
〜2の整数であり； tは 1〜3の整数であり； uは 1〜3の整数であり； s+t+uは 3〜5の 整数であり； qは 0〜2の整数であり； pは 1または 2である。 ] T is an integer from 1 to 3; u is an integer from 1 to 3; s + t + u is an integer from 3 to 5; q is an integer from 0 to 2 P is 1 or 2; ]
[0028] また、本発明の第七の態様は、下記一般式（1) 'で表される化合物（1) 'と下記一 般式 (2) 'で表される化合物 (2) 'とを酸性条件下で反応させて下記一般式 (I) 'で表 される化合物を得る工程を有する化合物の製造方法である。 [0028] Further, in the seventh aspect of the present invention, there is provided a compound (1) 'represented by the following general formula (1)' and a compound (2) 'represented by the following general formula (2)'. This is a method for producing a compound having a step of obtaining a compound represented by the following general formula (I) ′ by reacting under acidic conditions.
[0029] [化 14] [0029] [Chem. 14]
一 （2 ) One (2)
Figure imgf000013_0001
… （I )
Figure imgf000013_0001
… (I)
[式中、 R"〜R13はそれぞれ独立して炭素数 1〜10のアルキル基であり； sは 1〜2の 整数であり； tは 1〜3の整数であり； uは 1〜3の整数であり； s+t+uは 3〜5の整数で あり； qは 0〜2の整数であり； pは 1または 2である。 ] [Wherein, R ″ to R 13 are each independently an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is 1 to 3] S + t + u is an integer from 3 to 5; q is an integer from 0 to 2; p is 1 or 2.]
[0030] ここで、本請求の範囲及び明細書における「アルキル基」は、特に記載のない限り、 直鎖状、分岐状および環状の 1価の飽和炭化水素基を包含するものとする。 [0030] Here, unless otherwise specified, the "alkyl group" in the claims and the specification includes linear, branched, and cyclic monovalent saturated hydrocarbon groups.
発明の効果  The invention's effect
[0031] 本発明により、レジスト組成物用としての利用が可能な低分子化合物の製造に好適 に使用できる化合物、および該化合物の製造方法、前記化合物を用いて得られる低 分子化合物、該低分子化合物を含有するポジ型レジスト組成物、該ポジ型レジスト組 成物を用いるレジストパターン形成方法が提供される。  [0031] According to the present invention, a compound that can be suitably used for the production of a low-molecular compound that can be used as a resist composition, a method for producing the compound, a low-molecular compound obtained by using the compound, and the low-molecular compound A positive resist composition containing a compound and a resist pattern forming method using the positive resist composition are provided.
図面の簡単な説明  Brief Description of Drawings
[0032] [図 1]本発明の化合物を用いて得られる低分子化合物を含有するポジ型レジスト組 成物の、 EB照射量の変化による残膜率変化を示す EB露光残膜曲線。  [0032] [FIG. 1] An EB exposure residual film curve showing a change in residual film ratio due to a change in EB irradiation amount of a positive resist composition containing a low molecular weight compound obtained by using the compound of the present invention.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0033] 以下、本発明につ 、て詳しく説明する。 [0033] Hereinafter, the present invention will be described in detail.
本発明の化合物は、上記一般式 (I 0)で表される（以下、一般式 (I 0)で表される 化合物は、化合物（I 0)という。）ように、トリフエ-ルメタン骨格のフエ-ル基の 2つ に水酸基と R11と R12とが結合し、残りの 1つのフエ-ル基にカルボキシアルキルォキ シ基（― O— (CH ) — CO— OH)又はカルボキシ基（― COOH)、及び任意に R13と The compound of the present invention is represented by the above general formula (I 0) (hereinafter represented by the general formula (I 0)) The compound is referred to as compound (I 0). ), A hydroxyl group and R 11 and R 12 are bonded to two of the phenyl groups of the triphenylmethane skeleton, and a carboxyalkyloxy group (—O— (CH ) — CO—OH) or a carboxy group (—COOH), and optionally R 13
2 r  2 r
が結合した構造を有するトリス (ヒドロキシフエニル)メタン誘導体である。なお、上記残 りの 1つのフエ-ル基に結合する基としては、上記のカルボキシアルキルォキシ基や カルボキシ基に限らず、これら以外の基 (但し、本発明の範囲内）、及び任意に R13が 結合していてもよい。 Is a tris (hydroxyphenyl) methane derivative having a structure in which The group bonded to the remaining one phenol group is not limited to the above carboxyalkyloxy group or carboxy group, but other groups (however, within the scope of the present invention) and optionally R 13 may be bonded.
上記一般式 (1— 0)中、 R"〜R13、 s、 t、 u、 q、 pは、後述する一般式 (I)中の 1〜!^ 3、 s、 t、 u、 q、 pと同様である。上記式 (I 0)中の Qは酸素原子又は単結合であり、 r は 0〜3の整数である。 rが 0の場合とは、単結合を意味する。 In the general formula (1-0), R "to R 13 , s, t, u, q, and p are 1 to! ^ 3, s, t, u, q, It is the same as p.Q in the above formula (I 0) is an oxygen atom or a single bond, and r is an integer of 0 to 3. The case where r is 0 means a single bond.
上記式 (I 0)中の Qが酸素原子で、 rが 1〜3の場合、後述する一般式 (I)で表され る化合物である。  When Q in the above formula (I 0) is an oxygen atom and r is 1 to 3, it is a compound represented by the following general formula (I).
上記一般式 (I 0)中の Qが単結合で、 rが 0の場合、後述する一般式 (I) 'で表され る化合物である。  When Q in the general formula (I 0) is a single bond and r is 0, it is a compound represented by the general formula (I) ′ described later.
[0034] 上記本発明の化合物 (I 0)は、レジスト組成物用としての利用が可能な低分子化合 物の製造に好適に使用でき、例えば、上記一般式 (A— 1— 0)または (A— 2— 0)で 表される低分子化合物 (以下、低分子化合物 (A1— 0) t 、う）の製造に好適に使用 できる。  [0034] The compound (I 0) of the present invention can be suitably used for the production of a low molecular weight compound that can be used as a resist composition. For example, the compound represented by the general formula (A-1-0) or ( It can be suitably used for the production of a low molecular compound represented by A-2-0) (hereinafter referred to as low molecular compound (A1-0) t).
一般式 (A— 1— 0)または (A— 2— 0)中、 〜 ， R5〜R8はそれぞれ独立して水 素原子、ハロゲン原子、アルキル基またはハロゲン化アルキル基であり、 R3"〜R4", R9 -〜 R1G"はそれぞれ独立して上記一般式 (1—11— 0)で表される基であり、 1, m, 1' , m，はそれぞれ独立して 1〜3の整数であり、 n, n'は 1〜3の整数であり、 Yは（n+ 1)価の有機基であり、 Zは (η' + 1)価の有機基である。 Formula (A- 1-0) or (A- 2-0) in, ~, R 5 to R 8 are each independently water atom, a halogen atom, an alkyl group or a halogenated alkyl group, R 3 "~R 4", R 9 -~ R 1G " are each independently a group represented by the general formula (1-11- 0), 1, m , 1 ', m, is independently N and n ′ are integers of 1 to 3, Y is an (n + 1) -valent organic group, and Z is an (η ′ + 1) -valent organic group.
上記一般式 (1—11—0)中、 RU〜R13はそれぞれ炭素数 1〜： L0のアルキル基であり 、 sは 1〜2の整数であり、 tは 1〜3の整数であり、 uは 1〜3の整数であり、 s+t+uは 3〜5の整数であり、 qは 0〜2の整数であり、 Qは酸素原子又は単結合であり、 rは 0 〜3の整数である。 rが 0の場合とは、単結合を意味する。 In the above general formula (1-11-0), R U to R 13 are each an alkyl group having 1 to L carbon atoms, s is an integer of 1 to 2, and t is an integer of 1 to 3. , U is an integer of 1 to 3, s + t + u is an integer of 3 to 5, q is an integer of 0 to 2, Q is an oxygen atom or a single bond, r is 0 to 3 Is an integer. The case where r is 0 means a single bond.
[0035] 上記一般式 (A— 1— 0)または (A— 2— 0)において、上記一般式 (1—11— 0)中 の Qが酸素原子で、 rが 1〜3の場合、後述する一般式 (A—1)または (A— 2)で表さ れる低分子化合物である。 [0035] In the general formula (A—1—0) or (A—2—0), When Q is an oxygen atom and r is 1 to 3, it is a low molecular compound represented by the following general formula (A-1) or (A-2).
上記一般式 (A— 1 0)または（A— 2— 0)にお!/、て、上記一般式 (I 11 0)中の Qが単結合で、 rが 0の場合、後述する一般式 (A— 1) 'または (A— 2) 'で表される低 分子化合物である。  In the above general formula (A—10) or (A—2—0)! /, When Q in the above general formula (I 11 0) is a single bond and r is 0, the general formula described below It is a low molecular weight compound represented by (A-1) 'or (A-2)'.
[0036] また、本発明のポジ型レジスト組成物は、酸の作用によりアルカリ可溶性が増大する 基材成分 (A— 0) (以下、（A—0)成分という）、および放射線の照射により酸を発生 する酸発生剤成分 (B) (以下、（B)成分という）を含有するポジ型レジスト組成物であ つて、  [0036] Further, the positive resist composition of the present invention comprises a base component (A-0) (hereinafter referred to as (A-0) component) whose alkali solubility is increased by the action of an acid, and an acid upon irradiation with an acid. A positive resist composition containing an acid generator component (B) (hereinafter referred to as component (B)) that generates
上記基材成分 ( A— 0)が、上記一般式 ( A— 1— 0)または ( A— 2— 0)で表される 低分子化合物 (A1— 0)を含有する。  The substrate component (A-0) contains a low molecular compound (A1-0) represented by the general formula (A-1-0) or (A-2-0).
このポジ型レジスト組成物は、基材成分 (A— 0)力 上記一般式 (A— 1— 0)または (A— 2— 0)で表される低分子化合物 (A1— 0)を含有する以外は、後述する第四又 は第九の実施形態のポジ型レジスト組成物と同様である。  This positive resist composition contains a base component (A—0) force and a low molecular compound (A1—0) represented by the above general formula (A—1—0) or (A—2—0) Except for this, it is the same as the positive resist composition of the fourth or ninth embodiment described later.
なお、上記ポジ型レジスト組成物中の (A—0)成分の含有量は、形成しょうとするレ ジスト膜厚に応じて調整すればよい。（A— 0)成分は、後述する任意の榭脂成分（(A 2)成分)を含有して!/、てもよ！、。  The content of the component (A-0) in the positive resist composition may be adjusted according to the resist film thickness to be formed. The component (A-0) contains an optional oil component (component (A 2)) described later! ,.
上記のような構成のポジ型レジスト組成物は、後述する第五又は第十の実施形態と 同様にレジストパターン形成方法に使用できる。  The positive resist composition having the above structure can be used in a resist pattern forming method as in the fifth or tenth embodiment described later.
[0037] 《第一の実施形態の化合物〉〉 [0037] << Compound of First Embodiment >>
本発明の第一の実施形態の化合物（以下、化合物 (I)という。）は、上記一般式 (I) で表されるように、トリフエ-ルメタン骨格のフエニル基の 2つに水酸基と R11と R12とが 結合し、残りの 1つのフエ-ル基にカルボキシアルキルォキシ基（ O— (CH ) — C The compound of the first embodiment of the present invention (hereinafter referred to as compound (I)) has a hydroxyl group and R 11 as two phenyl groups of the triphenylmethane skeleton, as represented by the above general formula (I). And R 12 combine, and the remaining one phenol group is a carboxyalkyloxy group (O— (CH) — C
2 r 2 r
O-OH)と任意に R13とが結合した構造を有するトリス (ヒドロキシフエ-ル)メタン誘導 体である。 This is a tris (hydroxyphenol) methane derivative having a structure in which O-OH) and optionally R 13 are combined.
[0038] 一般式 (I)中、 RU〜R13は炭素数 1〜10の直鎖状、分岐状または環状のアルキル 基である。前記アルキル基としては、炭素数 1〜5の直鎖状または分岐状の低級アル キル基、または炭素数 5〜6の環状アルキル基が好まし 、。 前記低級アルキル基としては、メチル基、ェチル基、プロピル基、イソプロピル基、 n ブチル基、イソブチル基、 tert ブチル基、ペンチル基、イソペンチル基、ネオペ ンチル基などの直鎖状または分岐状のアルキル基が挙げられ、これらの中でも、メチ ル基が好ましい。 In general formula (I), R U to R 13 are linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms. As the alkyl group, a linear or branched lower alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 5 to 6 carbon atoms is preferable. Examples of the lower alkyl group include linear or branched alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an nbutyl group, an isobutyl group, a tertbutyl group, a pentyl group, an isopentyl group, and a neopentyl group. Among these, a methyl group is preferable.
前記環状アルキル基としてはシクロへキシル基、シクロペンチル基等が挙げられる pは 1又は 2である。本発明においては、特に、該化合物を用いて製造される化合物 がレジスト組成物用として好適であるため、 pが 1であることが好ましい。すなわち、化 合物 (I)は、下記一般式 (I 1)で表される化合物であることが好ましい。  Examples of the cyclic alkyl group include a cyclohexyl group and a cyclopentyl group. P is 1 or 2. In the present invention, it is particularly preferable that p is 1 because a compound produced using the compound is suitable for a resist composition. That is, the compound (I) is preferably a compound represented by the following general formula (I 1).
[0039] [化 15] [0039] [Chemical 15]
Figure imgf000016_0001
Figure imgf000016_0001
•••(1- 1) ••• (1-1)
[式（1—1)中、 1〜!^13, s, t, u, q, rは、式（I)中の Rn〜R13, s, t, u, q, rと同様 である。 ] Wherein (1-1), 1 ~! ^ 13, s, t, u, q, r are the same as R n ~R 13, s, t , u, q, r in the formula (I) is there. ]
[0040] qは 0〜2の整数であり、好ましくは 0または 1であり、最も好ましくは 0である。  [0040] q is an integer of 0 to 2, preferably 0 or 1, and most preferably 0.
rは 1〜3の整数であり、好ましくは 1または 2であり、最も好ましくは 1である。 カルボキシアルキルォキシ基 [ O— (CH ) — CO— OH]の結合位置は、特に限  r is an integer of 1 to 3, preferably 1 or 2, and most preferably 1. The bonding position of the carboxyalkyloxy group [O— (CH) — CO— OH] is particularly limited.
2 r  2 r
定されないが、得られる化合物を用いて製造される化合物がレジスト組成物用として 好適であること、合成しやすさ等の点で、少なくとも、フエニル基のパラ位 (4位）に結 合していることが好ましい。  Although not specified, the compound produced using the resulting compound is suitable for use as a resist composition, is easy to synthesize, and is bonded to at least the para position (position 4) of the phenyl group. Preferably it is.
R13の結合位置は、特に限定されないが、合成のしゃすさ等の点で、カルボキシァ ルキルォキシ基が結合した炭素原子に隣接する炭素原子の少なくとも一方に結合し ていることが好ましい。 The bonding position of R 13 is not particularly limited, but it is bonded to at least one of the carbon atoms adjacent to the carbon atom to which the carboxyalkyloxy group is bonded in view of synthesis. It is preferable.
[0041] sは 1〜2の整数であり、好ましくは 1である。  [0041] s is an integer of 1 to 2, preferably 1.
tは 1〜3の整数であり、好ましくは 1または 2であり、最も好ましくは 1である。  t is an integer of 1 to 3, preferably 1 or 2, and most preferably 1.
uは 1〜3の整数であり、好ましくは 1または 2であり、最も好ましくは 1である。  u is an integer of 1 to 3, preferably 1 or 2, and most preferably 1.
s+t+uは 3〜5の整数であり、好ましくは 3または 4であり、最も好ましくは 3である。 水酸基の結合位置は、特に限定されないが、得られる化合物を用いて製造される 化合物がレジスト組成物用として好適であること、合成しやすさ等の点で、少なくとも 、フエ-ル基のパラ位 (4位）に結合していることが好ましい。  s + t + u is an integer of 3 to 5, preferably 3 or 4, and most preferably 3. The bonding position of the hydroxyl group is not particularly limited, but at least the para position of the phenol group is preferable in that the compound produced using the resulting compound is suitable for a resist composition and easy to synthesize. It is preferable that it is bonded to (position 4).
RU〜R12の結合位置は、特に限定されないが、合成のしゃすさ等の点で、水酸基 が結合した炭素原子に隣接する炭素原子の少なくとも一方に、 R11または R12が結合 していることが好ましぐ特に、水酸基が結合した炭素原子に隣接する炭素原子の両 方に R11または R12が結合して 、ることが好まし!/、。 The bonding position of R U to R 12 is not particularly limited, but R 11 or R 12 is bonded to at least one of the carbon atoms adjacent to the carbon atom to which the hydroxyl group is bonded, in terms of synthesis and the like. it is particularly preferred instrument, hydroxyl bonded R 11 or R 12 is to both of the carbon atoms adjacent to the carbon atom attached, is preferably Rukoto! /,.
[0042] 本発明の化合物 (I)としては、特に、下記一般式 (Π)で表される化合物が、該化合 物を用いて製造される化合物がレジスト組成物用として好適であるため好ましい。 As the compound (I) of the present invention, a compound represented by the following general formula (IV) is particularly preferable because a compound produced using the compound is suitable for a resist composition.
[0043] [化 16] [0043] [Chemical 16]
Figure imgf000017_0001
Figure imgf000017_0001
< Π )  <Π)
[式 (Π)中、 Ru R まそれぞれ炭素数 1〜10のアルキル基であり； rは 1〜3の整数 であり； pは 1又は 2である。 ] [In the formula (Π), Ru R is an alkyl group having 1 to 10 carbon atoms; r is an integer of 1 to 3; p is 1 or 2. ]
[0044] 式 (Π)中、 RU〜R12、 rおよび pは式 (I)中の RU〜R12、 rおよび pと同様である。 During [0044] Formula (Π), R U ~R 12 , r and p are the same as R U ~R 12, r and p in formula (I).
なかでも、 pが 1である化合物が好ましぐ特に、カルボキシアルキルォキシ基がフエ ニル基のパラ位に結合した下記一般式 (Π— 1)で表される化合物が好ましい Of these, compounds in which p is 1 are preferred. Compounds represented by the following general formula (Π-1) bonded to the para-position of the nyl group are preferred
[0045] [化 17] [0045] [Chemical 17]
Figure imgf000018_0001
Figure imgf000018_0001
[式中、 R 〜R はそれぞれ炭素数 1〜10のアルキル基であり、 rは 1〜3の整数であ る。] [Wherein R to R are each an alkyl group having 1 to 10 carbon atoms, and r is an integer of 1 to 3. ]
[0046] 式 (Π)で表される化合物としては、特に、合成しやすさ等の点で、下記一般式 (II— As the compound represented by the formula (Π), the following general formula (II—
2)または (Π— 3)で表される化合物が好ま 、。 The compound represented by 2) or (Π-3) is preferred.
[0047] [化 18] [0047] [Chemical 18]
Figure imgf000018_0002
Figure imgf000018_0002
[式中、 R 〜R はそれぞれ炭素数 1〜10のアルキル基であり、 rは 1〜3の整数であ り、 pは 1又は 2である。 ] [Wherein R to R are each an alkyl group having 1 to 10 carbon atoms, and r is an integer of 1 to 3] P is 1 or 2. ]
[0048] 化合物 (I)は、従来公知の方法により製造でき、たとえば、置換基を有していてもよ いアルコキシカルボ-ルアルキルォキシベンズアルデヒドと置換基を有するフエノー ルイ匕合物とを酸性条件下で脱水縮合させることによりトリス (ヒドロキシフエニル)メタン を得、該トリス (ヒドロキシフエ-ル)メタンの水酸基に、ブロモアセテート誘導体等のハ ロゲン化カルボン酸を反応させてカルボキシアルキルォキシ基を導入することにより 製造できる。しかし、このような従来公知の方法では、カルボキシアルキルォキシ基が 導入される水酸基の位置や数を制御しにくぐカルボキシアルキルォキシ基が 1つの ベンゼン環に結合したィ匕合物 (I)の収率が低 、と 、う問題がある。  [0048] Compound (I) can be produced by a conventionally known method. For example, compound (I) is obtained by acidifying an optionally substituted alkoxy carboalkyloxybenzaldehyde and a phenol compound having a substituent. By dehydration condensation under conditions, tris (hydroxyphenyl) methane is obtained, and a hydroxyl group of the tris (hydroxyphenyl) methane is reacted with a halogenated carboxylic acid such as a bromoacetate derivative to produce a carboxyalkyloxy group. Can be manufactured. However, in such a conventionally known method, a compound (I) in which a carboxyalkyloxy group that is difficult to control the position and number of hydroxyl groups into which a carboxyalkyloxy group is introduced is bonded to one benzene ring (I) There is a problem that the yield of is low.
そのため、化合物 (I)は、下記本発明の製造方法により製造されることが好ましい。  Therefore, the compound (I) is preferably produced by the following production method of the present invention.
[0049] 《第二の実施形態の化合物 (I)の製造方法〉〉 [0049] << Method for Producing Compound (I) of Second Embodiment >>
本発明の第二の実施形態の化合物 (I)の製造方法は、上記一般式（1)で表される 化合物（1)と上記一般式 (2)で表される化合物（2)とを反応させて上記一般式 (3)で 表される化合物（3)を得る工程 (以下、化合物（3)形成工程と ヽぅ）と、  The method for producing the compound (I) of the second embodiment of the present invention comprises reacting the compound (1) represented by the general formula (1) with the compound (2) represented by the general formula (2). A step of obtaining a compound (3) represented by the above general formula (3) (hereinafter referred to as compound (3) formation step and ヽ ぅ),
前記化合物 (3)と上記一般式 (4)で表される化合物 (4)とを酸性条件下で反応させ て本発明の化合物 (I)を得る工程 (以下、化合物 (I)形成工程と ヽぅ）とを有する。 以下、各工程についてより詳細に説明する。  A step of obtaining the compound (I) of the present invention by reacting the compound (3) with the compound (4) represented by the general formula (4) under acidic conditions (hereinafter referred to as the compound (I) formation step) Ii). Hereinafter, each process will be described in more detail.
[0050] <化合物（3)形成工程 > [0050] <Compound (3) formation step>
一般式（1)〜（3)中、 R13、 q、 p、 rは、上記一般式 (I)中の R13、 q、 p、 rと同様である 一般式 (2)中、 Xのハロゲン原子としては、臭素原子、塩素原子、フッ素原子等が 挙げられる。反応性に優れることから、臭素原子が好ましい。 In the general formula (1) ~ (3), R 13, q, p, r are, R 13, q in the general formula (I), p, in the formula is the same as r (2), the X Examples of the halogen atom include a bromine atom, a chlorine atom, and a fluorine atom. A bromine atom is preferable because of excellent reactivity.
Rの保護基は、化合物（1)と化合物（2)とを反応させる際に反応せず、かつ、次の 化合物 (I)形成工程にお!ヽて化合物（3)を反応させる際の酸性条件下で解離する基 であれば特に限定されず、一般的に保護基として提案されているもののなかから任 意に選択できる。  The protecting group for R does not react when the compound (1) is reacted with the compound (2), and it is acidic when the compound (3) is reacted in the next step of forming the compound (I). The group is not particularly limited as long as it is a group capable of dissociating under conditions, and can be arbitrarily selected from those generally proposed as protecting groups.
力かる保護基としては、 KrFエキシマレーザーや ArFエキシマレーザー用の化学 増幅型レジスト組成物に用いられるベース榭脂において酸解離性溶解抑制基として 提案されているものが例示でき、具体的には、第 3級アルキル基、第 3級アルキルォ キシカルボ-ル基、アルコキシカルボ-ルアルキル基、アルコキシアルキル基、環状 エーテル基等が挙げられる。 As a powerful protective group, it can be used as an acid dissociable, dissolution inhibiting group in the base resin used in chemically amplified resist compositions for KrF excimer lasers and ArF excimer lasers. Examples of the compounds that have been proposed include tertiary alkyl groups, tertiary alkyloxycarbon groups, alkoxycarboalkyl groups, alkoxyalkyl groups, and cyclic ether groups.
[0051] 第 3級アルキル基としては、炭素数 4〜 12であることが好ましぐ炭素数 4〜10であ ることがより好ましい。具体的には、 tert—ブチル基、 tert—ァミル基等の鎖状の第 3 級アルキル基、 2—メチルー 2—ァダマンチル基、 2—ェチルー 2—ァダマンチル基 等の、脂肪族多環式基を含む第 3級アルキル基等が挙げられる。  [0051] The tertiary alkyl group preferably has 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms. Specifically, an aliphatic polycyclic group such as a chain-like tertiary alkyl group such as tert-butyl group or tert-amyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, etc. And tertiary alkyl group containing.
ここで、本請求の範囲及び明細書における「脂肪族」とは、芳香族に対する相対的 な概念であって、芳香族性を持たない基、化合物等を意味するものと定義する。「脂 肪族環式基」は、芳香族性を持たない単環式基または多環式基であることを示す。  Here, “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.
[0052] 第 3級アルキルォキシカルボ-ル基における第 3級アルキル基としては、上記と同 様のものが挙げられる。  [0052] Examples of the tertiary alkyl group in the tertiary alkyloxycarbonyl group include the same groups as described above.
第 3級アルキルォキシカルボ-ル基として、具体的には、 tert—ブチルォキシカル ボニル基、 tert—ァミルォキシカルボニル基等が挙げられる。  Specific examples of the tertiary alkyloxycarbonyl group include a tert-butyloxycarbonyl group and a tert-amyloxycarbonyl group.
[0053] アルコキシカルボ-ルアルキル基としては、下記一般式 (pi)で表される基が挙げら れる。  [0053] Examples of the alkoxycarboalkyl group include a group represented by the following general formula (pi).
一（CH ) — CO— OR21 · · · (pi) One (CH) — CO— OR 21 · · · (pi)
2 h  2 h
一般式 (pl)において、 hは 1〜3の整数であり、 1であることが好ましい。 R21は直鎖状、分岐状または環状のアルキル基であって、その構造中にヘテロ原子 を含んでもよい。すなわち、 R21としてのアルキル基は、水素原子の一部または全部 がへテロ原子を含む基 (ヘテロ原子そのものの場合も含む)で置換されて 、てもよく、 該アルキル基の炭素原子の一部がヘテロ原子で置換されて 、てもよ 、。 In the general formula (pl), h is an integer of 1 to 3, and is preferably 1. R 21 is a linear, branched or cyclic alkyl group, and may contain a hetero atom in its structure. That is, in the alkyl group as R 21 , part or all of the hydrogen atoms may be substituted with a group containing a hetero atom (including a hetero atom itself), and one of the carbon atoms of the alkyl group may be substituted. Part may be substituted with a heteroatom.
ヘテロ原子としては、酸素原子、硫黄原子、窒素原子、フッ素原子等が挙げられる ヘテロ原子を含む基としては、ヘテロ原子自体であってもよぐまた、ヘテロ原子と 炭素原子および Zまたは水素原子とからなる基、たとえばアルコキシ基等であっても よい。  Hetero atoms include oxygen atoms, sulfur atoms, nitrogen atoms, fluorine atoms, etc. The group containing hetero atoms may be a hetero atom itself, or a hetero atom, a carbon atom, and a Z or hydrogen atom. It may be a group consisting of, for example, an alkoxy group.
水素原子の一部または全部がヘテロ原子を含む基で置換されたアルキル基の例と しては、たとえば、水素原子の一部または全部がフッ素原子で置換された炭素数 1〜 5のフッ素化低級アルキル基、同一の炭素原子に結合した 2つの水素原子が 1つの 酸素原子で置換された基 (すなわちカルボニル基 (c = o)を有する基)、同一の炭素 原子に結合した 2つの水素原子力^つの硫黄原子で置換された基 (すなわちチォカ ルポニル基 (C = S)を有する基)等が挙げられる。 Examples of alkyl groups in which some or all of the hydrogen atoms are substituted with groups containing heteroatoms For example, a fluorinated lower alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced with fluorine atoms, or two hydrogen atoms bonded to the same carbon atom are replaced with one oxygen atom. Group (i.e. a group having a carbonyl group (c = o)), a group substituted by two sulfur atoms bonded to the same carbon atom (i.e. a group having a thiocarbonyl group (C = S)) ) And the like.
アルキル基の炭素原子の一部がヘテロ原子を含む基で置換されている基としては 、たとえば、炭素原子が窒素原子で置換されている例（たとえば、その構造中に—C H を含む分岐状または環状のアルキル基において該 CH—が—NH で置換 Examples of the group in which a part of the carbon atoms of the alkyl group is substituted with a group containing a hetero atom include, for example, an example in which the carbon atom is substituted with a nitrogen atom (for example, branched or In a cyclic alkyl group, the CH— is replaced by —NH
2 2 twenty two
された基)や、炭素原子が酸素原子で置換されている例 (たとえば、その構造中に—Group) or examples in which a carbon atom is replaced by an oxygen atom (for example, in its structure—
CH を含む分岐状または環状のアルキル基において該 CH—が—O で置換In a branched or cyclic alkyl group containing CH, the CH— is replaced by —O
2 2 twenty two
された基)等が挙げられる。 Group) and the like.
R21としての直鎖状のアルキル基は、炭素数が 1〜5であることが好ましぐ具体的に はメチル基、ェチル基、 n プロピル基、 n ブチル基、イソブチル基、 n ペンチル 基が挙げられ、メチル基又はェチル基であることが好ま 、。 The linear alkyl group as R 21 preferably has 1 to 5 carbon atoms. Specifically, a methyl group, an ethyl group, an n propyl group, an n butyl group, an isobutyl group, and an n pentyl group may be used. And preferred are a methyl group or an ethyl group.
R21としての分岐状のアルキル基は、炭素数力 〜 10であることが好ましぐ 4〜8で あることがより好ましい。具体的には、イソブチル基、 tert ブチル基、イソペンチル 基、ネオペンチル基、 tert ペンチル基等が挙げられ、 tert ブチル基であることが 好ましい。 The branched alkyl group as R 21 preferably has 4 to 8 carbon atoms, more preferably 4 to 8 carbon atoms. Specific examples include an isobutyl group, a tert butyl group, an isopentyl group, a neopentyl group, a tert pentyl group, and the like, preferably a tert butyl group.
R21としての環状のアルキル基は、炭素数が 3〜20であることが好ましぐ 4〜14で あることがより好ましく、 5〜 12であることが最も好まし 、。 The cyclic alkyl group as R 21 preferably has 3 to 20 carbon atoms, more preferably 4 to 14 carbon atoms, and most preferably 5 to 12 carbon atoms.
該環状のアルキル基における基本環 (置換基を除 、た基本の環）の構造は、単環 でも多環でもよぐ特に、本発明の効果に優れることから、多環であることが好ましい。 また、基本環は、炭素および水素力 構成された炭化水素環であってもよぐ炭化水 素環を構成する炭素原子の一部がヘテロ原子で置換された複素環であってもよい。 本発明においては、特に、基本環が炭化水素環であることが好ましい。炭化水素環 の具体例としては、たとえば、モノシクロアルカン、ビシクロアルカン、トリシクロアルカ ン、テトラシクロアルカンなどを例示できる。具体的には、シクロペンタン、シクロへキ サン等のモノシクロアルカンや、ァダマンタン、ノルボルナン、イソボルナン、トリシクロ デカン、テトラシクロドデカンなどのポリシクロアルカンが挙げられる。これらのなかでも 、ァダマンタン、ノルボルナン、トリシクロデカン、テトラシクロドデカンが好ましぐ特に ァダマンタンが好ましい。これらの基本環は、その環上に置換基を有していてもよい し、有していなくてもよい。置換基としては、低級アルキル基、フッ素原子、フッ素化低 級アルキル基、酸素原子（=o)等が挙げられる。該低級アルキル基としては、メチル 基、ェチル基等の炭素数 1〜5の直鎖状または分岐状のアルキル基が挙げられる。 上記フッ素化低級アルキル基としては、上記低級アルキル基の水素原子の一部また は全部がフッ素原子で置換された基である。基本環が置換基を有する場合、置換基 の数は、 1〜3が好ましぐ 1がより好ましい。ここで、「置換基を有する」とは、基本環を 構成する炭素原子に結合した水素原子が置換基で置換されていることを意味する。 The structure of the basic ring in the cyclic alkyl group (except the substituent) may be monocyclic or polycyclic. In particular, since the effect of the present invention is excellent, polycyclic is preferable. The basic ring may be a hydrocarbon ring composed of carbon and hydrogen, or may be a heterocycle in which a part of carbon atoms constituting the hydrocarbon ring is substituted with a heteroatom. In the present invention, the basic ring is particularly preferably a hydrocarbon ring. Specific examples of the hydrocarbon ring include monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Specifically, monocycloalkanes such as cyclopentane and cyclohexane, adamantane, norbornane, isobornane, tricyclo Examples include polycycloalkanes such as decane and tetracyclododecane. Among these, adamantane, norbornane, tricyclodecane, and tetracyclododecane are preferable, and adamantane is particularly preferable. These basic rings may or may not have a substituent on the ring. Examples of the substituent include a lower alkyl group, a fluorine atom, a fluorinated lower alkyl group, and an oxygen atom (= o). Examples of the lower alkyl group include linear or branched alkyl groups having 1 to 5 carbon atoms such as a methyl group and an ethyl group. The fluorinated lower alkyl group is a group in which part or all of the hydrogen atoms of the lower alkyl group are substituted with fluorine atoms. When the basic ring has a substituent, the number of substituents is preferably 1 to 3, and more preferably 1. Here, “having a substituent” means that a hydrogen atom bonded to a carbon atom constituting the basic ring is substituted with a substituent.
R21の環状のアルキル基としては、これらの基本環から 1つの水素原子を除 、た基 が挙げられる。 R21においては、該 R21に隣接する酸素原子が結合する炭素原子が、 上記のような基本環を構成する炭素原子の 1つであることが好ましぐ特に、 R21に隣 接する酸素原子に結合する炭素原子が、低級アルキル基等の置換基が結合した第 3級炭素原子であることが好ま 、。 Examples of the cyclic alkyl group represented by R 21 include groups obtained by removing one hydrogen atom from these basic rings. In R 21 , it is preferred that the carbon atom to which the oxygen atom adjacent to R 21 is bonded is one of the carbon atoms constituting the basic ring as described above, in particular, the oxygen atom adjacent to R 21 The carbon atom bonded to is preferably a tertiary carbon atom bonded to a substituent such as a lower alkyl group.
アルコキシアルキル基としては、下記一般式 (p2)で表される基が挙げられる。  Examples of the alkoxyalkyl group include a group represented by the following general formula (p2).
CHR23— O— R22 , · · (ρ2) CHR 23 — O— R 22 , · · (ρ2)
式 (ρ2)中、 R22としては、直鎖状、分岐状または環状のアルキル基であって、その 構造中にヘテロ原子を含んでもよぐ該 R22としては、上記 R21と同様のものが挙げら れる。 In formula (ρ2), R 22 is a linear, branched or cyclic alkyl group, and R 22 which may contain a hetero atom in the structure thereof is the same as R 21 above Can be mentioned.
R23は水素原子または低級アルキル基である。 R23の低級アルキル基は、炭素原子 数 1〜5のアルキル基であり、具体的には、メチル基、ェチル基、プロピル基、イソプロ ピル基、 η ブチル基、イソブチル基、 tert ブチル基、ペンチル基、イソペンチル基 、ネオペンチル基などの低級の直鎖状または分岐状のアルキル基が挙げられる。 R23 としては、工業上入手しやすい点で、水素原子またはメチル基が好ましぐ水素原子 であることがより好ましい。 R 23 is a hydrogen atom or a lower alkyl group. The lower alkyl group for R 23 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, a η butyl group, an isobutyl group, a tert butyl group, and a pentyl group. And a lower linear or branched alkyl group such as an isopentyl group and a neopentyl group. R 23 is more preferably a hydrogen atom or a hydrogen atom which is preferably a hydrogen atom or a methyl group in terms of industrial availability.
式 (P2)で表される基としては、 R22が直鎖状アルキル基である基が好ましぐたとえ ば、 1 エトキシェチル基、 1 エトキシメチル基、 1ーメトキシェチル基、 1ーメトキシメ チル基、 1ーメトキシプロピル基、 1 エトキシプロピル基、 l—n—ブトキシェチル基、 1 ペンタフルォロエトキシェチル基、 1 トリフルォロメトキシェチル基、 1 トリフル ォロメトキシメチル基等が挙げられる。 The group represented by the formula ( P2 ) is preferably a group in which R 22 is a linear alkyl group. For example, 1 ethoxyethyl group, 1 ethoxymethyl group, 1-methoxyethyl group, 1-methoxymethyl group Examples include til group, 1-methoxypropyl group, 1 ethoxypropyl group, l-n-butoxetyl group, 1 pentafluoroethoxyethyl group, 1 trifluoromethoxyethyl group, 1 trifluoromethoxymethyl group, etc. It is done.
[0056] 環状エーテル基として、具体的には、テトラヒドロビラ-ル基、テトラヒドロフラ -ル基 等が挙げられる。  [0056] Specific examples of the cyclic ether group include a tetrahydrovinyl group and a tetrahydrofuranyl group.
[0057] 本発明にお 、て、 Rの保護基としては、酸により解離しやす 、こと、入手の容易さ等 の点で、第 3級アルキル基またはアルコキシアルキル基が好ましぐ特に、鎖状のもの (鎖状の第 3級アルキル基;式 (p2)において、 R22が直鎖状または分岐状のアルキル 基であって、その構造中にヘテロ原子を含んでもよぐ R23が水素原子または直鎖状 または分岐状の低級アルキル基であるアルコキシアルキル基等）が好ましぐ鎖状の 第 3級アルキル基がより好ましぐ tert ブチル基が最も好ま 、。 In the present invention, the protecting group for R is preferably a tertiary alkyl group or an alkoxyalkyl group in view of ease of dissociation by an acid, availability, and the like. Jo ones (chain-like tertiary alkyl group; in the formula (p2), a R 22 a linear or branched alkyl group, Yogu R 23 may include a hetero atom in its structure hydrogen A tertiary tertiary alkyl group in which an atom or a linear or branched lower alkyl group is preferred, and a tertiary tertiary alkyl group is more preferred, and a tert butyl group is most preferred.
[0058] 上記化合物（1)と上記化合物（2)とは、公知の方法により反応させることができ、た とえば、テトラヒドロフラン (THF)等の有機溶剤に上記化合物（1)を溶解し、該溶液 中に炭酸カリウム等の塩基を添加し、撹拌しながら該溶液中に上記化合物（2)を添 カロすること〖こより反応させることができる。  [0058] The compound (1) and the compound (2) can be reacted by a known method. For example, the compound (1) is dissolved in an organic solvent such as tetrahydrofuran (THF), The reaction can be carried out by adding a base such as potassium carbonate to the solution and adding the compound (2) to the solution while stirring.
このとき使用する有機溶剤としては、上記化合物（1)〜（3)を溶解するものであれ ばよぐ一般的な有機溶剤から任意のものを選択すればよい。一般的な有機溶剤と しては、例えば、アセトン、メチルェチルケトン、メチルアミルケトン、シクロへキサノン 等のケトン類; THF、ジォキサン、グライム、プロピレングリコールモノメチルエーテル 等のエーテル類；酢酸ェチル、乳酸ェチル等のエステル類；プロピレングリコールメ チルエーテルアセテート等のエーテルエステル類； Ύ ブチロラタトン等のラタトン類 等を挙げることができ、これらを単独又は混合して用いることができる。 As the organic solvent used at this time, any organic solvent may be selected from general organic solvents that can dissolve the compounds (1) to (3). Examples of common organic solvents include ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, and cyclohexanone; ethers such as THF, dioxane, glyme, and propylene glycol monomethyl ether; esters such as Echiru; ether esters such as propylene glycol methylation ether acetate; Y Rataton, etc. can be exemplified such Buchirorataton, can be used alone or in combination.
反応温度は、 10〜60°Cが好ましぐ 20〜60°Cがより好ましぐ通常、室温（20〜2 The reaction temperature is preferably 10-60 ° C, more preferably 20-60 ° C, usually at room temperature (20-2
5°C)程度でよい。 About 5 ° C).
反応時間は、 1〜24時間が好ましぐ 4〜15時間がより好ましい。  The reaction time is preferably 1 to 24 hours, more preferably 4 to 15 hours.
反応終了後、反応液は、そのまま次の工程に用いてもよいが、水 Z酢酸ェチル等を 添加し、有機層（酢酸ェチル層等)を減圧濃縮して化合物（3)を得ることが好ま Uヽ。  After completion of the reaction, the reaction solution may be used in the next step as it is. However, it is preferable to add water Z ethyl acetate and the like, and concentrate the organic layer (ethyl acetate layer, etc.) under reduced pressure to obtain compound (3). U ヽ.
[0059] <化合物 (I)形成工程 > 一般式（3)、（4)、 (I)中、 Rn〜R13、 q、 p、 r、 R、 s、 t、 uは、上記と同様である。 上記化合物（3)と上記化合物 (4)との反応は、酸性条件下で行われる。これにより 、上記化合物（3)のホルミル基（-CHO)と上記化合物 (4)とが反応するとともに、保 護基 Rが解離してカルボキシ基が生成し、化合物 (I)が形成される。 [0059] <Compound (I) formation step> In the general formulas (3), (4), and (I), R n to R 13 , q, p, r, R, s, t, and u are the same as described above. The reaction between the compound (3) and the compound (4) is carried out under acidic conditions. As a result, the formyl group (—CHO) of the compound (3) reacts with the compound (4), and the protecting group R is dissociated to form a carboxy group to form the compound (I).
具体的には、例えば、化合物（3)をメタノール等の有機溶剤に溶解し、該溶液中に 、化合物（3)に対して約 2当量倍の化合物 (4)を添加し、さらに塩酸等の酸を添加す ること〖こより反応させることができる。  Specifically, for example, the compound (3) is dissolved in an organic solvent such as methanol, and about 2 equivalents of the compound (4) is added to the compound (3). The reaction can be carried out by adding an acid.
[0060] このとき使用する酸としては、化合物（3)と化合物 (4)とが反応し、かつ保護基尺が 解離するものであれば特に制限はない。好ましくは塩酸、硫酸、無水硫酸、 p トル エンスルホン酸、メタンスルホン酸、トリフルォロメタンスルホン酸、シユウ酸、ギ酸、リ ン酸、トリクロ口酢酸、トリフルォロ酢酸等を好ましい具体例として挙げることができる。 特に、塩酸が好ましく用いられる。これらの酸は、いずれか 1種を単独で用いてもよく 、 2種類以上混合して用いてもよい。 [0060] The acid used at this time is not particularly limited as long as the compound (3) reacts with the compound (4) and the protective base is dissociated. Preferred examples include hydrochloric acid, sulfuric acid, sulfuric anhydride, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid and the like. . In particular, hydrochloric acid is preferably used. Any one of these acids may be used alone, or two or more of these acids may be used in combination.
酸の添加量は、例えば、 35%質量塩酸の場合は、化合物（3) 100重量部に対して 、 1〜700重量部、好ましくは、 100〜600重量部の範囲で用いられる。  For example, in the case of 35% by mass hydrochloric acid, the acid is added in an amount of 1 to 700 parts by weight, preferably 100 to 600 parts by weight per 100 parts by weight of the compound (3).
反応温度は、 20〜80°Cが好ましぐ 30〜65°Cがより好ましい。  The reaction temperature is preferably 20 to 80 ° C, more preferably 30 to 65 ° C.
反応時間は、 2〜96時間が好ましぐ 5〜72時間がより好ましい。  The reaction time is preferably 2 to 96 hours, more preferably 5 to 72 hours.
[0061] 反応終了後、反応液から、化合物 (I)を回収する。 [0061] After completion of the reaction, the compound (I) is recovered from the reaction solution.
回収方法としては、特に限定されず、公知の方法が使用できる。具体的には、たと えば、反応液に水酸ィ匕ナトリウム等の塩基を添加して残った酸を中和した後、水 Z酢 酸ェチル等を添加して抽出操作を行い、得られた有機層（酢酸ェチル層等）を減圧 濃縮し、カラムクロマトグラフィー等を行うことによりィ匕合物 (I)を得ることができる。  It does not specifically limit as a collection method, A well-known method can be used. Specifically, for example, it was obtained by neutralizing the remaining acid by adding a base such as sodium hydroxide to the reaction solution, and then performing extraction operation by adding water Z ethyl acetate or the like. The compound (I) can be obtained by concentrating the organic layer (such as an ethyl acetate layer) under reduced pressure and performing column chromatography or the like.
[0062] 上記本発明の化合物 (I)は、レジスト組成物用としての利用が可能な低分子化合物 の製造に好適に使用できる。  [0062] The compound (I) of the present invention can be suitably used for the production of a low-molecular compound that can be used as a resist composition.
たとえば、上記一般式 (I 1)で表される化合物は、下記本発明の低分子化合物の 製造に好適に使用できる。  For example, the compound represented by the general formula (I 1) can be suitably used for the production of the low molecular compound of the present invention described below.
[0063] <第三の実施形態の低分子化合物 >  [0063] <Low molecular compound of third embodiment>
本発明の第三の実施形態の低分子化合物（以下、低分子化合物 (A1)という。）は 、一般式 (A— 1)または (A— 2)で表される。 The low molecular compound of the third embodiment of the present invention (hereinafter referred to as low molecular compound (A1)) is It is represented by the general formula (A-1) or (A-2).
[0064] [化 19] [0064] [Chemical 19]
( A— 1 )
Figure imgf000025_0001
(A— 1)
Figure imgf000025_0001
[式中、 〜 ， R5〜R8はそれぞれ独立して水素原子、ハロゲン原子、アルキル基 またはハロゲンィ匕アルキル基であり； R3〜R4, R9〜R1C)はそれぞれ独立して下記一般 式 (I 11)で表される基であり； 1, m, Ι' , m，はそれぞれ独立して 1〜3の整数であり ； n, n，は 1〜3の整数であり； Yは（n+ 1)価の有機基であり； Zは（n， + 1)価の有機 基である。 ] [Wherein, R 5 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group or a halogenated alkyl group; R 3 to R 4 , R 9 to R 1C) are each independently A group represented by the general formula (I 11); 1, m, Ι ′ and m are each independently an integer of 1 to 3; n, n are an integer of 1 to 3; Y Is an (n + 1) -valent organic group; Z is an (n, +1) -valent organic group. ]
[0065] [化 20] [0065] [Chemical 20]
Figure imgf000025_0002
Figure imgf000025_0002
13  13
[式中、 RU〜R , s, t, u, q, rは式（I)中の RU〜R", S, t, u, q, rと同様である。 ] 低分子化合物 (Al)は、上記のような構造を有することにより、たとえばポジ型レジ スト組成物に酸発生剤成分とともに配合された場合、露光により酸発生剤成分から発 生した酸の作用により、 R3〜R4および R9〜R1Gに隣接するカルボ-ル基の炭素原子 に結合した酸素原子と、該酸素原子に結合した炭素原子 ( 〜 、 R5〜R8等が結 合した炭素原子)との間の結合が切れて分解する。この分解により、分子量が小さく なると同時に R3— COOH、 R4 - COOH等のカルボン酸 (すなわち化合物（I) )が分 解物として生じるため、レジストの露光部分においてアルカリ可溶性が増大する。そ のため、アルカリ現像を行うことによりポジ型のレジストパターンが形成できる。 [Wherein, RU to R, s, t, u, q, r are the same as RU to R ", S, t, u, q, r in formula (I).] Low molecular weight compound (Al) Has a structure as described above, for example, when it is blended with a positive resist composition together with an acid generator component, R 3 to R 4 due to the action of an acid generated from the acid generator component upon exposure. And an oxygen atom bonded to a carbon atom of a carbo group adjacent to R 9 to R 1G and a carbon atom bonded to the oxygen atom (to, R 5 to R 8 etc. The bond between the bonded carbon atoms) is broken and decomposed. As a result of this decomposition, the molecular weight is reduced, and at the same time, carboxylic acids such as R 3 —COOH and R 4 —COOH (ie, compound (I)) are generated as decomposition products, so that alkali solubility increases in the exposed portion of the resist. Therefore, a positive resist pattern can be formed by performing alkali development.
このとき、分解物としては、たとえば一般式 (A—1)で表される化合物の場合、末端 部分が分解して生じる（n+ 1)個のカルボン酸（1個の R3— COOHおよび n個の R4— COOH)と、中心部分 (Y等を含む部分）に由来する 1個の化合物が生じると考えら れる。また、一般式 (A— 2)で表される化合物の場合、末端部分が分解して生じる (n ， + 1)個のカルボン酸（1個の R9—COOHおよび n，個の R1G—COOH)と、中心部 分 (Z等を含む部分）に由来する 1個の化合物が生じると考えられる。 In this case, as a decomposition product, for example, in the case of a compound represented by the general formula (A-1), (n + 1) carboxylic acids (1 R 3 —COOH and n) are generated by decomposition of the terminal portion. R 4 — COOH) and one compound derived from the central part (the part including Y etc.) is considered to be generated. In the case of the compound represented by the general formula (A-2), (n, + 1) carboxylic acids (1 R 9 —COOH and n, R 1G —) generated by decomposing the terminal portion COOH) and one compound derived from the central part (parts including Z etc.) are considered to be produced.
[0067] 一般式 (A— 1)中、 R1 !^はそれぞれ独立して、水素原子、ハロゲン原子、アルキ ル基、ハロゲン化アルキル基である。 In the general formula (A-1), R 1 ! ^ Each independently represents a hydrogen atom, a halogen atom, an alkyl group, or a halogenated alkyl group.
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げら れ、特にフッ素原子が好ましい。  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
I^〜R2のアルキル基としては、特に制限はなぐ例えば炭素数 1〜： LOの直鎖状、 分岐状または環状のアルキル基等が挙げられる。アルキル基としては、 1〜5の直鎖 状または分岐状の低級アルキル基または炭素数 5〜6の環状アルキル基が好ましい 。直鎖状または分岐状の低級アルキル基としては、メチル基、ェチル基、プロピル基 、イソプロピル基、 n—ブチル基、イソブチル基、 tert—ブチル基、ペンチル基、イソ ペンチル基、ネオペンチル基等が挙げられる。環状アルキル基としては、シクロへキ シル基、シクロペンチル基等が挙げられる。 The alkyl group of I ^ to R 2 is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups having 1 to C: LO. As the alkyl group, a linear or branched lower alkyl group having 1 to 5 or a cyclic alkyl group having 5 to 6 carbon atoms is preferable. Examples of the linear or branched lower alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n -butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. It is done. Examples of the cyclic alkyl group include a cyclohexyl group and a cyclopentyl group.
ハロゲン化アルキル基としては、上記で挙げたアルキル基の水素原子の一部また は全部がハロゲン原子で置換されたアルキル基が挙げられる。  Examples of the halogenated alkyl group include alkyl groups in which some or all of the hydrogen atoms of the alkyl groups listed above are substituted with halogen atoms.
I^〜R2としては、特に、水素原子が好ましい。 The I ^ to R 2, a hydrogen atom is particularly preferable.
[0068] R3〜R4は、それぞれ独立に一般式 (1—11)で表される基であり、一般式 (1—11) 中の！^11〜!^13, s, t, u, q, rは式（I)中の 1〜!^3, s, t, u, q, rと同様である。[0068] R 3 to R 4 are each independently a group represented by the general formula (1-11), and in the general formula (1-11)! ^ 11 to! ^ 13 , s, t, u, q, r are the same as 1 to! ^ 3 , s, t, u, q, r in the formula (I).
R3〜R4は、それぞれ同一であっても異なっていてもよいが、合成のしゃすさの点で 、同一であることが好ましい。 [0069] 1, mはそれぞれ独立して 1〜3の整数であり、好ましくは 1又は 2であり、最も好ましく は 1である。 R 3 to R 4 may be the same or different from each other, but are preferably the same in terms of synthesis. [0069] 1, m are each independently an integer of 1 to 3, preferably 1 or 2, and most preferably 1.
nは 1〜3の整数であり、好ましくは 1または 2であり、最も好ましくは 1である。 なお、 nが 2以上の整数である場合、つまり化合物 (A1)力 R4-COO- [C (R2) Hn is an integer of 1 to 3, preferably 1 or 2, and most preferably 1. When n is an integer of 2 or more, that is, the compound (A1) force R 4 -COO- [C (R 2 ) H
] 一 O—で表される基を 2以上有する場合、これらは相互に同一であっても、また、 相互に異なっていてもよい。 ] In the case of having two or more groups represented by 1 O—, these may be the same as or different from each other.
[0070] Yは（n+ 1)価の有機基である。 [0070] Y is an (n + 1) -valent organic group.
Yにおいて、有機基としては、直鎖、分岐または環状の飽和炭化水素基が好ましく In Y, the organic group is preferably a linear, branched or cyclic saturated hydrocarbon group.
、直鎖または分岐の飽和炭化水素基がより好ましい。また、該飽和炭化水素基は、炭 素数が 1〜15であることが好ましぐ炭素数 1〜： L0がより好ましぐ炭素数 1〜6がさら に好ましい。 A linear or branched saturated hydrocarbon group is more preferred. In addition, the saturated hydrocarbon group preferably has 1 to 15 carbon atoms, and more preferably 1 to 6 carbon atoms in which L0 is more preferable.
飽和炭化水素基は置換基を有していても良い。該置換基としては、特に制限はなく 、たとえばフッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、炭素数 1〜6の直鎖、分岐または環状のアルキル基等が挙げられる。ここで、「置換基を有す る」とは、飽和炭化水素基の水素原子の一部または全部が置換基で置換されている ことを意味する。  The saturated hydrocarbon group may have a substituent. The substituent is not particularly limited, and examples thereof include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, and linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms. Here, “having a substituent” means that part or all of the hydrogen atoms of the saturated hydrocarbon group are substituted with a substituent.
また、 Yとしては、上述のような飽和炭化水素基の炭素原子の一部が、酸素原子、 窒素原子、硫黄原子等のへテロ原子で置換された基も挙げられる。  Examples of Y include a group in which a part of carbon atoms of the saturated hydrocarbon group as described above is substituted with a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
[0071] Yとしては、特に、 2価又は 3価の飽和炭化水素基が好ましぐ特には 2価の飽和炭 化水素基 (アルキレン基)が好ましい。飽和炭化水素基としては、直鎖、分岐または 環状のいずれでもよい。 [0071] As Y, a divalent or trivalent saturated hydrocarbon group is particularly preferable, and a divalent saturated hydrocarbon group (alkylene group) is particularly preferable. The saturated hydrocarbon group may be linear, branched or cyclic.
3価の直鎖または分岐の飽和炭化水素基としては、メタン、ェタン、プロパン、ブタ ン、ペンタン、へキサン、ヘプタン、オクタン等から 3個の水素原子を除いた基が挙げ られる。  Examples of the trivalent linear or branched saturated hydrocarbon group include groups in which three hydrogen atoms have been removed from methane, ethane, propane, butane, pentane, hexane, heptane, octane and the like.
3価の環状の飽和炭化水素基としては、シクロペンタン、シクロへキサン、シクロへ プタン、ノルボルナン、イソボルナン、ァダマンタン、トリシクロデカンン、テトラシクロド デカン等の飽和炭化水素環から水素原子を 3個除いた環式基、該環式基に直鎖ま たは分岐のアルキレン基が結合した基などが挙げられる。 直鎖または分岐のアルキレン基としては、メチレン基、エチレン基、プロピレン基、ィ ソプロピレン基、 n—ブチレン基、イソブチレン基、 tert—ブチレン基、ペンチレン基、 イソペンチレン基、ネオペンチレン基等が挙げられる。 As the trivalent cyclic saturated hydrocarbon group, three hydrogen atoms were removed from a saturated hydrocarbon ring such as cyclopentane, cyclohexane, cycloheptane, norbornane, isobornane, adamantane, tricyclodecane, tetracyclododecane, etc. Examples thereof include a cyclic group and a group in which a linear or branched alkylene group is bonded to the cyclic group. Examples of the linear or branched alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a tert-butylene group, a pentylene group, an isopentylene group, and a neopentylene group.
環状のアルキレン基としては、シクロペンタン、シクロへキサン、ノルボルナン、イソ ボルナン、ァダマンタン、トリシクロデカン、テトラシクロドデカン等の飽和炭化水素環 から水素原子を 2個除 、た環式基、該環式基に直鎖または分岐のアルキレン基が結 合した基などが挙げられる。  The cyclic alkylene group includes a cyclic group obtained by removing two hydrogen atoms from a saturated hydrocarbon ring such as cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, and tetracyclododecane. And a group in which a linear or branched alkylene group is bonded to the group.
Yとしては、直鎖または分岐のアルキレン基が好ましぐ直鎖のアルキレン基がより 好ましぐエチレン基またはプロピレン基が特に好ま U、。  Y is particularly preferably an ethylene group or a propylene group, more preferably a linear alkylene group, more preferably a linear or branched alkylene group.
[0072] 一般式 (A— 2)中、 R5〜R8のアルキル基、ハロゲン化アルキル基としては、一般式 In the general formula (A-2), the alkyl group and halogenated alkyl group of R 5 to R 8 are represented by the general formula
(A- 1)における！^〜 のアルキル基、ハロゲン化アルキル基と同様のものが挙げら れる。  In (A-1)! Examples are the same as the alkyl group and halogenated alkyl group.
R9〜R1Gとしては、一般式 (A— 1)における R3〜R4と同様のものが挙げられる。 、 m'、 n'、 Zとしては、それぞれ、一般式 (A— 1)中の 1、 m、 n、 Yと同様のものが 挙げられる。 Examples of R 9 to R 1G include the same as R 3 to R 4 in formula (A-1). , M ′, n ′, and Z are the same as 1, m, n, and Y in general formula (A-1), respectively.
[0073] 低分子化合物 (A1)は、スピンコート法によりアモルファス (非晶質)な膜を形成しう る材料である。ここで、アモルファスな膜とは、結晶化しない光学的に透明な膜を意 味する。スピンコート法は、一般的に用いられている薄膜形成手法の 1つであり、当 該化合物がスピンコート法によりアモルファスな膜を形成しうる材料であるかどうかは 、 8インチシリコンゥエーハ上にスピンコート法により形成した塗膜が全面透明である か否かにより判別できる。より具体的には、例えば以下のようにして判別できる。まず 、当該化合物に、一般的にレジスト溶剤に用いられている溶剤を用いて、例えば低分 子化合物（A1) 100質量部をプロピレングリコールモノメチルエーテルアセテート 157 0質量部の有機溶剤に溶解し、超音波洗浄器を用いて超音波処理 (溶解処理)を施 して溶解させ、該溶液を、ウェハ上に 1500rpmにてスピンコートし、任意に乾燥べ一 ク（PAB, Post Applied Bake)を 110°C、 90秒の条件で施し、この状態で、 目視 にて、透明かどうかによりアモルファスな膜が形成されているかどうかを確認する。な お、透明でな ヽ曇った膜はァモノレファスな膜ではな ヽ。 本発明において、低分子化合物 (A1)は、上述のようにして形成されたァモルファ スな膜の安定性が良好であることが好ましぐ例えば上記 PAB後、室温環境下で 2週 間放置した後でも、アモルファスな状態が維持されて 、ることが好ま U、。 The low molecular compound (A1) is a material that can form an amorphous film by spin coating. Here, the amorphous film means an optically transparent film that does not crystallize. The spin coating method is one of the commonly used thin film forming methods, and whether or not the compound is a material capable of forming an amorphous film by the spin coating method is determined on an 8-inch silicon wafer. It can be discriminated by whether or not the coating film formed by the spin coating method is completely transparent. More specifically, for example, the determination can be made as follows. First, using a solvent generally used as a resist solvent for the compound, for example, 100 parts by mass of a low molecular compound (A1) is dissolved in 1570 parts by mass of an organic solvent of propylene glycol monomethyl ether acetate. Ultrasonic treatment (dissolution treatment) is performed using a sonic cleaner, and the solution is spin-coated on the wafer at 1500 rpm, and optionally a dry baking (PAB, Post Applied Bake) of 110 °. C, apply for 90 seconds, and in this state, visually check whether an amorphous film is formed depending on whether it is transparent or not. It should be noted that the transparent film is not a monolithic film. In the present invention, it is preferable that the low molecular weight compound (A1) has good stability of the amorphous film formed as described above. For example, after the PAB, the low molecular compound (A1) is allowed to stand in a room temperature environment for 2 weeks. Even later, it is preferable to maintain an amorphous state.
[0074] 低分子化合物 (A1)は、たとえば、 1種または 2種以上の化合物 (I)を、テトラヒドロフ ラン等の溶媒に溶解し、トリェチルァミン等の触媒の存在下で、下記一般式 (a— 1)ま たは (a— 2)で表されるビスクロロ化合物と反応させることにより合成できる。  [0074] The low molecular compound (A1) is, for example, one or more compounds (I) dissolved in a solvent such as tetrahydrofuran in the presence of a catalyst such as triethylamine and the following general formula (a — It can be synthesized by reacting with the bischloro compound represented by 1) or (a-2).
[0075] [化 21]  [0075] [Chemical 21]
■CI
Figure imgf000029_0001
■ CI
Figure imgf000029_0001
( a— 1 ) ( a - 2 )  (a— 1) (a-2)
[式中、 R1〜！ T、 R5〜R8、 Y、 Ζ、 1、 m、 1，、 m，は上記一般式 (A— 1)〜（Α—2)中の R^R2, R5〜R8、 Y、 Z、 1、 m、 1，、 m，と同様である。 ] [Where R 1 ~! T, R 5 to R 8 , Y, Ζ, 1, m, 1, and m are R ^ R 2 , R 5 to R 8 , Y in the above general formulas (A-1) to (Α—2) , Z, 1, m, 1, m. ]
[0076] 上記低分子化合物 (Al)は、酸の作用によりアルカリ可溶性が増大する基材成分（ A)、および放射線の照射により酸を発生する酸発生剤成分 (B)を含有するポジ型レ ジスト組成物において、前記基材成分 (A)として好適に使用できる。 [0076] The low molecular weight compound (Al) is a positive type resin containing a base component (A) whose alkali solubility is increased by the action of an acid and an acid generator component (B) which generates an acid upon irradiation with radiation. In the dyst composition, it can be suitably used as the substrate component (A).
低分子化合物 (A1)を含有するポジ型レジスト組成物を用いることにより、高解像性 のレジストパターンを形成できる。また、ラフネスも低減できる。  By using a positive resist composition containing the low molecular compound (A1), a high-resolution resist pattern can be formed. In addition, roughness can be reduced.
これは、低分子化合物 (A1)の均一性によると推測される。すなわち、レジスト材料 の基材成分として高分子量の重合体 (榭脂)を用いる従来のレジストは、分子量分散 やアルカリ溶解性分散を制御することが難しい。そのため、これらの分散や、その分 子サイズそのものが原因となる LERなどの低減には限界がある。  This is presumed to be due to the uniformity of the low molecular weight compound (A1). That is, it is difficult to control molecular weight dispersion and alkali-soluble dispersion in conventional resists that use a high molecular weight polymer (resin) as a base material component of the resist material. For this reason, there is a limit to the reduction of LER caused by such dispersion and the molecular size itself.
また、上記問題の解決策として考えられている従来の低分子化合物も、上述した非 特許文献 1, 2等に記載されているように、アルカリ可溶性基を酸解離性溶解抑制基 で保護することから、保護されるアルカリ可溶性基の位置やその保護率などにバラッ キが発生し、結果、その性質にもバラツキが生じて上記と同様の問題が生じる。  In addition, as described in Non-Patent Documents 1 and 2 and the like described above, conventional low molecular weight compounds considered as a solution to the above problem also protect an alkali-soluble group with an acid dissociable, dissolution inhibiting group. Therefore, variation occurs in the position of the alkali-soluble group to be protected and the protection rate thereof, and as a result, the property is also varied, resulting in the same problem as described above.
一方、本発明の低分子化合物 (A1)は、低分子量の非重合体であり、また、従来化 学増幅型ポジ型レジストに用いられている榭脂や、上述した非特許文献 1, 2等で提 案されて!ヽる従来の低分子化合物のように、アルカリ可溶性基を酸解離性溶解抑制 基により保護しなくてよいため、その構造が明確で、分子量にもムラが少ない。そのた め、アルカリ溶解性や親水性 ·疎水性等の性質が均一であり、そのため、均一な性質 のレジスト膜が形成できる。 On the other hand, the low molecular weight compound (A1) of the present invention is a low molecular weight non-polymer, Inhibition of acid-dissociable dissolution of alkali-soluble groups, such as those used in chemically amplified positive resists and the conventional low-molecular compounds proposed in Non-Patent Documents 1 and 2 mentioned above Since it does not need to be protected by a group, the structure is clear and the molecular weight is less uneven. Therefore, properties such as alkali solubility and hydrophilicity / hydrophobicity are uniform, and therefore, a resist film having uniform properties can be formed.
そして、該レジスト膜中において、低分子化合物 (A1)は、露光により発生した酸の 作用によって分解して分解物を 2〜4個生じ、アルカリ溶解性が増大する力 この分 解後においても、突出して大きな分子量のものが残らず、相対的に、生じる分解物の 個々の分子量の差が小さくなる。そのため、分解物もレジスト膜中で均一に分布し、 また分解物間のアルカリ現像液に対する溶解挙動の差も小さい。  In the resist film, the low molecular weight compound (A1) is decomposed by the action of the acid generated by exposure to produce 2 to 4 decomposition products, and the ability to increase alkali solubility. There is no large molecular weight protruding, and the difference in the individual molecular weights of the resulting degradation products becomes relatively small. For this reason, the decomposed products are evenly distributed in the resist film, and the difference in dissolution behavior of the decomposed products in the alkaline developer is small.
このように、低分子化合物 (A1)を用いることにより、露光前、露光後とも均一な性質 のレジスト膜を形成でき、それによつて高解像性のレジストパターンを形成でき、また 、ラフネスも低減できると推測される。  In this way, by using the low molecular weight compound (A1), a resist film having a uniform property can be formed before and after exposure, thereby forming a resist pattern with high resolution and reducing roughness. Presumed to be possible.
[0077] さらに、上述したように、低分子化合物 (A1)の性質が均一で、均一な性質 (アル力 リ性ゃ親水性'疎水性等)のレジスト膜を形成できると考えられることから、低分子化 合物 (A1)を用いることにより、ディフエタトも低減できる。ここで、ディフエタトとは、例 えば、 KLAテンコール社の表面欠陥観察装置（商品名「KLA」）により、現像後のレ ジストパターンを真上力も観察した際に検知される不具合全般のことである。この不 具合とは、例えば現像後のスカム、泡、ゴミ、レジストパターン間のブリッジ、色むら、 析出物等である。 [0077] Further, as described above, since the properties of the low molecular weight compound (A1) are uniform, it is considered that a resist film having uniform properties (such as strength, hydrophilicity, hydrophobicity, etc.) can be formed. By using the low molecular weight compound (A1), the diffetat can also be reduced. Here, diffetats are, for example, general defects detected when the resist pattern after development is also observed by the KLA Tencor surface defect observation device (trade name “KLA”). . This defect includes, for example, scum after development, bubbles, dust, bridges between resist patterns, uneven color, and precipitates.
また、低分子化合物 (A1)の性質が均一で、有機溶剤等に対する溶解性も均一で あると考えられることから、低分子化合物 (A1)を含有するポジ型レジスト組成物の保 存安定性も向上する。  Further, since the properties of the low molecular compound (A1) are uniform and the solubility in organic solvents is considered uniform, the storage stability of the positive resist composition containing the low molecular compound (A1) is also improved. improves.
[0078] <第四の実施形態のポジ型レジスト組成物 > <Positive Resist Composition of Fourth Embodiment>
本発明の第四の実施形態のポジ型レジスト組成物は、酸の作用によりアルカリ可溶 性が増大する基材成分 (A) (以下、（A)成分という。）、および放射線の照射により酸 を発生する酸発生剤成分 (B) (以下、（B)成分という。）を含有するポジ型レジスト組 成物であって、前記 (A)成分として一般式 (A— 1)または (A— 2)で表される低分子 化合物 (Al)を含有する。 The positive resist composition of the fourth embodiment of the present invention comprises a base component (A) (hereinafter referred to as “component (A)”) whose alkali solubility is increased by the action of an acid, and an acid upon irradiation with an acid. A positive resist composition containing an acid generator component (B) (hereinafter referred to as the component (B)) that generates a hydrogen atom, wherein the component (A) is represented by the general formula (A-1) or (A— Small molecule represented by 2) Contains compound (Al).
(A)成分および (B)成分を含有するポジ型レジスト組成物にお!ヽては、露光により 前記 (B)成分から発生した酸が前記 (A)成分に作用すると、 (A)成分全体がアル力 リ不溶性カゝらアルカリ可溶性に変化する。そのため、レジストパターンの形成におい て、該ポジ型レジスト組成物力 なるレジスト膜を選択的に露光すると、または露光に 加えて露光後加熱すると、露光部はアル力リ可溶性へ転じる一方で未露光部はアル カリ不溶性のまま変化しないので、アルカリ現像することによりポジ型のレジストパター ンが形成できる。  In the positive resist composition containing the component (A) and the component (B), when the acid generated from the component (B) by exposure acts on the component (A) by exposure, the whole component (A) However, it is changed to alkali-soluble from Al-insoluble silica. Therefore, in the formation of the resist pattern, when the resist film having the positive resist composition strength is selectively exposed or heated after exposure in addition to the exposure, the exposed portion turns to be soluble in the Al force while the unexposed portion is changed. Since it remains insoluble in alkali and does not change, a positive resist pattern can be formed by alkali development.
[0079] [ (A)成分] [0079] [(A) component]
(A)成分は、上記低分子化合物 (A1)を含有する。  The component (A) contains the low molecular compound (A1).
低分子化合物 (A1)は、 1種単独で用いてもよぐ 2種以上を併用してもよい。  The low molecular compound (A1) may be used alone or in combination of two or more.
(A)成分中、低分子化合物 (A1)の割合は、 40質量％超であることが好ましぐ 50 質量％超であることがより好ましぐ 80質量％超がさらに好ましぐ最も好ましくは 100 質量％である。  In the component (A), the proportion of the low molecular weight compound (A1) is preferably more than 40% by mass, more preferably more than 50% by mass, and most preferably more than 80% by mass. Is 100% by mass.
(A)成分中の低分子化合物 (A1)の割合は、逆相クロマトグラフィー等の手段により 測定できる。  The proportion of the low molecular compound (A1) in component (A) can be measured by means such as reverse phase chromatography.
[0080] (A)成分は、さらに、低分子化合物 (A1)を用いることによる効果を損なわな 、範囲 で、これまで化学増幅型レジスト層の基材成分として提案されて!、る任意の榭脂成分 (以下、（A2)成分と 、うことがある）を含有して!/、てもよ!/、。  [0080] The component (A) has been proposed as a base material component of a chemically amplified resist layer to the extent that the effect of using the low molecular compound (A1) is not impaired. Contains a fat component (hereinafter sometimes referred to as (A2) component)! /, May! /.
かかる (A2)成分としては、例えば従来の化学増幅型の KrF用ポジ型レジスト組成 物、 ArF用ポジ型レジスト組成物等のベース榭脂として提案されて ヽるものが挙げら れ、レジストパターン形成時に用いる露光光源の種類に応じて適宜選択できる。  Examples of the component (A2) include those proposed as base resins for conventional chemically amplified KrF positive resist compositions, ArF positive resist compositions, and the like. It can be suitably selected according to the type of exposure light source used sometimes.
[0081] ポジ型レジスト組成物中の (A)成分の含有量は、形成しょうとするレジスト膜厚に応 じて調整すればよい。  [0081] The content of the component (A) in the positive resist composition may be adjusted according to the resist film thickness to be formed.
[0082] [ (B)成分]  [0082] [Component (B)]
(B)成分としては、特に限定されず、これまでィ匕学増幅型レジスト用の酸発生剤とし て提案されて 、るものを使用することができる。  The component (B) is not particularly limited, and any component that has been proposed as an acid generator for chemical amplification resists can be used.
このような酸発生剤としては、これまで、ョードニゥム塩やスルホ -ゥム塩などのォ- ゥム塩系酸発生剤、ォキシムスルホネート系酸発生剤、ビスアルキルまたはビスァリ 一ルスルホ -ルジァゾメタン類、ポリ（ビススルホ -ル）ジァゾメタン類などのジァゾメタ ン系酸発生剤、ニトロべンジルスルホネート系酸発生剤、イミノスルホネート系酸発生 剤、ジスルホン系酸発生剤など多種のものが知られて 、る。 Such acid generators have so far been iodenium salts and sulfo-salt salts. Um salt-based acid generator, oxime sulfonate-based acid generator, bisalkyl or bis-aryl sulfo-diazomethanes, diazomethane-based acid generators such as poly (bissulfol) diazomethanes, nitrobenzyl sulfonate-based acids Various generators such as generators, iminosulfonate acid generators, disulfone acid generators are known.
[0083] ォ-ゥム塩系酸発生剤としては、例えば下記一般式 (b— 0)で表される酸発生剤が 例示できる。  Examples of form salt-based acid generators include acid generators represented by the following general formula (b-0).
[0084] [化 22] [0084] [Chemical 22]
Figure imgf000032_0001
Figure imgf000032_0001
[式中、 R51は、直鎖、分岐鎖若しくは環状のアルキル基、または直鎖、分岐鎖若しく は環状のフッ素化アルキル基を表し; R52は、水素原子、水酸基、ハロゲン原子、直 鎖、分岐鎖状もしくは環状のアルキル基、直鎖若しくは分岐鎖状のハロゲン化アルキ ル基、または直鎖若しくは分岐鎖状のアルコキシ基であり； R53は置換基を有していて もよぃァリール基であり；u，，は 1〜3の整数である。 ] [Wherein R 51 represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group; R 52 represents a hydrogen atom, a hydroxyl group, a halogen atom, a straight chain, branched or cyclic alkyl group, a linear or branched halogenated alkyl group or a linear or branched alkoxy group,; R 53 is substituted Moyoi Is an aryl group; u, and are integers 1 to 3. ]
[0085] 一般式 (b— 0)において、 R51は、直鎖、分岐鎖若しくは環状のアルキル基、または 直鎖、分岐鎖若しくは環状のフッ素化アルキル基を表す。 In the general formula (b-0), R 51 represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group.
前記直鎖若しくは分岐鎖状のアルキル基としては、炭素数 1〜10であることが好ま しぐ炭素数 1〜8であることがさらに好ましぐ炭素数 1〜4であることが最も好ましい。 前記環状のアルキル基としては、炭素数 4〜 12であることが好ましぐ炭素数 5〜1 0であることがさらに好ましぐ炭素数 6〜： LOであることが最も好ましい。  The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. The cyclic alkyl group preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and still more preferably 6 to carbon atoms: LO.
前記フッ素化アルキル基としては、炭素数 1〜： LOであることが好ましぐ炭素数 1〜 8であることがさらに好ましぐ炭素数 1〜4であることが最も好ましい。また。該フツイ匕 アルキル基のフッ素化率 (アルキル基中全水素原子の個数に対する置換したフッ素 原子の個数の割合）は、好ましくは 10〜100%、さらに好ましくは 50〜100%であり、 特に水素原子をすベてフッ素原子で置換したもの力 酸の強度が強くなるので好まし い。 R51としては、直鎖状のアルキル基または直鎖状のフッ素化アルキル基であることが 最も好ましい。 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 fluorination rate of the alkyl group (the ratio of the number of substituted fluorine atoms to the total number of hydrogen atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%, particularly hydrogen atoms. This is preferable because the strength of the acid increases. R 51 is most preferably a linear alkyl group or a linear fluorinated alkyl group.
[0086] R52は、水素原子、水酸基、ハロゲン原子、直鎖、分岐鎖若しくは環状のアルキル 基、直鎖、若しくは分岐鎖状のハロゲンィヒアルキル基、または直鎖若しくは分岐鎖状 のアルコキシ基である。 [0086] R 52 is a hydrogen atom, a hydroxyl group, a halogen atom, a linear, branched or cyclic alkyl group, a linear or branched halogen-I human alkyl group or a linear or branched alkoxy group, It is.
R52において、ハロゲン原子としては、フッ素原子、臭素原子、塩素原子、ヨウ素原 子などが挙げられ、フッ素原子が好ましい。 In R 52 , examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and a fluorine atom is preferable.
R52において、直鎖または分岐鎖状のアルキル基としては、炭素数が 1〜5であるこ とが好ましぐ特に炭素数が 1〜4であることがさらに好ましぐさらには炭素数力^〜 3 であることが最も望ましい。 In R 52 , the linear or branched alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably carbon number power ^ Most preferred is ~ 3.
R52において、環状のアルキル基としては、炭素数 4〜 12が好ましぐ炭素数 4〜10 力 Sさらに好ましぐ炭素数 5〜： LOであることが最も好ましい。 In R 52, the alkyl group of cyclic, number 4-10 force preferred instrument carbon 4-12 carbon atoms S further preferred instrument carbon atoms 5: most preferably LO.
R52において、ハロゲン化アルキル基は、アルキル基中の水素原子の一部または全 部がハロゲン原子で置換された基である。ここでのアルキル基は、前記 R52における「 直鎖または分岐鎖状アルキル基」と同様のものが挙げられる。置換するハロゲン原子 としては上記 R52における「ハロゲン原子」について説明したものと同様のものが挙げ られる。 In R 52 , the halogenated alkyl group is a group in which part or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms. Examples of the alkyl group herein are the same as the “linear or branched alkyl group” in R 52 . Examples of the halogen atom to be substituted include the same as those described for the “halogen atom” in R 52 above.
ハロゲン化アルキル基において、水素原子の全個数の 50〜100%がハロゲン原子 で置換されて 、ることが望ましく、全て置換されて 、ることがより好まし!/、。  In the halogenated alkyl group, it is desirable that 50 to 100% of the total number of hydrogen atoms are substituted with halogen atoms, and it is more preferable that all are substituted! /.
R52において、アルコキシ基としては、直鎖状または分岐鎖状であり、その炭素数は 好ましくは 1〜5、特に 1〜4、さらには 1〜3であることが望ましい。 In R 52 , the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.
R52としては、これらの中でも水素原子が好ましい。 Among these, R 52 is preferably a hydrogen atom.
[0087] R53は置換基を有して 、てもよ 、ァリール基であり、置換基を除!、た基本環 (母体環 )の構造としては、ナフチル基、フエ-ル基、アントラセ-ル基などが挙げられ、本発 明の効果や ArFエキシマレーザーなどの露光光の吸収の観点から、フエ-ル基が望 ましい。 [0087] R 53 may have a substituent, but may be an aryl group, and the structure of the basic ring (matrix ring) may be a naphthyl group, a phenyl group, an anthracene group. From the viewpoint of the effect of the present invention and the absorption of exposure light such as ArF excimer laser, the phenyl group is desirable.
置換基としては、水酸基、低級アルキル基 (直鎖または分岐鎖状であり、その好まし い炭素数は 5以下であり、特にメチル基が好ましい）などを挙げることができる。 R53のァリール基としては、置換基を有しな 、ものがより好ま 、。 Examples of the substituent include a hydroxyl group and a lower alkyl group (straight or branched chain, preferably having 5 or less carbon atoms, particularly preferably a methyl group). As the aryl group for R 53 , those having no substituent are more preferable.
u' 'は 1〜3の整数であり、 2または 3であることが好ましぐ特に 3であることが望まし い。  u ′ ′ is an integer of 1 to 3, 2 or 3 is preferred, and 3 is particularly desirable.
[0088] 一般式 (b— O)で表される酸発生剤の好ましいものとしては、以下の化学式で表さ れるものを挙げることができる。  [0088] Preferable examples of the acid generator represented by the general formula (b-O) include those represented by the following chemical formula.
[0089] [化 23] [0089] [Chemical 23]
Figure imgf000034_0001
Figure imgf000034_0001
[0090] 中でも下記化学式 (b— 0— 1)で表される化合物が好ましい。 [0090] Among them, a compound represented by the following chemical formula (b-0-1) is preferable.
[0091] [化 24] [0091] [Chemical 24]
Figure imgf000034_0002
Figure imgf000034_0002
[0092] 一般式 (b— O)で表される酸発生剤は 1種または 2種以上混合して用いることができ る。 [0092] The acid generators represented by the general formula (b—O) can be used alone or in combination.
[0093] 一般式 (b— 0)で表される酸発生剤の他のォ-ゥム塩系酸発生剤としては、例えば 下記一般式 (b— 1)または (b— 2)で表される化合物が挙げられる。  [0093] Other acid salt acid generators of the acid generator represented by the general formula (b-0) include, for example, those represented by the following general formula (b-1) or (b-2). Compounds.
[0094] [化 25]
Figure imgf000035_0001
[0094] [Chemical 25]
Figure imgf000035_0001
[式中、 R1"^3", R5"〜R6"は、それぞれ独立に、ァリール基またはアルキル基を 表し; R4"は、直鎖、分岐または環状のアルキル基またはフッ素化アルキル基を表し； ，，〜 "のうち少なくとも 1っはァリール基を表し、 R5"〜R6"のうち少なくとも 1つは ァリール基を表す。 ] [Wherein 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. ]
式 (b— 1)中、 "〜 "はそれぞれ独立にァリール基またはアルキル基を表す。 R 〜 "のうち、少なくとも 1っはァリール基を表す。 ，，〜 "のうち、 2以上がァリー ル基であることが好ましぐ Rlw〜R3"のすべてがァリール基であることが最も好ましい In the formula (b-1), “to” each independently represents an aryl group or an alkyl group. At least one of R to “represents an aryl group. Of,, to“, two or more are preferably aryl groups. R lw to R 3 ”are all aryl groups. Most preferred
Rlw〜R3"のァリール基としては、特に制限はなぐ例えば、炭素数 6〜20のァリー ル基であって、該ァリール基は、その水素原子の一部または全部がアルキル基、ァ ルコキシ基、ハロゲン原子等で置換されていてもよぐされていなくてもよい。ァリール 基としては、安価に合成可能なことから、炭素数 6〜： LOのァリール基が好ましい。具 体的には、たとえばフエ-ル基、ナフチル基が挙げられる。 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.
前記ァリール基の水素原子が置換されていても良いアルキル基としては、炭素数 1 〜5のアルキル基が好ましぐメチル基、ェチル基、プロピル基、 n-ブチル基、 tert- ブチル基であることが最も好まし 、。  Examples of the 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.
前記ァリール基の水素原子が置換されていても良いアルコキシ基としては、炭素数 1〜5のアルコキシ基が好ましぐメトキシ基、エトキシ基が最も好ましい。  As the 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.
前記ァリール基の水素原子が置換されていても良いハロゲン原子としては、フッ素 原子であることが好ましい。 The halogen atom that may be substituted for the hydrogen atom of the aryl group is preferably a fluorine atom.
"〜 "のアルキル基としては、特に制限はなぐ例えば炭素数 1〜10の直鎖状 、分岐状または環状のアルキル基等が挙げられる。解像性に優れる点から、炭素数 1 〜5であることが好ましい。具体的には、メチル基、ェチル基、 n—プロピル基、イソプ 口ピル基、 n—ブチル基、イソブチル基、 n—ペンチル基、シクロペンチル基、へキシ ル基、シクロへキシル基、ノニル基、デカニル基等が挙げられ、解像性に優れ、また 安価に合成可能なことから好ましいものとして、メチル基を挙げることができる。 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, Decanyl group, etc., excellent resolution, A methyl group is preferable because it can be synthesized at a low cost.
これらの中で、 "〜 "はすべてフエ-ル基であることが最も好ましい。  Among these, it is most preferable that all of “˜” are a phenol group.
[0096] R4"は、直鎖、分岐または環状のアルキル基またはフッ素化アルキル基を表す。 [0096] R 4 "represents a linear, branched or cyclic alkyl group or fluorinated alkyl group.
前記直鎖又は分岐のアルキル基としては、炭素数 1〜10であることが好ましぐ炭 素数 1〜8であることがさらに好ましぐ炭素数 1〜4であることが最も好ましい。  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.
前記環状のアルキル基としては、前記 R1"で示したような環式基であって、炭素数 4 〜 15であることが好ましぐ炭素数 4〜 10であることがさらに好ましぐ炭素数 6〜10 であることが最も好ましい。 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.
前記フッ素化アルキル基としては、炭素数 1〜： LOであることが好ましぐ炭素数 1〜8 であることがさらに好ましぐ炭素数 1〜4であることが最も好ましい。また。該フッ化ァ ルキル基のフッ素化率（アルキル基中のフッ素原子の割合）は、好ましくは 10〜： LOO %、さらに好ましくは 50〜100%であり、特に水素原子をすベてフッ素原子で置換し たものが、酸の強度が強くなるので好ましい。  The fluorinated alkyl group is most preferably 1 to 4 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. Also. The fluorination rate (ratio of fluorine atoms in the alkyl group) of the fluorinated alkyl group is preferably 10 to: LOO%, 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.
R4"としては、直鎖または環状のアルキル基、またはフッ素化アルキル基であること が最も好ましい。 R 4 ″ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.
[0097] 式 (b— 2)中、 R5"〜R6"はそれぞれ独立にァリール基またはアルキル基を表す。 R 5，，〜R6，，のうち、少なくとも 1っはァリール基を表す。 R5"〜R6，，のすべてがァリール基 であることが好ましい。 In formula (b-2), R 5 ″ to R 6 ″ each independently represents an aryl group or an alkyl group. Of R 5, ˜˜R 6 , at least one represents an aryl group. All of R 5 ″ to R 6 , are preferably aryl groups.
R5"〜R6"のァリール基としては、 ，，〜 "のァリール基と同様のものが挙げられる Examples of the aryl group of R 5 "to R 6 " include the same as the aryl group of,, ~ "
R5"〜R6"のアルキル基としては、 ，，〜 "のアルキル基と同様のものが挙げられ る。 Examples of the alkyl group for R 5 "to R 6 " include the same alkyl groups as for,, to ".
これらの中で、 R5"〜R6"はすべてフエ-ル基であることが最も好ましい。 式 (b— 2)中の R4"としては上記式 (b - 1)の R4"と同様のものが挙げられる。 Among these, it is most preferable that all of 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.
[0098] 上記一般式 (b— 1)または (b— 2)で表されるォニゥム塩系酸発生剤の具体例とし ては、ジフエ-ルョードニゥムのトリフルォロメタンスルホネートまたはノナフルォロブタ ンスルホネート、ビス（4— tert—ブチルフエ-ル）ョードニゥムのトリフルォロメタンス ルホネートまたはノナフルォロブタンスルホネート、トリフエ-ルスルホ-ゥムのトリフル ォロメタンスルホネート、そのヘプタフルォロプロパンスルホネートまたはそのノナフル ォロブタンスルホネート、トリ（4 メチルフエ-ル）スルホ -ゥムのトリフルォロメタンス ルホネート、そのヘプタフルォロプロパンスルホネートまたはそのノナフルォロブタン スルホネート、ジメチル（4ーヒドロキシナフチル）スルホ -ゥムのトリフルォロメタンスル ホネート、そのヘプタフルォロプロパンスルホネートまたはそのノナフルォロブタンス ルホネート、モノフエ-ルジメチルスルホ-ゥムのトリフルォロメタンスルホネート、その ヘプタフルォロプロパンスルホネートまたはそのノナフルォロブタンスルホネート、ジ フエ-ルモノメチルスルホ-ゥムのトリフルォロメタンスルホネート、そのヘプタフルォ 口プロパンスルホネートまたはそのノナフルォロブタンスルホネート、（4 メチルフエ -ル）ジフエ-ルスルホ-ゥムのトリフルォロメタンスルホネート、そのヘプタフルォロ プロパンスルホネートまたはそのノナフルォロブタンスルホネート、（4ーメトキシフエ- ル）ジフエ-ルスルホ-ゥムのトリフルォロメタンスルホネート、そのヘプタフルォロプロ パンスルホネートまたはそのノナフルォロブタンスルホネート、トリ（4—tert ブチル） フエ-ルスルホ-ゥムのトリフルォロメタンスルホネート、そのヘプタフルォロプロパン スルホネートまたはそのノナフルォロブタンスルホネート、ジフエ-ル（1一（4ーメトキ シ）ナフチル）スルホ -ゥムのトリフルォロメタンスルホネート、そのヘプタフルォロプロ パンスルホネートまたはそのノナフルォロブタンスルホネートなどが挙げられる。また、 これらのォ -ゥム塩のァ-オン部がメタンスルホネート、 n—プロパンスルホネート、 n -ブタンスルホネート、 n -オクタンスルホネートに置き換えたォ-ゥム塩も用 、ること ができる。 [0098] Specific examples of the onion salt-based acid generator represented by the above general formula (b-1) or (b-2) include trifluoromethanesulfonate, nonafluorobutanesulfonate, bis (4 — Tert-Butylphenol) Jodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, triphenylsulfur trifluoride Fluorosulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tri (4 methylphenol) sulfo-trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorolob Tan sulfonate, dimethyl (4-hydroxynaphthyl) sulfone trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, monophenyl dimethyl sulfone trifluoromethanesulfonate , The heptafluoropropane sulfonate or the nonafluorobutane sulfonate, trifluoromethane sulfonate of diphenyl monomethyl sulfome, the heptafluoro oral propane sulfonate or Nonafluorobutanesulfonate, (4-methylphenol) diphenylsulfotrifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, (4-methoxyphenyl) diphenylsulfone Trifluoromethanesulfonate, its heptafluoropropanosulfonate, or its nonafluorobutanesulfonate, tri (4-tertbutyl) phenolsulfotrifluoromethanesulfonate, its heptafluoropropane sulfonate, Nonafluorobutane sulfonate, diphenyl (1- (4-methoxy) naphthyl) sulfone trifluoromethane sulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate I can get lost. In addition, it is also possible to use an ohmic salt in which the cation part of these ohmic salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate.
[0099] また、前記一般式 (b— 1)又は (b— 2)において、ァニオン部を下記一般式 (b— 3) 又は (b— 4)で表されるァ-オン部に置き換えたォ-ゥム塩系酸発生剤も用いること ができる (カチオン部は (b— 1)又は (b— 2)と同様)。  [0099] In addition, in the general formula (b-1) or (b-2), the anion part is replaced with a caron part represented by the following general formula (b-3) or (b-4). A -um salt-based acid generator can also be used (the cation moiety is the same as (b-1) or (b-2)).
[0100] [化 26]  [0100] [Chemical 26]
Figure imgf000037_0001
[式中、 X"は、少なくとも 1つの水素原子がフッ素原子で置換された炭素数 2〜6のァ ルキレン基を表し; Υ"、 Ζ"は、それぞれ独立に、少なくとも 1つの水素原子がフッ素 原子で置換された炭素数 1〜10のアルキル基を表す。 ]
Figure imgf000037_0001
[Wherein X "represents a C 2-6 alkylene group in which at least one hydrogen atom is replaced by a fluorine atom; Υ", Ζ "each independently represents at least one hydrogen atom is fluorine. Represents an alkyl group having 1 to 10 carbon atoms substituted with an atom.
[0101] X"は、少なくとも 1つの水素原子がフッ素原子で置換された直鎖状または分岐状の アルキレン基であり、該アルキレン基の炭素数は 2〜6であり、好ましくは炭素数 3〜5 、最も好ましくは炭素数 3である。 [0101] X "is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 3 carbon atoms. 5 and most preferably 3 carbon atoms.
Υ"、 Ζ"は、それぞれ独立に、少なくとも 1つの水素原子がフッ素原子で置換された 直鎖状または分岐状のアルキル基であり、該アルキル基の炭素数は 1〜 10であり、 好ましくは炭素数 1〜7であり、より好ましくは炭素数 1〜3である。  Υ "and Ζ" 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.
X"のアルキレン基の炭素数または Υ"、 Ζ"のアルキル基の炭素数は、上記炭素数 の範囲内において、レジスト溶媒への溶解性も良好である等の理由により、小さいほ ど好まし ヽ。  The carbon number of the alkylene group of X "or the carbon number of the alkyl group of Υ" and Ζ "is preferably as small as possible because it has good solubility in the resist solvent within the above carbon number range.ヽ.
また、 X"のアルキレン基または Υ"、 Ζ"のアルキル基において、フッ素原子で置換さ れている水素原子の数が多いほど、酸の強度が強くなり、また 200nm以下の高エネ ルギ一光や電子線に対する透明性が向上するので好ま U、。該アルキレン基または アルキル基中のフッ素原子の割合、すなわちフッ素化率は、好ましくは 70〜100%、 さらに好ましくは 90〜： LOO%であり、最も好ましくは、全ての水素原子がフッ素原子で 置換されたパーフルォロアルキレン基またはパーフルォロアルキル基である。  In addition, in the alkylene group of X "or the alkyl group of Υ" and Ζ ", the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength and the higher the energy of 200 nm or less. And 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 LOO%. Most preferably, it is a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
[0102] 本明細書において、ォキシムスルホネート系酸発生剤とは、下記一般式 (B— 1)で 表される基を少なくとも 1つ有する化合物であって、放射線の照射によって酸を発生 する特性を有するものである。この様なォキシムスルホネート系酸発生剤は、化学増 幅型レジスト組成物用として多用されているので、任意に選択して用いることができる [0102] In this specification, the oxime sulfonate 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.
[0103] [化 27]
Figure imgf000038_0001
[0103] [Chemical 27]
Figure imgf000038_0001
(式 (B— 1)中、 R31、 R32はそれぞれ独立に有機基を表す。 ) [0104] R31、 R32の有機基は、炭素原子を含む基であり、炭素原子以外の原子 (たとえば水 素原子、酸素原子、窒素原子、硫黄原子、ハロゲン原子 (フッ素原子、塩素原子等） 等）を有していてもよい。 (In the formula (B-1), R 31 and R 32 each independently represents an organic group.) [0104] The organic group of R 31 and R 32 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.).
R31の有機基としては、直鎖、分岐または環状のアルキル基またはァリール基が好 ましい。これらのアルキル基、ァリール基は置換基を有していても良い。該置換基とし ては、特に制限はなぐたとえばフッ素原子、炭素数 1〜6の直鎖、分岐または環状の アルキル基等が挙げられる。ここで、「置換基を有する」とは、アルキル基またはァリー ル基の水素原子の一部または全部が置換基で置換されていることを意味する。 As the organic group for R 31 , a linear, branched or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent. The substituent is not particularly limited, and examples thereof include a fluorine atom and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. 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.
アルキル基としては、炭素数 1〜20が好ましぐ炭素数 1〜10がより好ましぐ炭素 数 1〜8がさらに好ましぐ炭素数 1〜6が特に好ましぐ炭素数 1〜4が最も好ましい。 アルキル基としては、特に、部分的または完全にハロゲンィ匕されたアルキル基 (以下 、ハロゲン化アルキル基ということがある）が好ましい。なお、部分的にハロゲンィ匕され たアルキル基とは、水素原子の一部がハロゲン原子で置換されたアルキル基を意味 し、完全にハロゲンィ匕されたアルキル基とは、水素原子の全部がハロゲン原子で置 換されたアルキル基を意味する。ハロゲン原子としては、フッ素原子、塩素原子、臭 素原子、ヨウ素原子等が挙げられ、特にフッ素原子が好ましい。すなわち、ハロゲン 化アルキル基は、フッ素化アルキル基であることが好まし!/、。  As the 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. As the alkyl group, 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. Examples of the halogen atom 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! /.
ァリール基は、炭素数 4〜20が好ましぐ炭素数 4〜： LOがより好ましぐ炭素数 6〜1 0が最も好ましい。ァリール基としては、特に、部分的または完全にハロゲン化された ァリール基が好ましい。なお、部分的にハロゲン化されたァリール基とは、水素原子 の一部がハロゲン原子で置換されたァリール基を意味し、完全にハロゲン化されたァ リール基とは、水素原子の全部がハロゲン原子で置換されたァリール基を意味する。  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. As the aryl group, 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. An aryl group substituted with an atom.
R31としては、特に、置換基を有さない炭素数 1〜4のアルキル基、または炭素数 1 〜4のフッ素化アルキル基が好まし 、。 R 31 is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms.
[0105] R32の有機基としては、直鎖、分岐または環状のアルキル基、ァリール基またはシァ ノ基が好ましい。 R32のアルキル基、ァリール基としては、前記 R31で挙げたアルキル 基、ァリール基と同様のものが挙げられる。 As the organic group for R 32 , a linear, branched or cyclic alkyl group, aryl group or cyan group is preferable. Examples of the alkyl group and aryl group for R 32 include the same alkyl groups and aryl groups as those described above for R 31 .
R32としては、特に、シァノ基、置換基を有さない炭素数 1〜8のアルキル基、または 炭素数 1〜8のフッ素化アルキル基が好ましい。 As R 32 , in particular, 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 is preferred.
[0106] ォキシムスルホネート系酸発生剤として、さらに好ましいものとしては、下記一般式 ( B- 2)または (B— 3)で表される化合物が挙げられる。  [0106] More preferable examples of the oxime sulfonate acid generator include compounds represented by the following general formula (B-2) or (B-3).
[0107] [化 28]
Figure imgf000040_0001
[0107] [Chemical 28]
Figure imgf000040_0001
[式 (B— 2)中、 R33は、シァノ基、置換基を有さないアルキル基またはハロゲンィ匕ァ ルキル基である。 R34はァリール基である。 R35は置換基を有さないアルキル基または ハロゲン化アルキル基である。 ] [In the formula (B-2), R 33 represents a cyano group, an alkyl group having no substituent, or a halogenalkyl group. R 34 is an aryl group. R 35 represents an alkyl group having no substituent or a halogenated alkyl group. ]
[0108] [化 29]  [0108] [Chemical 29]
Figure imgf000040_0002
Figure imgf000040_0002
[式 (Β— 3)中、 R36はシァノ基、置換基を有さないアルキル基またはハロゲンィ匕アル キル基である。 R37は 2または 3価の芳香族炭化水素基である。 R38は置換基を有さな いアルキル基またはハロゲン化アルキル基である。 ρ'，は 2または 3である。 ] [In the formula (Β-3), R 36 represents a cyano group, an alkyl group having no substituent, or a halogenalkyl group. R 37 is a divalent or trivalent aromatic hydrocarbon group. R 38 is an alkyl group having no substituent or a halogenated alkyl group. ρ ', is 2 or 3. ]
[0109] 前記一般式 (Β— 2)において、 R33の置換基を有さないアルキル基またはハロゲン 化アルキル基は、炭素数が 1〜： L0であることが好ましぐ炭素数 1〜8がより好ましぐ 炭素数 1〜6が最も好ましい。 [0109] In the general formula (Β-2), the alkyl group or halogenated alkyl group having no substituent of R 33 preferably has 1 to 8 carbon atoms: 1 to 8 carbon atoms. Is more preferred. Carbon number 1 to 6 is most preferred.
R33としては、ハロゲンィ匕アルキル基が好ましぐフッ素化アルキル基がより好ましい R 33 is more preferably a fluorinated alkyl group, preferably a halogenated alkyl group.
R33におけるフッ素化アルキル基は、アルキル基の水素原子が 50%以上フッ素化さ れていることが好ましぐより好ましくは 70%以上、さらに好ましくは 90%以上フッ素 化されて!/、ることが好まし!/、。 The fluorinated alkyl group in R 33 is preferably fluorinated with 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, and even more preferably 90% or more. I like it! /
[0110] R3のァリール基としては、フエ-ル基、ビフヱ-ル（biphenyl)基、フルォレ -ル（fl uorenyl)基、ナフチル基、アントラセル（anthracyl)基、フエナントリル基等の、芳香 族炭化水素の環力 水素原子を 1つ除いた基、およびこれらの基の環を構成する炭 素原子の一部が酸素原子、硫黄原子、窒素原子等のへテロ原子で置換されたへテ ロアリール基等が挙げられる。これらのなかでも、フルォレニル基が好ましい。 [0110] The aryl group of R 3 includes an aromatic group such as a phenol group, a biphenyl group, a fluoro group, a naphthyl group, an anthracyl group, a phenanthryl group, and the like. Group hydrocarbon ring force A group in which one hydrogen atom has been removed, and some of the carbon atoms constituting the ring of these groups have been substituted with heteroatoms such as oxygen, sulfur, and nitrogen atoms. And a roaryl group. Among these, a fluorenyl group is preferable.
R34のァリール基は、炭素数 1〜10のアルキル基、ハロゲン化アルキル基、アルコキ シ基等の置換基を有して 、ても良 、。該置換基におけるアルキル基またはハロゲン 化アルキル基は、炭素数が 1〜8であることが好ましぐ炭素数 1〜4がさらに好ましい 。また、該ハロゲン化アルキル基は、フッ素化アルキル基であることが好ましい。 The aryl group of R 34 may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group. The alkyl group or halogenated alkyl group in the substituent preferably has 1 to 4 carbon atoms, more preferably 1 to 4 carbon atoms. The halogenated alkyl group is preferably a fluorinated alkyl group.
[0111] R35の置換基を有さないアルキル基またはハロゲンィ匕アルキル基は、炭素数が 1〜 10であることが好ましぐ炭素数 1〜8がより好ましぐ炭素数 1〜6が最も好ましい。[0111] The alkyl group or halogenated alkyl group having no substituent of R 35 preferably has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. Most preferred.
R35としては、ハロゲンィ匕アルキル基が好ましぐ部分的又は完全にフッ素化された アルキル基が好ましい。 R 35 is preferably a partially or fully fluorinated alkyl group, preferably a halogenated alkyl group.
R35におけるフッ素化アルキル基は、アルキル基の水素原子が 50%以上フッ素化さ れていることが好ましぐより好ましくは 70%以上、さらに好ましくは 90%以上フッ素 化されていること力 発生する酸の強度が高まるため好ましい。最も好ましくは、水素 原子が 100%フッ素置換された完全フッ素化アルキル基である。 The fluorinated alkyl group in R 35 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.
[0112] 前記一般式 (B— 3)において、 R36の置換基を有さないアルキル基またはハロゲン 化アルキル基としては、上記 R33の置換基を有さな 、アルキル基またはハロゲンィ匕ァ ルキル基と同様のものが挙げられる。 In the general formula (B-3), the alkyl group or halogenated alkyl group having no substituent of R 36 is an alkyl group or halogenalkyl having no substituent of the above R 33. The same thing as a group is mentioned.
R37の 2または 3価の芳香族炭化水素基としては、上記 R34のァリール基力もさらに 1 または 2個の水素原子を除 、た基が挙げられる。 Examples of the divalent or trivalent aromatic hydrocarbon group for R 37 include groups in which the aryl group strength of R 34 is one or two hydrogen atoms removed.
R38の置換基を有さな 、アルキル基またはハロゲンィ匕アルキル基としては、上記 5 の置換基を有さないアルキル基またはハロゲンィ匕アルキル基と同様のものが挙げら れる。 Do no substituent of R 38, the alkyl group or Harogeni spoon alkyl group, the same alkyl group or Harogeni spoon alkyl group containing no substituent group of the 5 like et be.
P' 'は好ましくは 2である。  P ′ ′ is preferably 2.
[0113] ォキシムスルホネート系酸発生剤の具体例としては、 α—（p トルエンスルホ-ル ォキシィミノ）一ベンジルシア-ド、 α - (ρ クロ口ベンゼンスルホ -ルォキシィミノ） —ベンジルシア-ド、 α - (4—二トロベンゼンスルホ -ルォキシィミノ）—ベンジルシ アニド、 ひ一（4 -トロー 2 トリフルォロメチルベンゼンスルホ -ルォキシィミノ） ベンジルシア-ド、 α - (ベンゼンスルホ -ルォキシィミノ）—4—クロ口べンジルシア -ド、 α (ベンゼンスルホ -ルォキシィミノ）— 2, 4 ジクロロべンジルシア-ド、 α —(ベンゼンスルホ -ルォキシィミノ）— 2, 6 ジクロロべンジルシア-ド、 α (ベン ゼンスルホ -ルォキシィミノ） 4—メトキシベンジルシア-ド、 α - (2—クロ口べンゼ ンスルホ -ルォキシィミノ）—4—メトキシベンジルシア-ド、 α - (ベンゼンスルホ- ルォキシィミノ）—チェン— 2—ィルァセトニトリル、 at - (4—ドデシルベンゼンスルホ -ルォキシィミノ）—ベンジルシア-ド、 α - [ (ρ トルエンスルホ -ルォキシィミノ） - 4—メトキシフエ-ル]ァセトニトリル、 α [ (ドデシルベンゼンスルホ -ルォキシィミノ )—4—メトキシフエ-ル]ァセトニトリル、 at - (トシルォキシィミノ）—4—チェ-ルシア -ド、 α (メチルスルホ -ルォキシィミノ）— 1—シクロペンテ-ルァセトニトリル、 α - (メチルスルホ -ルォキシィミノ）— 1—シクロへキセ-ルァセトニトリル、 OC - (メチ ルスルホ -ルォキシィミノ） 1ーシクロヘプテュルァセトニトリル、 α （メチルスルホ -ルォキシィミノ）— 1—シクロオタテュルァセトニトリル、 at - (トリフルォロメチルスル ホ -ルォキシィミノ）— 1—シクロペンテ-ルァセトニトリル、 α - (トリフルォロメチルス ルホ -ルォキシィミノ）ーシクロへキシルァセトニトリル、 α （ェチルスルホ-ルォキ シィミノ）—ェチルァセトニトリル、 OC - (プロピルスルホ -ルォキシィミノ）—プロピルァ セト-トリル、 α - (シクロへキシルスルホ -ルォキシィミノ）—シクロペンチルァセトニ トリル、 a - (シクロへキシルスルホ -ルォキシィミノ）—シクロへキシルァセトニトリル、 a - (シクロへキシルスルホ -ルォキシィミノ）— 1—シクロペンテ-ルァセトニトリル、 a - (ェチルスルホ -ルォキシィミノ）— 1—シクロペンテ-ルァセトニトリル、 α (ィ ソプロピルスルホ -ルォキシィミノ）— 1—シクロペンテ-ルァセトニトリル、 a - (η— ブチルスルホニルォキシィミノ） 1ーシクロペンテ二ルァセトニトリル、 α （ェチルス ルホ -ルォキシィミノ）— 1—シクロへキセ-ルァセトニトリル、 α - (イソプロピルスル ホ -ルォキシィミノ） 1ーシクロへキセ-ルァセトニトリル、 ひ （η—ブチルスルホ- ルォキシィミノ） 1ーシクロへキセ-ルァセトニトリル、 α （メチルスルホ -ルォキシ ィミノ）—フエ-ルァセトニトリル、 OC - (メチルスルホ -ルォキシィミノ）—ρ—メトキシフ ェ-ルァセトニトリル、 α - (トリフルォロメチルスルホ -ルォキシィミノ）—フエ-ルァ セト-トリル、 α - (トリフルォロメチルスルホ -ルォキシィミノ）—p—メトキシフエ-ル ァセトニトリル、 α - (ェチルスルホニルォキシィミノ）—ρ—メトキシフエ二ルァセトニト リル、 α—(プロピルスルホ -ルォキシィミノ） ρ メチルフエ-ルァセトニトリル、 α （メチルスルホ -ルォキシィミノ） ρ ブロモフエ-ルァセトニトリルなどが挙げられ る。 [0113] Specific examples of oxime sulfonate-based acid generators include α- (p-toluenesulfo-oxyximino) monobenzyl cyanide, α- (ρ chlorobenzene-sulfo-oxyoximino) -benzyl cyanide, α- ( 4-Nitrobenzenesulfo-ruximino) —Benzyl cyanide, Hiichi (4-troo 2 trifluoromethylbenzenesulfo-ruximino) Benzyl cyanide, α- (Benzenesulfo-Luximinomino) -4-chlorobenzoyl cyanide, α (Benzenesulfo-Luximinomino) -2, 4 Dichlorobenzil cyanide, α — (Benzenesulfo-Luximinomino) -2 6 Dichlorobenzil cyanide, α (Benzenesulfo-Luximinomino) 4-Methoxybenzyl cyanide, α- (2-Clorobenzonesulfo-Luximinomino) -4-Methoxybenzyl cyanide, α- (Benzenesulfo- (Luoxymino) —Chen—2-ylacetonitrile, at- (4-Dodecylbenzenesulfo-ruximino) —Benzyl cyanide, α-[(ρ Toluenesulfo-Luoximino) -4-methoxyphenyl] acetonitrile, α [( Dodecylbenzenesulfo-luximino))-4-methoxyphenyl] acetonitrile, at- (tosiloxymino) 4-Chelsiade, α (Methylsulfo-Luoxyimino) — 1-Cyclopentyl-Luacetonitrile, α- (Methylsulfo-Luoxyimino) — 1-Cyclohexyl-Luacetonitrile, OC-(Methylsulfo-Luoxyimino) 1-Cycloheptyl Asetonitoriru, alpha (Mechirusuruho - Ruokishiimino) - 1-cyclopropyl OTA Saturation Rua Seto nitrile, at - (triflate Ruo b methylsulfanyl e - Ruokishiimino) - 1-cyclopent - Ruasetonitoriru, alpha - (triflate Ruo b methyl sulfo - Ruokishiimino ) -Cyclohexylacetonitrile, α (Ethylsulfo-Luximino) -Ethylacetonitrile, OC-(Propylsulfo-Luoxyimino) -Propylaceto-tolyl, α- (Cyclohexylsulfo-Luoxyimino) -Cyclopentylacetonitrile , A-(to cyclo Xylsulfo-ruximino) -cyclohexylhexonitrile, a- (cyclohexylsulfo-ruximino) -1-cyclopente-rucetonitrile, a- (ethylsulfo-ruximino)-1-cyclopente-rucetonitrile, α (isopropylsulfo-ruximino) ) — 1-Cyclopentylacetonitrile, a-(η-Butylsulfonyloxyimino) 1-Cyclopentenylacetonitrile, α (Ethylsulfo-ruximino) — 1-Cyclohexyl-acetonitrile, α- (Isopropylsulfuroxymino) 1-Cyclohexylacetonitrile, （( η -butylsulfo-oxyximino) 1-Cyclohexylacetonitrile, α (methylsulfo-ruxitimino)-phenolacetonitrile, OC-(Methylsulfo-oxyximino) ) —Ρ—Methoxyphenylacetonitrile, α- (trifluoromethylsulfo-oxyximino) —ferroaceto-tolyl, α- (trifluoromethylsulfo-oxyximino) —p-methoxyphenol Acetonitrile, α- (ethylsulfonyloxyimino) -ρ-methoxyphenylacetononitrile, α- (propylsulfo-oxyximino) ρ methylphenylacetonitrile, α (methylsulfo-oxyximino) ρ bromophenylacetonitrile, and the like.
また、特開平 9 - 208554号公報 (段落 [0012]〜 [0014]の [化 18]〜 [化 19] )に 開示されて!、るォキシムスルホネート系酸発生剤、 WO2004Z074242A2 (65〜8 5頁目の Examplel〜40)に開示されているォキシムスルホネート系酸発生剤も好適 に用いることができる。  Also disclosed in JP-A-9-208554 (paragraphs [0012] to [0014], [Chemical Formula 18] to [Chemical Formula 19]) !, Ruoxime sulfonate acid generator, WO2004Z074242A2 (65 to 85) The oxime sulfonate acid generators disclosed in Examples 1 to 40) on the page can also be suitably used.
また、好適なものとして以下のものを例示することができる。  Moreover, the following can be illustrated as a suitable thing.
[化 30] [Chemical 30]
Figure imgf000044_0001
Figure imgf000044_0001
[0115] 上記例示化合物の中でも、下記の 4つの化合物が好ましい。 [0115] Of the above exemplified compounds, the following four compounds are preferred.
[0116] [化 31] C4H3 -。 一 O一 N=C ~ - ^ [0116] [Chemical 31] C 4 H 3- . One O One N = C ~-^
Figure imgf000045_0001
Figure imgf000045_0001
[0117] ジァゾメタン系酸発生剤のうち、ビスアルキルまたはビスァリールスルホ -ルジァゾメ タン類の具体例としては、ビス（イソプロピルスルホ -ル）ジァゾメタン、ビス（p トルェ ンスルホ -ル）ジァゾメタン、ビス（ 1 , 1—ジメチルェチルスルホ -ル）ジァゾメタン、ビ ス（シクロへキシルスルホ -ル）ジァゾメタン、ビス（2, 4 ジメチルフエ-ルスルホ-ル )ジァゾメタン等が挙げられる。 [0117] Among diazomethane acid generators, specific examples of 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.
また、特開平 11— 035551号公報、特開平 11— 035552号公報、特開平 11— 03 5573号公報に開示されているジァゾメタン系酸発生剤も好適に用いることができる。 また、ポリ（ビススルホ -ル）ジァゾメタン類としては、例えば、特開平 11 322707 号公報に開示されている、 1, 3 ビス（フエ-ルスルホ-ルジァゾメチルスルホ -ル） プロノ ン、 1, 4 ビス（フエ-ルスルホ-ルジァゾメチルスルホ -ル）ブタン、 1, 6 ビ ス（フエ-ルスルホ-ルジァゾメチルスルホ -ル）へキサン、 1 , 10—ビス（フエ-ルス ルホ-ルジァゾメチルスルホ -ル）デカン、 1, 2—ビス（シクロへキシルスルホ -ルジ ァゾメチルスルホ -ル）ェタン、 1, 3 ビス（シクロへキシルスルホ-ルジァゾメチルス ルホ -ル）プロパン、 1, 6 ビス（シクロへキシルスルホ-ルジァゾメチルスルホ -ル） へキサン、 1, 10—ビス（シクロへキシルスルホ-ルジァゾメチルスルホ -ル）デカンな どを挙げることができる。  Further, diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552 and JP-A-11-035573 can also be suitably used. Examples of poly (bissulfol) diazomethanes include 1,3 bis (phenylsulfol diazomethylsulfol) pronone, 1, 4 disclosed in JP-A-11 322707. Bis (phenylsulfodiazomethylsulfol) butane, 1,6-bis (phenolsulfodiazomethylsulfol) hexane, 1,10-bis (phenolsulfoldiol) Zomethylsulfo) decane, 1,2-bis (cyclohexylsulfodiazomethylsulfo) ethane, 1,3 bis (cyclohexylsulfodiazomethylsulfo) propane, 1,6 bis (cyclohexylsulfo-) (Luazomethylsulfol) hexane, 1,10-bis (cyclohexylsulfoldiazomethylsulfol) decane, and the like.
[0118] (B)成分としては、これらの酸発生剤を 1種単独で用いてもよいし、 2種以上を組み 合わせて用いてもよい。 [0118] As the component (B), one type of these acid generators may be used alone, or two or more types may be used in combination.
ポジ型レジスト組成物における（B)成分の含有量は、（A)成分 100質量部に対し、 0. 5〜30質量部が好ましぐ 1〜15質量部がより好ましい。上記範囲とすることでパ ターン形成が十分に行われる。また、均一な溶液が得られ、保存安定性が良好となる ため好ましい。 [0119] [任意成分] The content of the component (B) in the positive resist composition is preferably 1 to 15 parts by mass, more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the component (A). Pattern formation is sufficiently performed when the amount falls within the above range. Further, it is preferable because a uniform solution can be obtained and the storage stability becomes good. [0119] [Optional components]
本発明のポジ型レジスト組成物には、レジストパターン形状、引き置き経時安定性（ post exposure stability of the latent image formed oy the pattern-wise exposure of t he resist layer)などを向上させるために、さらに任意の成分として、含窒素有機化合 物 (D) (以下、（D)成分という）を配合させることができる。  The positive resist composition of the present invention is further optional in order to improve the resist pattern shape, post exposure stability of the latent image formed oy the pattern-wise exposure of the resist layer, and the like. As the component, nitrogen-containing organic compound (D) (hereinafter referred to as component (D)) can be blended.
この（D)成分は、既に多種多様なものが提案されているので、公知のものから任意 に用いれば良ぐ例えば、 n キシルァミン、 n プチルァミン、 n—ォクチルアミ ン、 n—ノ-ルァミン、 n—デシルァミン等のモノアルキルァミン；ジェチルァミン、ジ— n—プロピルァミン、ジ—n プチルァミン、ジ—n—ォクチルァミン、ジシクロへキシ ルァミン等のジアルキルァミン；トリメチルァミン、トリエチルァミン、トリ—n—プロピル ァミン、トリー n—ブチルァミン、トリー n キシルァミン、トリー n—ペンチルァミン、ト リー n プチルァミン、トリー n—ォクチルァミン、トリー n—ノニルァミン、トリー n—デ 力-ルァミン、トリ—n—ドデシルァミン等のトリアルキルァミン；ジエタノールァミン、トリ エタノールァミン、ジイソプロパノールァミン、トリイソプロパノールァミン、ジ一 n—オタ タノールァミン、トリー n—ォクタノールァミン等のアルキルアルコールァミンが挙げら れる。これらの中でも、特に第 2級脂肪族アミンゃ第 3級脂肪族ァミンが好ましぐ炭 素数 5 10のトリアルキルァミンがさらに好ましぐトリ一 n—ォクチルァミンが最も好ま しい。 Since a wide variety of components (D) have already been proposed, any known one can be used. For example, n xylamine, n ptylamine, n-octylamine, n-noramine, n- Monoalkylamines such as decylamine; dialkylamines such as jetylamine, di-n-propylamine, di-n-ptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri- n -propyl Trialkylamines such as triamine, tri- n- butyramine, tri- n- xylamine, tri- n- pentylamine, tri- n- ptyluamine, tri- n- octylamine, tri- n- nonylamine, tri- n -de-force-lamine, tri- n -dodecylamine Diethanolamine, triethanolamine, diisopropano Amin, triisopropanolamine § Min, di one n- OTA Tanoruamin, alkyl alcohols § Min such tree n- O click pentanol § Min like et be. Of these, secondary aliphatic amines are most preferred, and tri-n-octylamine, which is more preferred to trialkylamines having a carbon number of 510, which are preferred to tertiary aliphatic amines.
これらは単独で用いてもょ 、し、 2種以上を組み合わせて用いてもょ 、。  These can be used alone or in combination of two or more.
(D)成分は、（A)成分 100質量部に対して、通常 0. 01 5. 0質量部の範囲で用 いられる。  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).
[0120] 本発明のポジ型レジスト組成物には、前記 (D)成分の配合による感度劣化の防止 、またレジストパターン形状、引き置き経時安定性等の向上の目的で、さらに任意の 成分として、有機カルボン酸又はリンのォキソ酸若しくはその誘導体 (E) (以下、（E) 成分という）を含有させることができる。なお、（D)成分と (E)成分は併用することもで きるし、いずれ力 1種を用いることもできる。  [0120] In the positive resist composition of the present invention, 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, 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. In addition, the component (D) and the component (E) can be used in combination, or one force can be used.
有機カルボン酸としては、例えば、マロン酸、クェン酸、リンゴ酸、コハク酸、安息香 酸、サリチル酸などが好適である。 リンのォキソ酸若しくはその誘導体としては、リン酸、リン酸ジー n—ブチルエステル 、リン酸ジフエ-ルエステルなどのリン酸又はそれらのエステルのような誘導体、ホス ホン酸、ホスホン酸ジメチルエステル、ホスホン酸ージー n—ブチルエステル、フエ- ルホスホン酸、ホスホン酸ジフエ-ルエステル、ホスホン酸ジベンジルエステルなどの ホスホン酸及びそれらのエステルのような誘導体、ホスフィン酸、フエ-ルホスフィン 酸などのホスフィン酸及びそれらのエステルのような誘導体が挙げられ、これらの中 で特にホスホン酸が好まし 、。 As the 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 diphenol ester and other phosphoric acid or derivatives such as those esters, phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid Phosphonic acid such as n-butyl ester, phenol phosphonic acid, diphosphoric phosphonic acid ester, dibenzyl phosphonic acid ester and derivatives thereof, phosphinic acid such as phosphinic acid, phenol phosphinic acid and the like And derivatives such as esters, of which phosphonic acid is particularly preferred.
(E)成分は、（A)成分 100質量部当り 0. 01〜5. 0質量部の割合で用いられる。  Component (E) is used in a proportion of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).
[0121] 本発明のポジ型レジスト組成物には、さらに所望により混和性のある添加剤、例え ばレジスト膜の性能を改良するための付加的榭脂、塗布性を向上させるための界面 活性剤、溶解抑制剤、可塑剤、安定剤、着色剤、ハレーション防止剤、染料などを適 宜、添加含有させることができる。 [0121] In 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. Further, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, and the like can be appropriately added and contained.
[0122] ポジ型レジスト組成物は、材料を有機溶剤（以下、「（S)成分」と ヽぅことがある。 )に 溶解させて製造することができる。 [0122] The positive resist composition can be produced by dissolving the material in an organic solvent (hereinafter sometimes referred to as "component (S)").
(S)成分としては、使用する各成分を溶解し、均一な溶液とすることができるもので あればよぐ従来、化学増幅型レジストの溶剤として公知のものの中から任意のものを 1種または 2種以上適宜選択して用いることができる。  As the component (S), it is sufficient if each component to be used can be dissolved into a uniform solution. Any one of conventionally known solvents for chemically amplified resists can be used. Two or more kinds can be appropriately selected and used.
例えば、 γ —ブチロラタトン等のラタトン類；アセトン、メチルェチルケトン、シクロへ キサノン、メチルイソアミルケトン、 2—へプタノンなどのケトン類；エチレングリコール、 エチレングリコーノレモノアセテート、ジエチレングリコール、ジエチレングリコーノレモノ アセテート、プロピレングリコール、プロピレングリコールモノアセテート、ジプロピレン グリコール、若しくはジプロピレングリコールモノアセテート、またはこれらのモノメチル エーテル、モノェチルエーテル、モノプロピルエーテル、モノブチルエーテルまたは モノフエ-ルエーテルなどの多価アルコール類およびその誘導体；ジォキサンのよう な環式エーテル類；、乳酸メチル、乳酸ェチル (EL)、酢酸メチル、酢酸ェチル、酢酸 ブチル、ピルビン酸メチル、ピルビン酸ェチル、メトキシプロピオン酸メチル、エトキシ プロピオン酸ェチルなどのエステル類などを挙げることができる。  For example, γ-latatones such as butyrolatatatone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, ethylene glycolol monoacetate, diethylene glycol, diethylene glycololmonomonoacetate , Propylene glycol, propylene glycol monoacetate, dipropylene glycol, or dipropylene glycol monoacetate, or polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and their derivatives Cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate , It may be mentioned Echiru pyruvate, methyl methoxypropionate, and esters such as Echiru ethoxy propionate.
これらの有機溶剤は単独で用いてもよぐ 2種以上の混合溶剤として用いてもょ 、。 また、（S)成分として、プロピレングリコールモノメチルエーテルアセテート（PGME A)と極性溶剤とを混合した混合溶媒も好ましい。その配合比（質量比）は、 PGMEA と極性溶剤との相溶性等を考慮して適宜決定すればよいが、好ましくは 1 : 9〜9 : 1、 より好ましくは 2： 8〜8： 2の範囲内とすることが好まし 、。 These organic solvents can be used alone or as a mixed solvent of two or more. Further, as the component (S), a mixed solvent obtained by mixing propylene glycol monomethyl ether acetate (PGME A) and a polar solvent is also 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. Preferably within the range.
より具体的には、極性溶剤として ELを配合する場合は、 PGMEA :ELの質量比が 好ましくは 1： 9〜9： 1、より好ましくは 2： 8〜8： 2であると好まし!/、。  More specifically, when EL is added as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. ,.
また、（S)成分として、その他には、 PGMEA及び ELの中カゝら選ばれる少なくとも 1 種と γ—プチ口ラタトンとの混合溶剤も好ましい。この場合、混合割合としては、前者 と後者の質量比が好ましくは 70： 30-95 : 5とされる。  In addition, as the component (S), a mixed solvent of at least one selected from among PGMEA and EL and γ-petit-mouth rataton is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70: 30-95: 5.
(S)成分の使用量は特に限定しないが、基板等に塗布可能な濃度で、塗布膜厚に 応じて適宜設定されるものである力 一般的にはレジスト組成物の固形分濃度 2〜2 0質量％、好ましくは 5〜15質量％の範囲内となる様に用いられる。  The amount of component (S) used is not particularly limited, but it is a concentration that can be applied to a substrate, etc., and can be appropriately set according to the coating film thickness. Generally, the solid content concentration of the resist composition is 2 to 2. It is used so as to be in the range of 0% by mass, preferably 5 to 15% by mass.
<第五の実施形態のレジストパターン形成方法 > <Method for Forming Resist Pattern of Fifth Embodiment>
上記第四の実施形態のポジ型レジスト組成物は、該第四の実施形態のポジ型レジ スト組成物を用いて基板上にレジスト膜を形成する工程、前記レジスト膜を露光する 工程、および前記レジスト膜を現像してレジストパターンを形成する工程を含むレジス トパターン形成方法 (第五の実施形態のレジストパターン形成方法）に使用できる。 該レジストパターン形成方法は、たとえば以下のようにして実施できる。  The positive resist composition of the fourth embodiment includes a step of forming a resist film on a substrate using the positive resist composition of the fourth embodiment, a step of exposing the resist film, and the step of It can be used for a resist pattern forming method (resist pattern forming method of the fifth embodiment) including a step of developing a resist film to form a resist pattern. The resist pattern forming method can be performed, for example, as follows.
すなわち、まずシリコンゥエーハのような基板上に、上記第四の実施形態のポジ型 レジスト組成物をスピンナーなどで塗布し、任意にプレベータ（ΡΑΒ)を施してレジス ト膜を形成する。形成されたレジスト膜を、例えば ArF露光装置、電子線描画装置、 EUV露光装置等の露光装置を用いて、マスクパターンを介した露光、またはマスク ノ ターンを介さない電子線の直接照射による描画等により選択的に露光した後、 PE B (露光後加熱）を施す。続いて、アルカリ現像液を用いて現像処理した後、リンス処 理を行って、基板上の現像液および該現像液によって溶解したレジスト組成物を洗 い流し、乾燥させて、レジストパターンを得る。  That is, first, the positive resist composition of the fourth embodiment is applied onto a substrate such as a silicon wafer with a spinner or the like, and optionally subjected to pre-beta (ΡΑΒ) to form a resist film. The formed resist film is exposed through a mask pattern using an exposure apparatus such as an ArF exposure apparatus, an electron beam drawing apparatus, or an EUV exposure apparatus, or drawn by direct irradiation of an electron beam without using a mask pattern. After selective exposure with PEB (post-exposure heating). Subsequently, after developing with an alkali developer, rinsing is performed, and the developer on the substrate and the resist composition dissolved by the developer are washed away and dried to obtain a resist pattern.
これらの工程は、周知の手法を用いて行うことができる。操作条件等は、使用する ポジ型レジスト組成物の組成や特性に応じて適宜設定することが好ましい。 露光光源は、特に限定されず、 ArFエキシマレーザー、 KrFエキシマレーザー、 F These steps can be performed using a known method. The operating conditions and the like are preferably set as appropriate according to the composition and characteristics of the positive resist composition to be used. The exposure light source is not particularly limited. ArF excimer laser, KrF excimer laser, F
2 エキシマレーザー、 EUV (極紫外線）、 VUV (真空紫外線）、電子線、 X線、軟 X線な どの放射線を用いて行うことができる。特に、上記ポジ型レジスト組成物は、 ArFェキ シマレーザー、電子線または EUV、特に ArFエキシマレーザーまたは電子線に対し て有効である。  2 Can be performed using radiation such as excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), electron beam, X-ray, soft X-ray. In particular, the positive resist composition is effective for ArF excimer laser, electron beam or EUV, particularly ArF excimer laser or electron beam.
なお、場合によっては、上記アルカリ現像後ポストベータ工程を含んでもよいし、基 板とレジスト膜との間には、有機系または無機系の反射防止膜を設けてもよい。  In some cases, a post-beta step after the alkali development may be included, and an organic or inorganic antireflection film may be provided between the substrate and the resist film.
[0124] <溶解抑制剤 > [0124] <Dissolution inhibitor>
上記低分子化合物 (A1)は、ポジ型レジスト組成物用の溶解抑制剤としても好適に 用いることができる。上記低分子化合物 (A1)力もなる溶解抑制剤を用いることにより 、該溶解抑制剤を含有するポジ型レジスト組成物を用いて得られるレジスト膜 (露光 前)のアルカリ溶解性が抑制される。そのため、該レジスト膜を選択的に露光した際に 、露光部と未露光部との間のアルカリ溶解性の差 (溶解コントラスト）が大きくなり、解 像性や形状が良好なレジストパターンが形成できる。  The low molecular compound (A1) can also be suitably used as a dissolution inhibitor for a positive resist composition. By using a dissolution inhibitor that also has the low molecular compound (A1) power, the alkali solubility of the resist film (before exposure) obtained using the positive resist composition containing the dissolution inhibitor is suppressed. Therefore, when the resist film is selectively exposed, the difference in alkali solubility (dissolution contrast) between the exposed portion and the unexposed portion is increased, and a resist pattern with good resolution and shape can be formed. .
かかる溶解抑制剤は、酸解離性溶解抑制基を有する榭脂成分と酸発生剤成分とを 含む 2成分系の化学増幅型レジスト組成物に添加して用いることができ、また、酸解 離性溶解抑制基を有さな ヽ榭脂成分と酸発生剤成分と溶解抑制剤とを用いる、 Vヽゎ ゆる 3成分系の化学増幅型のレジスト組成物としても用いることができる。  Such a dissolution inhibitor can be used by being added to a two-component chemically amplified resist composition containing a resin component having an acid dissociable dissolution inhibiting group and an acid generator component. It can also be used as a V-type three-component chemically amplified resist composition using a resin component, an acid generator component and a dissolution inhibitor that do not have a dissolution inhibitor group.
[0125] 《第六の実施形態の化合物〉〉 [0125] << Compound of Sixth Embodiment >>
本発明の第六の実施形態の化合物（以下、化合物 (I) 'という。）は、上記一般式 (I ) 'で表されるように、トリフエ-ルメタン骨格のフエニル基の 2つに水酸基と R11と R12と が結合し、残りの 1つのフエ-ル基に、カルボキシ基（― COOH)、および任意に R13 が結合した構造を有するトリス (ヒドロキシフエニル)メタン誘導体である。 The compound of the sixth embodiment of the present invention (hereinafter referred to as compound (I) ′) has a hydroxyl group in two of the phenyl groups of the trimethane skeleton, as represented by the general formula (I) ′. This is a tris (hydroxyphenyl) methane derivative having a structure in which R 11 and R 12 are bonded, and the remaining one group is bonded to a carboxy group (—COOH) and optionally R 13 .
[0126] 一般式 (I)，中、 RU〜R13は、上記第一の実施形態の一般式 (I)中の RU〜R13と同 様である。 In general formula (I), R U to R 13 are the same as R U to R 13 in general formula (I) of the first embodiment.
[0127] pは 1または 2である。本発明においては、特に、該化合物を用いて製造される化合 物がレジスト組成物用として好適であるため、 pが 1であることが好ましい。すなわち、 化合物 (I) 'は、下記一般式 (I 1) 'で表される化合物であることが好ましい。 [0128] [化 32] [0127] p is 1 or 2. In the present invention, it is particularly preferable that p is 1 because a compound produced using the compound is suitable for a resist composition. That is, the compound (I) ′ is preferably a compound represented by the following general formula (I 1) ′. [0128] [Chemical 32]
Figure imgf000050_0001
Figure imgf000050_0001
13  13
[式（I— 1)，中、 RU〜R , s, t, u, qは、式（I)，中の RU〜R", S, t, u, qと同様であ る。]  [Formula (I-1), where RU to R, s, t, u, q are the same as RU to R ", S, t, u, q in Formula (I)].
[0129] qは 0〜2の整数であり、好ましくは 0または 1であり、最も好ましくは 0である。  [0129] q is an integer of 0 to 2, preferably 0 or 1, and most preferably 0.
カルボキシ基の結合位置は、特に限定されないが、得られる化合物を用いて製造 される化合物がレジスト組成物用として好適であること、合成しやすさ等の点で、少な くとも 1つ力 フエ-ル基のパラ位 (4位）に結合していることが好ましい。  The bonding position of the carboxy group is not particularly limited, but at least one of the strengths of the compound produced using the obtained compound is suitable for the resist composition and the ease of synthesis. It is preferably bonded to the para position (position 4) of the ru group.
R13の結合位置は、特に限定されないが、合成のしゃすさ等の点で、カルボキシァ ルキルォキシ基が結合した炭素原子に隣接する炭素原子の少なくとも一方に結合し ていることが好ましい。 The bonding position of R 13 is not particularly limited, but is preferably bonded to at least one of the carbon atoms adjacent to the carbon atom to which the carboxyalkyloxy group is bonded, from the viewpoint of synthesis.
[0130] sは 1〜2の整数であり、好ましくは 1である。 [0130] s is an integer of 1 to 2, preferably 1.
tは 1〜3の整数であり、好ましくは 1または 2であり、最も好ましくは 1である。 uは 1〜3の整数であり、好ましくは 1または 2であり、最も好ましくは 1である。 s+t+uは 3〜5の整数であり、好ましくは 3または 4であり、最も好ましくは 3である。 水酸基の結合位置は、特に限定されないが、得られる化合物を用いて製造される 化合物がレジスト組成物用として好適であること、合成しやすさ等の点で、少なくとも 1 つ力 フエ-ル基のパラ位 (4位）に結合していることが好ましい。  t is an integer of 1 to 3, preferably 1 or 2, and most preferably 1. u is an integer of 1 to 3, preferably 1 or 2, and most preferably 1. s + t + u is an integer of 3 to 5, preferably 3 or 4, and most preferably 3. The bonding position of the hydroxyl group is not particularly limited, but the compound produced using the obtained compound is suitable for a resist composition and has at least one force group in view of ease of synthesis. It is preferably bonded to the para position (position 4).
RU〜R12の結合位置は、特に限定されないが、合成のしゃすさ等の点で、水酸基 が結合した炭素原子に隣接する炭素原子の少なくとも一方に、 R11または R12が結合 していることが好ましぐ特に、水酸基が結合した炭素原子に隣接する炭素原子の両 方に R11または R12が結合して 、ることが好まし!/、。 The bonding position of R U to R 12 is not particularly limited, but R 11 or R 12 is bonded to at least one of the carbon atoms adjacent to the carbon atom to which the hydroxyl group is bonded, in terms of synthesis and the like. In particular, R 11 or R 12 is preferably bonded to both carbon atoms adjacent to the carbon atom to which the hydroxyl group is bonded! /.
[0131] 本発明の化合物 (I) 'としては、特に、下記一般式 (Π) 'で表される化合物が、該化 合物を用いて製造される化合物がレジスト組成物用として好適であるため好ましい。 [0131] As the compound (I) 'of the present invention, in particular, a compound represented by the following general formula (Π)', and a compound produced by using the compound are suitable for resist compositions. Therefore, it is preferable.
[0132] [化 33] [0132] [Chemical 33]
Figure imgf000051_0001
Figure imgf000051_0001
[式 (Π)，中、 R"〜R "はそれぞれ独立して炭素数 1〜： LOのアルキル基であり； pは 1 または 2である。 ] [In the formula (Π), R "to R" are each independently an alkyl group having 1 to C: LO; p is 1 or 2. ]
[0133] 式 (II)，中、 RU〜R12および pは式 (I)，中の RU〜R12および pと同様である。 [0133] Formula (II), in, R U to R 12 and p are the same as R U to R 12 and p in formula (I),.
なかでも、 pが 1である化合物が好ましぐ特に、カルボキシ基が当該フヱ-ル基の パラ位に結合した下記一般式 (II—1) 'で表される化合物が好ましい。  Among these, a compound having p of 1 is preferable, and a compound represented by the following general formula (II-1) ′ in which a carboxy group is bonded to the para position of the phenyl group is preferable.
[0134] [化 34] [0134] [Chemical 34]
Figure imgf000052_0001
'·' ( I【一 Π
Figure imgf000052_0001
'·' (I
[式中、 R"〜R はそれぞれ独立して炭素数 1〜： LOのアルキル基である。 ] [Wherein R ″ to R are each independently an alkyl group having 1 to carbon atoms: LO.]
[0135] 式 (Π) 'で表される化合物としては、特に、合成しやすさ等の点で、下記一般式 (II[0135] As the compound represented by the formula (Π) ', the following general formula (II)
— 2) 'または (Π— 3) 'で表される化合物が好ましい。 — 2) A compound represented by 'or (Π— 3)' is preferred.
[0136] [化 35] [0136] [Chemical 35]
Figure imgf000052_0002
Figure imgf000052_0002
[式中、 R"〜R はそれぞれ独立して炭素数 1〜： L0のアルキル基であり、 pは 1また は 2である。 ] [0137] 化合物 (I)，は、置換基 Rn〜R13の種類を選択することにより、種々の特性、たとえ ばアルカリ溶解性等を調節することができる。たとえば、上記式 (Π) '中の、フエノール 性水酸基のオルト位に結合した置換基 R11がシクロへキシル基等の嵩高い基である 化合物は、他の構造が同じであって、 R11がメチル基等の嵩高くない基である化合物 に比べ、アルカリ溶解性が小さい。このように、化合物 (I)，のアルカリ溶解性を調節 することにより、たとえば後述するような、当該化合物 (I) 'を用いて得られる低分子化 合物 (A1) 'のアルカリ溶解性を調節することができる。つまり、低分子化合物 (A1) ' を含有するポジ型レジスト組成物のアルカリ現像液に対する溶解性を調節することが できる。 [Wherein R ″ to R are each independently an alkyl group having 1 to C0 carbon atoms, and p is 1 or 2.] [0137] Compound (I), is, by selecting the type of the substituents R n to R 13, various characteristics, it is possible to adjust the alkali solubility and the like, for example. For example, the compound in which the substituent R 11 bonded to the ortho position of the phenolic hydroxyl group in the above formula (Π) ′ is a bulky group such as a cyclohexyl group has the same structure, and R 11 Compared with a compound in which is a non-bulky group such as a methyl group, the alkali solubility is small. Thus, by adjusting the alkali solubility of the compound (I), the alkali solubility of the low molecular weight compound (A1) ′ obtained by using the compound (I) ′ as described later, for example, can be increased. Can be adjusted. That is, the solubility of the positive resist composition containing the low molecular compound (A1) ′ in an alkaline developer can be adjusted.
[0138] 化合物 (I) 'は、従来公知の方法を適用することにより製造できる。また、下記本発 明の化合物 (I) 'の製造方法に示すように、置換基を有して 、てもよ 、カルボキシべ ンズアルデヒドと、置換基を有するフエノールイ匕合物とを、酸性条件下で反応 (脱水 縮合)させること〖こより製造できる。  [0138] Compound (I) 'can be produced by applying a conventionally known method. Further, as shown in the following production method of the compound (I) ′ of the present invention, a carboxybenzaldehyde having a substituent and a phenol compound having a substituent may be subjected to acidic conditions. It can be produced from coconut paste by reaction (dehydration condensation) below.
[0139] 《第七の実施形態の化合物 (I) 'の製造方法〉〉 << Method for Producing Compound (I) 'of Seventh Embodiment >>
本発明の第七の実施形態の化合物 (I) 'の製造方法は、上記一般式（1) 'で表され る化合物（1) 'と上記一般式 (2) 'で表される化合物（2) 'とを酸性条件下で反応させ て本発明の化合物 (I) 'を得る工程 (以下、化合物 (I) '形成工程という）を有する。  The production method of the compound (I) ′ according to the seventh embodiment of the present invention includes the compound (1) ′ represented by the general formula (1) ′ and the compound (2) ′ represented by the general formula (2) ′. ) And reacting under acidic conditions to obtain compound (I) ′ of the present invention (hereinafter referred to as compound (I) ′ forming step).
[0140] <化合物 (I) '形成工程 > [0140] <Compound (I) 'Formation process>
一般式（1)，、 (2)，中の RU〜R13、 s、 t、 u、 q、 pは、上記一般式 (I)，中の RU〜R13 、 s、 t、 u、 q、 pと同様である。 Formula (1) ,, (2), R U ~R 13, s in, t, u, q, p, the above general formula (I), R U ~R 13 , s in, t, u Same as q, p.
化合物（1) 'と化合物（2) 'との反応は、酸性条件下で行われる。これにより、化合 物（1) 'のホルミル基（一 CHO)と化合物（2) 'とが反応し、化合物 (I) 'が形成される。 具体的には、例えば、化合物（1) 'をメタノール等の有機溶剤に溶解し、該溶液中 に、化合物（1) 'に対して約 2当量倍の化合物（2) 'を添加し、さらに塩酸等の酸を添 カロすること〖こより反応させることができる。  The reaction between compound (1) ′ and compound (2) ′ is carried out under acidic conditions. As a result, the formyl group (one CHO) of compound (1) ′ reacts with compound (2) ′ to form compound (I) ′. Specifically, for example, compound (1) ′ is dissolved in an organic solvent such as methanol, and about 2 equivalents of compound (2) ′ is added to compound (1) ′. By adding an acid such as hydrochloric acid, the reaction can be carried out.
[0141] このとき使用する有機溶剤としては、化合物（1) '〜（2) 'を溶解するものであればよ ぐ一般的な有機溶剤力 任意のものを選択すればよぐたとえばメタノール、ェタノ ール等の炭素数 1〜4のアルコール、テトラヒドロフラン (THF)等が挙げられる。これ らの有機溶剤は、いずれカゝ 1種を単独で用いてもよぐ 2種類以上混合して用いても よい。 [0141] The organic solvent used at this time may be any organic solvent that can dissolve the compounds (1) 'to (2)'. Any organic solvent may be selected. For example, methanol, ethano C1-C4 alcohol such as alcohol, tetrahydrofuran (THF) and the like. this Any of these organic solvents may be used alone or in admixture of two or more.
このとき使用する酸としては、化合物（1) 'と化合物（2) 'との反応を生じさせるもの であれば特に制限はない。好ましくは塩酸 (塩ィヒ水素水溶液）、硫酸、無水硫酸、 p —トルエンスルホン酸、メタンスルホン酸、トリフルォロメタンスルホン酸、シユウ酸、ギ 酸、リン酸、トリクロ口酢酸、トリフルォロ酢酸等を好ましい具体例として挙げることがで きる。特に、塩酸が好ましく用いられる。これらの酸は、いずれ力 1種を単独で用いて もよぐ 2種類以上混合して用いてもよい。  The acid used at this time is not particularly limited as long as it causes a reaction between compound (1) ′ and compound (2) ′. Preferred are hydrochloric acid (aqueous salt hydrogen chloride solution), sulfuric acid, sulfuric anhydride, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid, etc. Specific examples can be given. In particular, hydrochloric acid is preferably used. Any one of these acids may be used alone, or two or more of these acids may be used in combination.
酸の添加量は、化合物（1) 'と化合物（2) 'との反応を生じさせる量であればよぐ例 えば、 35%質量塩酸の場合は、化合物（1) ' 100質量部に対して、好ましくは 1〜70 0質量部、より好ましくは 100〜600質量部の範囲で用いられる。  The acid may be added in an amount that causes a reaction between compound (1) ′ and compound (2) ′. For example, in the case of 35% by mass hydrochloric acid, compound (1) ′ is added to 100 parts by mass. The amount is preferably 1 to 700 parts by mass, more preferably 100 to 600 parts by mass.
反応温度は、 20〜80°Cが好ましぐ 30〜65°Cがより好ましい。  The reaction temperature is preferably 20 to 80 ° C, more preferably 30 to 65 ° C.
反応時間は、 2〜96時間が好ましぐ 5〜72時間がより好ましい。  The reaction time is preferably 2 to 96 hours, more preferably 5 to 72 hours.
[0142] 反応終了後、反応液に水酸ィ匕ナトリウム等の塩基を添加して、反応液中の酸を中 和する。このとき、たとえば反応液に用いる有機溶剤としてメタノール等のアルコール を用いた場合、カルボキシ基が該アルコールにより若干エステルイ匕して 、る場合があ る。そのため、エステルを加水分解させるために、過剰の塩基をカ卩えることが好ましい このようにして得られる反応液中には、化合物 (I) 'が、塩となって溶解している。そ のため、たとえば反応液を分液ロートに移し、水 Zジェチルエーテル等で洗浄して原 料 (反応に用いたィ匕合物等）を除去し、次いで水層を抜き取り、塩酸水溶液で中和す ると、沈殿が生じる。この沈殿物をろ過等によって回収することにより、化合物 (I) 'が 得られる。 [0142] After completion of the reaction, a base such as sodium hydroxide or sodium hydroxide is added to the reaction solution to neutralize the acid in the reaction solution. At this time, for example, when an alcohol such as methanol is used as the organic solvent used in the reaction solution, the carboxy group may be slightly esterified by the alcohol. Therefore, in order to hydrolyze the ester, it is preferable to remove an excess base. In the reaction solution thus obtained, compound (I) ′ is dissolved as a salt. Therefore, for example, the reaction solution is transferred to a separatory funnel and washed with water Z-jetyl ether to remove the raw materials (compounds used in the reaction, etc.), and then the aqueous layer is taken out and washed with an aqueous hydrochloric acid solution. When neutralized, precipitation occurs. By collecting this precipitate by filtration or the like, compound (I) ′ can be obtained.
このようにして得られる化合物 (I) 'に対して、さらに、水洗浄、再沈等の精製処理を 行ってもよい。  The compound (I) ′ thus obtained may be further subjected to purification treatment such as washing with water and reprecipitation.
[0143] <第八の実施形態の低分子化合物 > <Low Molecular Compound of Eighth Embodiment>
上記本発明の化合物 (I) 'は、レジスト組成物用としての利用が可能な低分子化合 物の製造に好適に使用できる。 たとえば、上記一般式 (I 1) 'で表される化合物（以下、化合物 (I 1) 'という。）は 、下記一般式 (A— 1) 'または (A— 2) 'で表される低分子化合物 (A1) 'の製造に好 適に使用できる。 The compound (I) ′ of the present invention can be suitably used for the production of a low molecular weight compound that can be used for a resist composition. For example, a compound represented by the above general formula (I 1) ′ (hereinafter referred to as compound (I 1) ′) is a low compound represented by the following general formula (A—1) ′ or (A—2) ′. It can be suitably used for the production of molecular compound (A1) '.
[化 36]  [Chemical 36]
Figure imgf000055_0001
Figure imgf000055_0001
[式中、 〜 ， R5〜R8はそれぞれ独立して水素原子、ハロゲン原子、アルキル基 またはハロゲンィ匕アルキル基であり； R3，〜R4 ' , R9，〜R10，はそれぞれ独立して下 記一般式 (I 11) 'で表される基であり； 1, m, Ι' , m，はそれぞれ独立して 1〜3の整 数であり； n, n，は 1〜3の整数であり； Yは（n+ 1)価の有機基であり； Zは（n， + 1)価 の有機基である。 ] [In the formula, ˜, R 5 ˜R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group or a halogenoalkyl group; R 3 , ˜R 4 ′, R 9 , ˜R 10 , are each independently In the following general formula (I 11) ′, 1, m, Ι ′ and m are each independently an integer of 1 to 3; n, n and 1 to 3 Y is an (n + 1) valent organic group; Z is an (n, +1) valent organic group. ]
[0145] [化 37] [0145] [Chemical 37]
Figure imgf000055_0002
( I一 1 1 )
Figure imgf000055_0002
(I 1 1 1)
[式中、 1〜!^13, s, t, u, qは式（I)，中の Rn〜R13, s, t, u, qと同様である。 ] [0146] 低分子化合物 (A1) 'は、上記のような構造を有することにより、たとえばポジ型レジ スト組成物に酸発生剤成分とともに配合された場合、露光により酸発生剤成分から発 生した酸の作用により、 R3，〜R4，および R9，〜R1G，に隣接するカルボ-ル基の炭 素原子に結合した酸素原子と、該酸素原子に結合した炭素原子 ( 〜 、 R5〜R8 等が結合した炭素原子)との間の結合が切れて分解する。この分解により、分子量が 小さくなると同時に R3'— COOH、 R4'— COOH等のカルボン酸 (すなわち化合物（I ) '、さらに具体的には化合物 (I 1) ' )が分解物として生じるため、レジストの露光部 分においてアルカリ可溶性が増大する。そのため、アルカリ現像を行うことによりポジ 型のレジストパターンが形成できる。 [Where 1 to! ^ 13 , s, t, u, q are the same as R n to R 13 , s, t, u, q in equation (I). [0146] The low molecular weight compound (A1) 'has the structure as described above. For example, when it is blended with the acid generator component in a positive resist composition, it is generated from the acid generator component by exposure. Carbon group carbon adjacent to R 3 , ~ R 4 , and R 9 , ~ R 1G The bond between the oxygen atom bonded to the elementary atom and the carbon atom bonded to the oxygen atom (˜, R 5 to R 8 etc. bonded) is broken and decomposed. As a result of this decomposition, the molecular weight is reduced, and at the same time, carboxylic acids such as R 3 '—COOH and R 4 ' —COOH (that is, compound (I) ', more specifically compound (I 1)') are generated as decomposition products. In addition, alkali solubility increases in the exposed portion of the resist. Therefore, a positive resist pattern can be formed by performing alkali development.
このとき、分解物としては、たとえば上記一般式 (A—1) 'で表される化合物の場合 、末端部分が分解して生じる（n+ 1)個のカルボン酸（1個の R3'— COOHおよび n 個の R4'— COOH)と、中心部分 (Y等を含む部分）に由来する 1個の化合物が生じ ると考えられる。また、上記一般式 (A— 2) 'で表される化合物の場合、末端部分が分 解して生じる（n， + 1)個のカルボン酸（1個の R9'— COOHおよび n，個の R1G，—CO OH)と、中心部分 (Z等を含む部分）に由来する 1個の化合物が生じると考えられる。 At this time, as the degradation product, for example 'the case of the compound represented by the results distal portion is decomposed (n + 1) number of carboxylic acid (1 R 3' the general formula (A-1) - COOH And n R 4 '—COOH) and one compound derived from the central part (the part including Y, etc.). Also, 'if the compound represented by the results terminal portion with decomposition (n, + 1) number of carboxylic acid (1 R 9' the general formula (A- 2) - COOH and n, pieces R 1G , —CO OH) and one compound derived from the central part (the part including Z, etc.)
[0147] 一般式 (A— 1)，中、 〜 は、前記一般式 (A— 1)中の I^〜R2と同様である。 [0147] Formula (A- 1), in ~ is the same as the I ^ to R 2 in the general formula (A- 1) in.
[0148] R3'〜R4，は、それぞれ独立に一般式 (1—11)，で表される基であり、一般式 (1—1 1)，中の 1〜!^13, s, t, u, qは式（I)，中の 1〜!^13, s, t, u, qと同様である。 [0148] R 3 'to R 4 are each independently a group represented by general formula (1-11), and 1 to! ^ 13 , s, in general formula (1-11-1) t, u, q are the same as in formula (I), 1 to! ^ 13 , s, t, u, q.
R3，〜R4，は、それぞれ同一であっても異なっていてもよいが、合成のしゃすさの 点で、同一であることが好ましい。 R 3 to R 4 may be the same or different from each other, but are preferably the same in terms of synthesis.
[0149] 1, mはそれぞれ独立して 1〜3の整数であり、好ましくは 1または 2であり、最も好まし くは 1である。 [0149] 1, m are each independently an integer of 1 to 3, preferably 1 or 2, and most preferably 1.
nは 1〜3の整数であり、好ましくは 1または 2であり、最も好ましくは 1である。 なお、 nが 2以上の整数である場合、つまり化合物 (A1)，が、 R4' -COO- [C (R2 n is an integer of 1 to 3, preferably 1 or 2, and most preferably 1. In addition, when n is an integer of 2 or more, that is, the compound (A1), R 4 '-COO- [C (R 2
) H] O で表される基を 2以上有する場合、これらは相互に同一であってもよぐ 相互に異なっていてもよい。 ) When two or more groups represented by H] O are present, these may be the same as each other or different from each other.
[0150] Yは (n+ 1)価の有機基であり、前記一般式 (A— 1)中の Yと同様の（n+ 1)価の有 機基が挙げられる。 [0150] Y is an (n + 1) -valent organic group, and includes the same (n + 1) -valent organic group as Y in the general formula (A-1).
[0151] 一般式 (A— 2)，中、 R5〜R8のアルキル基、ハロゲン化アルキル基としては、一般 式 (A— 1)又は一般式 (A— 1)，における！^1〜!^2のアルキル基、ハロゲン化アルキル 基と同様のものが挙げられる。 R9，〜R1g，としては、上記一般式 (A— 1)，における R3，〜R4，と同様のものが挙げ られる。 [0151] In general formula (A-2), the alkyl group and halogenated alkyl group of R 5 to R 8 are represented by general formula (A-1) or general formula (A-1)! Examples include the same alkyl groups and halogenated alkyl groups as ^ 1 to! ^ 2 . Examples of R 9 to R 1g include the same as R 3 to R 4 in the general formula (A-1).
、 m，、 n，、 Zとしては、それぞれ、一般式 (A— 1)，中の 1、 m、 n、 Yと同様のものが 挙げられる。  , M, n, and Z are the same as those in general formula (A-1), 1, m, n, and Y, respectively.
[0152] 低分子化合物 (A1)，は、その ，と R4'との間、または R9'と R1G，との間の鎖の構造 [0152] Low molecular weight compound (A1) has a chain structure between, and R 4 'or between R 9 ' and R 1G
(長さや分岐の度合い等)を調節することにより、種々の特性、たとえばガラス転移点（ Tg)等を調節することができる。たとえば、 nまたは nが 1である場合 (鎖が直鎖状で ある場合)、鎖の長さが短い (炭素数が少ない)化合物ほど、 Tgは低くなる。  Various characteristics such as glass transition point (Tg) can be adjusted by adjusting (length, degree of branching, etc.). For example, if n or n is 1 (the chain is linear), the shorter the chain length (the fewer the carbons), the lower the Tg.
[0153] 低分子化合物 (A1) 'は、第 3の実施形態の低分子化合物 (A1)と同様に、スピンコ ート法によりアモルファス (非晶質)な膜を形成しうる材料である。  [0153] The low molecular compound (A1) 'is a material capable of forming an amorphous film by the spin coat method, as with the low molecular compound (A1) of the third embodiment.
本発明において、低分子化合物 (A1) 'は、上述のようにして形成されたァモルファ スな膜の安定性が良好であることが好ましぐ例えば上記 PAB (Post Applied Ba ke)後、室温環境下で 2週間放置した後でも、アモルファスな状態が維持されている ことが好ましい。  In the present invention, it is preferable that the low molecular weight compound (A1) ′ has good stability of the amorphous film formed as described above. For example, after the PAB (Post Applied Bake), a room temperature environment is used. It is preferable that the amorphous state is maintained even after being left for 2 weeks.
[0154] 低分子化合物 (A1) 'は、たとえば、 1種または 2種以上の化合物 (I) ' (さらに具体 的には 1種または 2種以上の化合物 (1—1) ' )を、テトラヒドロフラン等の溶媒に溶解し 、トリェチルァミン等の触媒の存在下で、上記一般式 (a— 1)または（a— 2)で表され るビスクロロ化合物と反応させることにより合成できる。  [0154] The low molecular compound (A1) 'is, for example, one or more compounds (I)' (more specifically, one or more compounds (1-1) '), tetrahydrofuran, And can be synthesized by reacting with a bischloro compound represented by the above general formula (a-1) or (a-2) in the presence of a catalyst such as triethylamine.
[0155] 上記低分子化合物 (A1) 'は、酸の作用によりアルカリ可溶性が増大する基材成分  [0155] The low molecular weight compound (A1) 'is a base component whose alkali solubility is increased by the action of an acid.
(A) '、および放射線の照射により酸を発生する酸発生剤成分 (B)を含有するポジ型 レジスト組成物において、前記基材成分 (A) 'として好適に使用できる。  In a positive resist composition containing (A) ′ and an acid generator component (B) that generates an acid upon irradiation with radiation, it can be suitably used as the substrate component (A) ′.
低分子化合物 (A1) 'を含有するポジ型レジスト組成物を用いることにより、高解像 性のレジストパターンを形成できる。また、ラフネスも低減できる。  By using a positive resist composition containing the low molecular compound (A1) ′, a high resolution resist pattern can be formed. In addition, roughness can be reduced.
これは、低分子化合物 (A1) 'の均一性によると推測される。すなわち、レジスト材料 の基材成分として高分子量の重合体 (榭脂)を用いる従来のレジストは、分子量分散 やアルカリ溶解性分散を制御することが難しい。そのため、これらの分散や、その分 子サイズそのものが原因となる LERなどの低減には限界がある。  This is presumed to be due to the uniformity of the low molecular compound (A1) ′. That is, it is difficult to control molecular weight dispersion and alkali-soluble dispersion in conventional resists that use a high molecular weight polymer (resin) as a base material component of the resist material. For this reason, there is a limit to the reduction of LER caused by such dispersion and the molecular size itself.
また、上記問題の解決策として考えられている従来の低分子化合物も、上述した非 特許文献 1, 2等に記載されているように、アルカリ可溶性基を酸解離性溶解抑制基 で保護することから、保護されるアルカリ可溶性基の位置やその保護率などにバラッ キが発生し、結果、その性質にもバラツキが生じて上記と同様の問題が生じる。 一方、本発明の低分子化合物 (A1) 'は、低分子量の非重合体であり、また、従来 化学増幅型ポジ型レジストに用いられている榭脂や、上述した非特許文献 1, 2等で 提案されて!ヽる低分子化合物のように、アルカリ可溶性基を酸解離性溶解抑制基に より保護しなくてよいため、その構造が明確で、分子量にもムラが少ない。そのため、 アルカリ溶解性や親水性 ·疎水性等の性質が均一であり、そのため、均一な性質のレ ジスト膜が形成できる。 In addition, conventional low molecular weight compounds considered as a solution to the above problems are As described in Patent Documents 1 and 2, etc., since the alkali-soluble group is protected with an acid dissociable, dissolution-inhibiting group, variations occur in the position of the alkali-soluble group to be protected and its protection rate. As a result, the properties vary and the same problem as described above occurs. On the other hand, the low molecular weight compound (A1) ′ of the present invention is a low molecular weight non-polymer, and also has been used in conventional chemically amplified positive resists and the above-mentioned non-patent documents 1 and 2 etc. As in the low molecular weight compounds that are proposed, the alkali-soluble groups do not need to be protected by the acid-dissociable, dissolution-inhibiting groups, so the structure is clear and the molecular weight is less uneven. Therefore, properties such as alkali solubility and hydrophilicity / hydrophobicity are uniform, and therefore a resist film with uniform properties can be formed.
そして、該レジスト膜中において、本発明の低分子化合物 (A1) 'は、露光により発 生した酸の作用によって分解して分解物を 2〜4個生じ、アルカリ溶解性が増大する 1S この分解後においても、突出して大きな分子量のものが残らず、相対的に、生じ る分解物の個々の分子量の差が小さくなる。そのため、分解物もレジスト膜中で均一 に分布し、また分解物間のアルカリ現像液に対する溶解挙動の差も小さ ヽ。  In the resist film, the low molecular compound (A1) ′ of the present invention is decomposed by the action of the acid generated by exposure to produce 2 to 4 decomposition products, and the alkali solubility is increased. Later, no large molecular weight remains, and the difference in the individual molecular weights of the resulting degradation products becomes relatively small. For this reason, the decomposed products are evenly distributed in the resist film, and the difference in dissolution behavior in the alkaline developer between the decomposed products is small.
このように、低分子化合物 (A1) 'を用いることにより、露光前、露光後とも均一な性 質のレジスト膜を形成でき、それによつて高解像性のレジストパターンを形成でき、ま た、ラフネスも低減できると推測される。  In this way, by using the low molecular compound (A1) ′, a resist film having a uniform quality can be formed before and after exposure, thereby forming a resist pattern with high resolution. It is estimated that roughness can also be reduced.
さらに、上述したように、低分子化合物 (A1) 'の性質が均一で、均一な性質 (アル カリ性や親水性'疎水性等)のレジスト膜を形成できると考えられることから、低分子化 合物 (A1)，を用いることにより、ディフエタトも低減できる。ここで、ディフエタトとは、例 えば、 KLAテンコール社の表面欠陥観察装置（商品名「KLA」）により、現像後のレ ジストパターンを真上力も観察した際に検知される不具合全般のことである。この不 具合とは、例えば現像後のスカム、泡、ゴミ、レジストパターン間のブリッジ、色むら、 析出物等である。  Furthermore, as mentioned above, the low molecular weight compound (A1) 'has uniform properties, and it is thought that resist films with uniform properties (alkali and hydrophilic' hydrophobic, etc.) can be formed. By using compound (A1), diffetats can be reduced. Here, diffetats are, for example, general defects detected when the resist pattern after development is also observed by the KLA Tencor surface defect observation device (trade name “KLA”). . This defect includes, for example, scum after development, bubbles, dust, bridges between resist patterns, uneven color, and precipitates.
また、低分子化合物 (A1) 'の性質が均一で、有機溶剤等に対する溶解性も均一で あると考えられることから、低分子化合物 (A1) 'を含有するポジ型レジスト組成物の 保存安定性も向上する。  In addition, since the properties of the low molecular compound (A1) 'are uniform and the solubility in organic solvents is considered to be uniform, the storage stability of the positive resist composition containing the low molecular compound (A1)' is also considered. Will also improve.
以下に、低分子化合物 (A1) 'を用いたポジ型レジスト組成物の一実施態様を示す [0157] <第九の実施形態のポジ型レジスト組成物 > An embodiment of a positive resist composition using the low molecular compound (A1) ′ is shown below. <Positive Resist Composition of Ninth Embodiment>
第九の実施形態のポジ型レジスト組成物は、酸の作用によりアルカリ可溶性が増大 する基材成分 (A) ' (以下、（A) '成分という。）、および放射線の照射により酸を発生 する酸発生剤成分 (B) (以下、（B)成分という。）を含有するポジ型レジスト組成物で あって、前記 (A) '成分として一般式 (A— 1) 'または (A— 2) 'で表される低分子化 合物 (A1) 'を含有する。  The positive resist composition of the ninth embodiment generates a base component (A) ′ (hereinafter referred to as (A) ′ component) whose alkali solubility is increased by the action of an acid, and an acid upon irradiation with radiation. A positive resist composition containing an acid generator component (B) (hereinafter referred to as component (B)), wherein the component (A) is represented by the general formula (A-1) 'or (A-2) Contains a low molecular weight compound (A1) represented by '.
(A) '成分および (B)成分を含有するポジ型レジスト組成物においては、露光により 前記 (B)成分から発生した酸が前記 (A)成分に作用すると、 (A) '成分全体がアル カリ不溶性カゝらアルカリ可溶性に変化する。そのため、レジストパターンの形成にお いて、該ポジ型レジスト組成物力もなるレジスト膜を選択的に露光すると、または露光 に加えて露光後加熱すると、露光部はアルカリ可溶性へ転じる一方で未露光部はァ ルカリ不溶性のまま変化しないので、アルカリ現像することによりポジ型のレジストパタ ーンが形成できる。  In the positive resist composition containing the component (A) 'and the component (B), when the acid generated from the component (B) by exposure acts on the component (A) by exposure, the entire component (A)' It changes from alkali-insoluble to alkali-soluble. Therefore, in the formation of the resist pattern, when the resist film having the positive resist composition strength is selectively exposed or heated after exposure in addition to the exposure, the exposed portion turns into alkali-soluble while the unexposed portion becomes Since it remains insoluble in alkali and does not change, a positive resist pattern can be formed by alkali development.
[0158] [ (A) '成分]  [0158] [(A) 'component]
(A) '成分は、上記低分子化合物 (A1) 'を含有する。  (A) 'The component contains the low molecular compound (A1)'.
低分子化合物 (A1) 'は、 1種単独で用いてもよぐ 2種以上を併用してもよい。 The low molecular compound (A1) ′ may be used alone or in combination of two or more.
(A) '成分中、低分子化合物 (A1) 'の割合は、 40質量％超であることが好ましぐ 5(A) The proportion of 'low molecular weight compound (A1)' in the component is preferably more than 40% by mass 5
0質量％超であることがより好ましぐ 80質量％超がさらに好ましぐ最も好ましくは 10More preferably more than 0% by weight More preferably more than 80% by weight is most preferred 10
0質量％である。 0% by mass.
(A) '成分中の低分子化合物 (A1) 'の割合は、逆相クロマトグラフィー等の手段に より測定できる。  (A) The ratio of the “low molecular compound (A1)” in the component can be measured by means such as reverse phase chromatography.
[0159] (A) '成分は、さらに、低分子化合物 (A1) 'を用いることによる効果を損なわない範 囲で、これまで化学増幅型レジスト層の基材成分として提案されて!ヽる任意の榭脂成 分 (以下、（A2)成分と 、うことがある）を含有して!/、てもよ!/、。  [0159] (A) 'Component has been proposed as a base material component of a chemically amplified resist layer so far as it does not impair the effect of using low molecular weight compound (A1)'! Containing a coconut oil component (hereinafter sometimes referred to as component (A2))! /, May! /.
かかる (A2)成分としては、例えば従来の化学増幅型の KrF用ポジ型レジスト組成 物、 ArF用ポジ型レジスト組成物等のベース榭脂として提案されて ヽるものが挙げら れ、レジストパターン形成時に用いる露光光源の種類に応じて適宜選択できる。 [0160] 第九の実施形態のポジ型レジスト組成物中の (A) '成分の含有量は、形成しようと するレジスト膜厚に応じて調整すればょ 、。 Examples of the component (A2) include those proposed as base resins for conventional chemically amplified KrF positive resist compositions, ArF positive resist compositions, and the like. It can be suitably selected according to the type of exposure light source used sometimes. [0160] The content of the component (A) 'in the positive resist composition of the ninth embodiment may be adjusted according to the resist film thickness to be formed.
[0161] [ (B)成分] [0161] [Component (B)]
(B)成分としては、第 4の実施形態のポジ型レジスト組成物で挙げた (B)成分と同 様である。  The component (B) is the same as the component (B) mentioned in the positive resist composition of the fourth embodiment.
上記式 (b—l)中、 Rlw〜R3"は、それぞれ、フエ-ル基またはナフチル基であること が最も好ましい。 In the above formula (b-l), R lw to R 3 ″ are most preferably a phenyl group or a naphthyl group, respectively.
[0162] (B)成分としては、 1種の酸発生剤を単独で用いてもよいし、 2種以上を組み合わ せて用いてもよい。  [0162] As the component (B), one type of acid generator may be used alone, or two or more types may be used in combination.
第九の実施形態のポジ型レジスト組成物における（B)成分の含有量は、 (A) '成分 100質量部に対し、 0. 5〜30質量部が好ましぐ 1〜15質量部がより好ましい。上記 範囲とすることでパターン形成が十分に行われる。また、均一な溶液が得られ、保存 安定性が良好となるため好ま 、。  In the positive resist composition of the ninth embodiment, the content of the component (B) is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the (A) ′ component, and more preferably 1 to 15 parts by mass preferable. Pattern formation is sufficiently performed by setting the above range. In addition, it is preferable because a uniform solution is obtained and storage stability is good.
[0163] [任意成分] [0163] [Optional ingredients]
第九の実施形態のポジ型レジスト組成物には、レジストパターン形状、引き置き経 時安定性などを向上させるために、さらに任意の成分として、含窒素有機化合物 (D) (以下、（D)成分という）を配合させることができる。  In the positive resist composition of the ninth embodiment, a nitrogen-containing organic compound (D) (hereinafter referred to as (D) is further added as an optional component in order to improve the resist pattern shape, the stability over time, and the like. Component)).
この（D)成分は、既に多種多様なものが提案されているので、公知のものから任意 に用いれば良ぐなかでも脂肪族ァミン、特に第 2級脂肪族アミンゃ第 3級脂肪族アミ ンが好ましい。ここで、本請求の範囲及び明細書における「脂肪族」とは、芳香族に 対する相対的な概念であって、芳香族性を持たない基、化合物等を意味するものと 定義する。  Since a wide variety of components (D) have already been proposed, aliphatic amines, particularly secondary aliphatic amines and tertiary aliphatic amines, can be used arbitrarily from known ones. Is preferred. Here, “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.
「脂肪族環式基」は、芳香族性を持たない単環式基または多環式基であることを示す 脂肪族ァミンとしては、アンモニア NHの水素原子の少なくとも 1つを、炭素数 12以  An `` aliphatic cyclic group '' means a monocyclic group or a polycyclic group having no aromaticity. As an aliphatic amine, at least one hydrogen atom of ammonia NH must have at least 12 carbon atoms.
3  Three
下のアルキル基またはヒドロキシアルキル基で置換したァミン（アルキルアミンまたは アルキルアルコールァミン）又は環式ァミンが挙げられる。  Examples include amines substituted with alkyl groups or hydroxyalkyl groups below (alkylamines or alkylalcoholamines) or cyclic amines.
アルキルァミンおよびアルキルアルコールァミンの具体例としては、第四の実施形 態と同様のものが挙げられる。これらの中でも、炭素数 5〜10のトリアルキルァミンが さらに好ましく、トリ一 n—ォクチルァミンが最も好ま 、。 Specific examples of alkylamines and alkyl alcoholamines include the fourth embodiment. The thing similar to a state is mentioned. Among these, trialkylamines having 5 to 10 carbon atoms are more preferable, and tri-n-octylamine is most preferable.
環式ァミンとしては、たとえば、ヘテロ原子として窒素原子を含む複素環化合物が 挙げられる。該複素環化合物としては、単環式のもの (脂肪族単環式ァミン)であって も多環式のもの (脂肪族多環式ァミン)であってもよ 、。  Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound may be monocyclic (aliphatic monocyclic ammine) or polycyclic (aliphatic polycyclic ammine).
脂肪族単環式ァミンとして、具体的には、ピぺリジン、ピぺラジン等が挙げられる。 脂肪族多環式ァミンとしては、炭素数が 6〜 10のものが好ましぐ具体的には、 1, 5 Specific examples of the aliphatic monocyclic amine include piperidine and piperazine. As aliphatic polycyclic amines, those having 6 to 10 carbon atoms are preferred.
—ジァザビシクロ [4. 3. 0]— 5—ノネン、 1, 8—ジァザビシクロ [5. 4. 0]— 7—ゥン デセン、へキサメチレンテトラミン、 1, 4ージァザビシクロ [2. 2. 2]オクタン等が挙げ られる。 —Diazabicyclo [4. 3. 0] — 5—Nonene, 1, 8—Diazabicyclo [5. 4. 0] — 7—Undecene, Hexamethylenetetramine, 1,4-Diazabicyclo [2. 2. 2] Octane Etc.
これらは単独で用いてもょ 、し、 2種以上を組み合わせて用いてもょ 、。 These can be used alone or in combination of two or more.
(D)成分は、（A) '成分 100質量部に対して、通常 0. 01〜5. 0質量部の範囲で用 いられる。 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) ′.
[0164] ポジ型レジスト組成物には、前記 (D)成分の配合による感度劣化の防止、またレジ ストパターン形状、引き置き経時安定性等の向上の目的で、さらに任意の成分として 、第四の実施形態と同様の有機カルボン酸又はリンのォキソ酸若しくはその誘導体（ E) (以下、（E)成分という）を含有させることができる。なお、（D)成分と (E)成分は併 用することもできるし、 、ずれか 1種を用いることもできる。  [0164] In the positive resist composition, for the purpose of preventing sensitivity deterioration due to the blending of the component (D), and improving the resist pattern shape and the stability over time, the fourth component is further added as an optional component. The same organic carboxylic acid or phosphorous oxoacid or 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 of them can be used.
(E)成分は、（A) '成分 100質量部当り 0. 01〜5. 0質量部の割合で用いられる。  Component (E) is used in a proportion of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A) ′.
[0165] 第九の実施形態のポジ型レジスト組成物には、さらに所望により混和性のある添カロ 剤、例えばレジスト膜の性能を改良するための付加的榭脂、塗布性を向上させるた めの界面活性剤、溶解抑制剤、可塑剤、安定剤、着色剤、ハレーション防止剤、染 料などを適宜、添加含有させることができる。 [0165] The positive resist composition of the ninth embodiment further has a miscible additive, for example, an additional resin for improving the performance of the resist film, in order to improve coatability. These surfactants, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes and the like can be added and contained as appropriate.
[0166] 第九の実施形態のポジ型レジスト組成物は、材料を有機溶剤（以下、「（S)，成分」 ということがある。 )に溶解させて製造することができる。 [0166] The positive resist composition of the ninth embodiment can be produced by dissolving the material in an organic solvent (hereinafter, sometimes referred to as "(S), component").
(S) '成分としては、使用する各成分を溶解し、均一な溶液とすることができるもので あればよぐ従来、化学増幅型レジストの溶剤として公知のものの中から任意のものを 1種または 2種以上適宜選択して用いることができる。 例えば、 γ —ブチロラタトン等のラタトン類；アセトン、メチルェチルケトン、シクロへ キサノン、メチルー η—アミルケトン、メチルイソアミルケトン、 2—へプタノンなどのケト ン類；エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレン グリコールなどの多価アルコール類及びその誘導体；エチレングリコールモノァセテ ート、ジエチレングリコールモノアセテート、プロピレングリコールモノアセテート、また はジプロピレングリコールモノアセテート等のエステル結合を有する化合物；前記多 価アルコール類または前記エステル結合を有する化合物のモノメチルエーテル、モ ノエチノレエーテノレ、モノプロピノレエーテノレ、モノブチノレエーテノレ等のモノァノレキノレエ 一テルまたはモノフエ-ルエーテル等のエーテル結合を有する化合物等の多価アル コール類の誘導体；ジォキサンのような環式エーテル類や、乳酸メチル、乳酸ェチル(S) 'As the component, it is sufficient if each component to be used can be dissolved into a uniform solution. Any one of conventionally known solvents for chemically amplified resists can be used. Alternatively, two or more types can be appropriately selected and used. For example, latones such as γ-butyrolatatane; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-η-amyl ketone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol, dipropylene Polyhydric alcohols such as glycol and derivatives thereof; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; the above polyhydric alcohols or the above Monomethyl ether, monoethylenoatenore, monopropinoreatenore, monobutenoleatenore, etc. Hue - polyvalent derivatives of alcohol such as compounds having an ether bond such as ether, cyclic ethers and like Jiokisan, methyl lactate Echiru
(EL)、酢酸メチル、酢酸ェチル、酢酸ブチル、ピルビン酸メチル、ピルビン酸ェチル 、メトキシプロピオン酸メチル、エトキシプロピオン酸ェチルなどのエステル類などを挙 げることがでさる。 (EL), esters such as methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and the like.
これらの有機溶剤は単独で用いてもよぐ 2種以上の混合溶剤として用いてもょ 、。 中でも、プロピレングリコールモノメチルエーテルアセテート（PGMEA)、プロピレン グリコールモノメチルエーテル（PGME)、 ELが好ましい。  These organic solvents can be used alone or as a mixed solvent of two or more. Of these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and EL are preferable.
また、 PGMEAと極性溶剤とを混合した混合溶媒は好ましい。その配合比（質量比 )は、 PGMEAと極性溶剤との相溶性等を考慮して適宜決定すればよいが、好ましく は 1： 9〜9： 1、より好ましくは 2： 8〜8： 2の範囲内とすることが好まし!/、。  A mixed solvent in which PGMEA and a polar solvent are mixed 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. Preferably within range! /.
より具体的には、極性溶剤として ELを配合する場合は、 PGMEA:ELの質量比は 、好ましくは 1 : 9〜9 : 1、より好ましくは 2 : 8〜8： 2である。また、極性溶剤として PGM Eを配合する場合は、 PGMEA: PGMEの質量比は、好ましくは 1： 9〜9： 1、より好ま しくは 2： 8〜8： 2、さらに好ましくは 3： 7〜7： 3である。  More specifically, when EL is blended as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. When PGM E is blended as a polar solvent, the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: Three.
また、（S)，成分として、その他には、 PGMEA及び ELの中力も選ばれる少なくとも 1種と γ—プチ口ラタトンとの混合溶剤も好ましい。この場合、混合割合としては、前 者と後者の質量比が好ましくは 70： 30〜95： 5とされる。  In addition, as the component (S), a mixed solvent of at least one selected from among PGMEA and EL and γ-petit-mouthed ratatones is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70:30 to 95: 5.
(S) '成分の使用量は特に限定しないが、基板等に塗布可能な濃度で、塗布膜厚 に応じて適宜設定されるものであるが、一般的にはレジスト組成物の固形分濃度が 2 〜20質量％、好ましくは 5〜15質量％の範囲内となる様に用いられる。 (S) 'The amount of the component 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. 2 -20% by mass, preferably 5-15% by mass.
[0167] <第十の実施形態のレジストパターン形成方法 > <Resist Pattern Forming Method of Tenth Embodiment>
上記第九の実施形態のポジ型レジスト組成物は、該第九の実施形態のポジ型レジ スト組成物を用いて基板上にレジスト膜を形成する工程、前記レジスト膜を露光する 工程、および前記レジスト膜を現像してレジストパターンを形成する工程を含むレジス トパターン形成方法 (第十の実施形態のレジストパターン形成方法）に使用できる。 該レジストパターン形成方法は、ポジ型レジスト組成物として第九の実施形態のポ ジ型レジスト組成物を用いる以外は第五の実施形態のレジストパターン形成方法と 同様にして実施できる。  The positive resist composition of the ninth embodiment includes a step of forming a resist film on a substrate using the positive resist composition of the ninth embodiment, a step of exposing the resist film, and the It can be used for a resist pattern forming method (resist pattern forming method of the tenth embodiment) including a step of developing a resist film to form a resist pattern. The resist pattern forming method can be carried out in the same manner as the resist pattern forming method of the fifth embodiment except that the positive resist composition of the ninth embodiment is used as the positive resist composition.
[0168] <他の実施形態の溶解抑制剤 > [0168] <Dissolution inhibitor of other embodiment>
上記低分子化合物 (A1) 'は、ポジ型レジスト組成物用の溶解抑制剤としても好適 に用いることができる。上記低分子化合物 (A1) 'からなる溶解抑制剤を用いることに より、該溶解抑制剤を含有するポジ型レジスト組成物を用いて得られるレジスト膜 (露 光前)のアルカリ溶解性が抑制される。そのため、該レジスト膜を選択的に露光した 際に、露光部と未露光部との間のアルカリ溶解性の差 (溶解コントラスト）が大きくなり 、解像性や形状が良好なレジストパターンが形成できる。  The low molecular compound (A1) ′ can also be suitably used as a dissolution inhibitor for positive resist compositions. By using a dissolution inhibitor composed of the low molecular compound (A1) ′, the alkali solubility of a resist film (before exposure) obtained using a positive resist composition containing the dissolution inhibitor is suppressed. The Therefore, when the resist film is selectively exposed, the difference in alkali solubility (dissolution contrast) between the exposed portion and the unexposed portion is increased, and a resist pattern with good resolution and shape can be formed. .
かかる溶解抑制剤は、酸解離性溶解抑制基を有する榭脂成分と酸発生剤成分とを 含む 2成分系の化学増幅型レジスト組成物に添加して用いることができ、また、酸解 離性溶解抑制基を有さな ヽ榭脂成分と酸発生剤成分と溶解抑制剤とを用いる、 Vヽゎ ゆる 3成分系の化学増幅型のレジスト組成物としても用いることができる。  Such a dissolution inhibitor can be used by being added to a two-component chemically amplified resist composition containing a resin component having an acid dissociable dissolution inhibiting group and an acid generator component. It can also be used as a V-type three-component chemically amplified resist composition using a resin component, an acid generator component and a dissolution inhibitor that do not have a dissolution inhibitor group.
実施例  Example
[0169] 以下、本発明の実施例を説明するが、本発明の範囲はこれらの実施例に限定され るものではない。  Examples of the present invention will be described below, but the scope of the present invention is not limited to these examples.
実施例 1 (化合物（5)の合成）  Example 1 (Synthesis of Compound (5))
20gの 4—ヒドロキシベンズアルデヒド（1)に 200gのテトラヒドロフラン (THF)をカロえ 、溶解させた。そこへ 13. 8gの炭酸カリウム (K CO )を加え、 10分間室温で攪拌さ  200 g of tetrahydrofuran (THF) was dissolved in 20 g of 4-hydroxybenzaldehyde (1) and dissolved. Add 13.8 g of potassium carbonate (K 2 CO 3) and stir at room temperature for 10 minutes.
2 3  twenty three
せた。その後、 31. 9gの tert—ブチルブロモアセテート（2)をカ卩え、室温 (r. t)で 12 時間反応させた。 反応終了後、水 Z酢酸ェチル (質量比 ι:ι)で抽出、酢酸ェチル層を減圧濃縮し、Let Thereafter, 31.9 g of tert-butyl bromoacetate (2) was added and reacted at room temperature (r. T) for 12 hours. After completion of the reaction, extraction with water Z ethyl acetate (mass ratio ι: ι), the ethyl acetate layer was concentrated under reduced pressure,
31gの化合物（3)を得た。 31 g of compound (3) was obtained.
[0170] [化 38] [0170] [Chemical 38]
Figure imgf000064_0001
Figure imgf000064_0001
[0171] 10gの化合物（3)に 40gのメタノール（CH OH)を加え、溶解させた。そこへ 12.2 [0171] To 10 g of the compound (3), 40 g of methanol (CH OH) was added and dissolved. There 12.2
3  Three
gの 2, 6—ジメチルフエノール (4)をカ卩え、さらに 40gの 35質量0 /0塩酸水溶液 (HCla q. )を加え、 60°Cで 3日間反応させた。 2 g, 6- dimethyl off Ka卩E enol (4), a further 35 mass 0/0 hydrochloric acid aqueous solution of 40g (HCla q.) was added and allowed to react for 3 days at 60 ° C.
反応終了後、水酸ィ匕ナトリウム水溶液にて中和 (pH試験紙で中性を確認)し、水 Z 酢酸ェチル (質量比 1： 1)にて抽出を行った。酢酸ェチル層を減圧濃縮し、カラムク 口マトグラフィ（充填剤として SiO、展開溶剤としてヘプタン:酢酸ェチル =2:1を使  After completion of the reaction, the solution was neutralized with sodium hydroxide aqueous solution (neutrality was confirmed with a pH test paper) and extracted with water Z ethyl acetate (mass ratio 1: 1). Concentrate the ethyl acetate layer under reduced pressure and use column chromatography (SiO as filler and heptane: ethyl acetate = 2: 1 as developing solvent).
2  2
用）を行うことにより、 目的とする化合物（5)を 15. lg得た。  15 g of the desired compound (5) was obtained.
[0172] [化 39] [0172] [Chemical 39]
Figure imgf000064_0002
Figure imgf000064_0002
[0173] 化合物（5)について、 — NMR (プロトン核磁気共鳴スペクトル）、 IR (赤外吸収ス ベクトル）による分析を行った結果、化合物（5)が下記に示す構造を有することが確 認できた。 [0173] Compound (5) was analyzed by NMR (proton nuclear magnetic resonance spectrum) and IR (infrared absorption vector), and as a result, it was confirmed that compound (5) had the structure shown below. It was.
iH— NMR (重ジメチルスルホキシド（DMSO)、内部標準：テトラメチルシラン、 400 MHz)： δ (ppm)=7.97 brs lH(Ha), 6.95 d 2H(Hb)Jbc = 8.4Hz, 6.7 7 d 2H(Hc)jcb = 8.4Hz, 6.59 s 4H(Hd), 5.13 s lH(He), 4.59 s 2 H(Hf), 2.07 s 12H(HS)。 iH—NMR (deuterated dimethyl sulfoxide (DMSO), internal standard: tetramethylsilane, 400 MHz): δ (ppm) = 7.97 brs lH (H a ), 6.95 d 2H (H b ) Jbc = 8.4 Hz, 6.7 7 d 2H (H c ) jcb = 8.4 Hz, 6.59 s 4H (H d ), 5.13 s lH (H e ), 4.59 s 2 H (H f ), 2.07 s 12H (H S ).
IR:3450、 2921、 1737、 1509、 1488 (cm-1) [0174] [化 40]
Figure imgf000065_0001
IR: 3450, 2921, 1737, 1509, 1488 (cm -1 ) [0174] [Chemical 40]
Figure imgf000065_0001
[0175] 実施例 2 (化合物（7)の合成） [0175] Example 2 (Synthesis of Compound (7))
20gの化合物（3)に 70gのメタノールをカ卩え、溶解させた。そこへ 24.4gの 2, 5— ジメチルフエノール（6)をカ卩え、さらに 105gの 35質量0 /0塩酸水溶液をカ卩え、 60°Cで 3日間反応させた。 70 g of methanol was added to 20 g of compound (3) and dissolved. 2 of 24.4g thereto, 5- dimethyl phenol (6) Ka卩E further Ka卩E 35 mass 0/0 hydrochloric acid aqueous solution 105 g, was reacted for 3 days at 60 ° C.
反応終了後、水酸ィ匕ナトリウム水溶液にて中和 (pH試験紙で中性を確認)し、水 Z 酢酸ェチル (質量比 1： 1)にて抽出を行った。酢酸ェチル層を減圧濃縮し、カラムク 口マトグラフィ（充填剤として SiO、展開溶剤としてヘプタン:酢酸ェチル =2:1を使  After completion of the reaction, the solution was neutralized with sodium hydroxide aqueous solution (neutrality was confirmed with a pH test paper) and extracted with water Z ethyl acetate (mass ratio 1: 1). Concentrate the ethyl acetate layer under reduced pressure and use column chromatography (SiO as filler and heptane: ethyl acetate = 2: 1 as developing solvent).
2  2
用）を行うことにより、 目的とする化合物（7)を 25. lg得た。  To obtain 25. lg of the intended compound (7).
[0176] [化 41] [0176] [Chemical 41]
Figure imgf000065_0002
化合物（7)について、 — NMR、 IRによる分析を行った結果、化合物（7)が下記 に示す構造を有することが確認できた。
Figure imgf000065_0002
Compound (7) was analyzed by NMR and IR. As a result, it was confirmed that compound (7) had the structure shown below.
iH— NMR (重ジメチルスルホキシド（DMSO)、内部標準：テトラメチルシラン、 400 MHz)： δ (ppm)=8.91 s 2H(Ha), 6.91 d 2H(Hb)Jbc = 8.5Hz, 6.83 d 2H(Hc)jcb = 8.5Hz, 6.59 s 2H(Hd), 6.34 s 2H(He), 5.37 s 1H( Hf), 4.64 s 2H(He), 1.98 s 6H(Hh)、 1.93 s 611(1^)。 IR: 3403、 2954、 1747、 1587、 1509 (cm" ) iH—NMR (deuterated dimethyl sulfoxide (DMSO), internal standard: tetramethylsilane, 400 MHz): δ (ppm) = 8.91 s 2H (H a ), 6.91 d 2H (H b ) Jbc = 8.5 Hz, 6.83 d 2H (H c ) jcb = 8.5Hz, 6.59 s 2H (H d ), 6.34 s 2H (H e ), 5.37 s 1H (H f ), 4.64 s 2H (H e ), 1.98 s 6H (H h ), 1.93 s 611 (1 ^). IR: 3403, 2954, 1747, 1587, 1509 (cm ")
[0178] [化 42] [0178] [Chemical 42]
Figure imgf000066_0001
Figure imgf000066_0001
[0179] 実施例 3 (低分子化合物（8)の合成） [0179] Example 3 (Synthesis of Low Molecular Compound (8))
3gの化合物（5)を 25gのテトラヒドロフラン (THF)に溶解し、 lgのトリエチルァミン をカロえて室温で 10分攪拌し、 0. 59gの 1, 2—ビス（クロロメトキシ)エタンを滴下し、 室温で 10時間攪拌した。反応終了後、反応液をろ過し、ろ液を濃縮した後、該濃縮 液を水 Z酢酸ェチル (質量比 1： 1)にて抽出し、酢酸ェチル層を減圧濃縮し、化合物 (8)を 2. 5g得た。  3 g of compound (5) is dissolved in 25 g of tetrahydrofuran (THF), lg of triethylamine is added and stirred at room temperature for 10 minutes, 0.59 g of 1,2-bis (chloromethoxy) ethane is added dropwise, Stir at room temperature for 10 hours. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated. Then, the concentrate was extracted with water Z ethyl acetate (mass ratio 1: 1), the ethyl acetate layer was concentrated under reduced pressure, and compound (8) was obtained. 2. 5g was obtained.
[0180] [化 43]  [0180] [Chemical 43]
Figure imgf000066_0002
化合物（8)について、 H— NMR、 IRによる分析を行った。
Figure imgf000066_0002
Compound (8) was analyzed by 1 H-NMR and IR.
iH— NMR (重ジメチルスルホキシド（DMSO)、内部標準：テトラメチルシラン、 400 MHz)： δ (ppm) = 7. 98 brs 4H (Ha) , 6. 96 d 4H (Hb)J =8. 4Hz, 6. 81 d 4H(HC)J =8.4Hz, 6.59 s 8H(Hd), 5.32 s 4H(He), 5.15 iH—NMR (deuterated dimethyl sulfoxide (DMSO), internal standard: tetramethylsilane, 400 MHz): δ (ppm) = 7.98 brs 4H (H a ), 6. 96 d 4H (H b ) J = 8. 4Hz, 6. 81 d 4H (H C ) J = 8.4Hz, 6.59 s 8H (H d ), 5.32 s 4H (H e ), 5.15
cb  cb
(Hf), 4.77 s 4H(Hg), 3.67 s 4H(Hh), 2.08 s 2411 。 (H f ), 4.77 s 4H (H g ), 3.67 s 4H (H h ), 2.08 s 2411.
IR:3472、 2920、 2877、 1758、 1604、 1509 (cm-1) IR: 3472, 2920, 2877, 1758, 1604, 1509 (cm -1 )
上記の結果から、化合物（8)が下記に示す構造を有することが確認できた。  From the results shown above, it was confirmed that the compound (8) had a structure shown below.
[化 44]  [Chemical 44]
Figure imgf000067_0001
Figure imgf000067_0001
[0183] 実施例 4 (低分子化合物（9)の合成） [0183] Example 4 (Synthesis of Low Molecular Compound (9))
3gの化合物（5)を 25gの THFに溶解し、 lgのトリエチルァミンをカ卩えて室温で 10 分攪拌し、 0.64gの 1, 3—ビス (クロロメトキシ)プロパンを滴下し、室温で 10時間攪 拌した。反応終了後、反応液をろ過し、ろ液を濃縮した後、該濃縮液を水 Z酢酸ヱ チル (質量比 1： 1)にて抽出し、酢酸ェチル層を減圧濃縮し、化合物（9)を 2.4g得 た。  Dissolve 3 g of compound (5) in 25 g of THF, add lg of triethylamine, stir at room temperature for 10 minutes, add dropwise 0.64 g of 1,3-bis (chloromethoxy) propane, and add 10 g at room temperature. Stir for hours. After completion of the reaction, the reaction mixture was filtered and the filtrate was concentrated. The concentrate was extracted with water Z ethyl acetate (mass ratio 1: 1), the ethyl acetate layer was concentrated under reduced pressure, and the compound (9) 2.4g was obtained.
[0184] [化 45]  [0184] [Chemical 45]
Figure imgf000067_0002
化合物（9)について、 H— NMR、 IRによる分析を行った。
Figure imgf000067_0002
Compound (9) was analyzed by 1 H-NMR and IR.
H— NMR (重ジメチルスルホキシド（DMSO)、内部標準：テトラメチルシラン、 400 MHz)： δ (ppm)=7. 98 s 4H(Ha), 6. 95 d 4H(Hb)J =8.4Hz, 6.81 d be H—NMR (Heavy dimethyl sulfoxide (DMSO), internal standard: tetramethylsilane, 400 MHz): δ (ppm) = 7.98 s 4H (H a ), 6.95 d 4H (H b ) J = 8.4 Hz, 6.81 d be
4H(HC)J =8.4Hz, 6. 59 s 8H(Hd), 5. 28 s 4H(He), 5. 14 s 2H(Hf cb 4H (H C ) J = 8.4Hz, 6.59 s 8H (H d ), 5.28 s 4H (H e ), 5.14 s 2H (H f cb
), 4. 75 s 4H(Hg), 3. 58 t 4H(Hh)j =6. 2Hz, 2.09 s 2Α¥ί{ΐΐ) , 1.6 hj ), 4.75 s 4H (H g ), 3.58 t 4H (H h ) j = 6.2 Hz, 2.09 s 2Α ¥ ί {ΐΐ), 1.6 hj
0 quin 2H (Hj) J =6. 2Hz 0 quin 2H (H j ) J = 6.2 Hz
jh  jh
IR:3477、 2950、 1755、 1607、 1509 (cm-1) IR: 3477, 2950, 1755, 1607, 1509 (cm -1 )
上記の結果から、化合物（9)が下記に示す構造を有することが確認できた。 [化 46]  From the results shown above, it was confirmed that the compound (9) had a structure shown below. [Chem 46]
Figure imgf000068_0001
Figure imgf000068_0001
[0187] 実施例 5 (低分子化合物（10)の合成） Example 5 (Synthesis of Low Molecular Compound (10))
3gの化合物（5)を 25gの THFに溶解し、 lgのトリエチルァミンをカ卩えて室温で 10 分攪拌し、 0.89gの 1, 4—ビス（クロロメトキシメチル)シクロへキサンを滴下し、室温 で 10時間攪拌した。反応終了後、反応液をろ過し、ろ液を濃縮した後、該濃縮液を 水 Z酢酸ェチル (質量比 1:1)にて抽出し、酢酸ェチル層を減圧濃縮し、化合物（10 )を 2. 5g得た。  3 g of compound (5) is dissolved in 25 g of THF, lg of triethylamine is added and stirred at room temperature for 10 minutes, 0.89 g of 1,4-bis (chloromethoxymethyl) cyclohexane is added dropwise, Stir at room temperature for 10 hours. After completion of the reaction, the reaction mixture was filtered and the filtrate was concentrated. The concentrate was extracted with water Z ethyl acetate (mass ratio 1: 1), the ethyl acetate layer was concentrated under reduced pressure, and compound (10) was obtained. 2. 5g was obtained.
[0188] [化 47]  [0188] [Chemical 47]
Figure imgf000068_0002
[0189] 化合物（10)について、 H— NMR、 IRによる分析を行った。
Figure imgf000068_0002
[0189] Compound (10) was analyzed by 1 H-NMR and IR.
iH— NMR (重ジメチルスルホキシド（DMSO)、内部標準：テトラメチルシラン、 400 MHz)： δ (ppm)=7.99 s 4H(Ha), 6.96 d 4H(Hb)J =8.4Hz, 6.80 d iH—NMR (deuterium dimethyl sulfoxide (DMSO), internal standard: tetramethylsilane, 400 MHz): δ (ppm) = 7.99 s 4H (H a ), 6.96 d 4H (H b ) J = 8.4 Hz, 6.80 d
be  be
4H(HC)J =8.4Hz, 6.58 s 8H(Hd), 5.30 s 4H(He), 5.15 s 2H(Hf 4H (H C ) J = 8.4Hz, 6.58 s 8H (H d ), 5.30 s 4H (H e ), 5.15 s 2H (H f
cb  cb
), 4.76 s 4H(Hg), 3.26〜3.46 m 4H(Hh), 2.06 s 2^(^), 0.78 〜1.71 m 10H(Hj) ), 4.76 s 4H (H g ), 3.26 to 3.46 m 4H (H h ), 2.06 s 2 ^ (^), 0.78 to 1.71 m 10H (H j )
IR:3476、 2922、 2873、 1756、 1607、 1509 (cm-1) IR: 3476, 2922, 2873, 1756, 1607, 1509 (cm -1 )
上記の結果から、化合物（10)が下記に示す構造を有することが確認できた。  From the results shown above, it was confirmed that the compound (10) had a structure shown below.
[0190] [化 48] [0190] [Chemical 48]
Figure imgf000069_0001
Figure imgf000069_0001
[0191] 実施例 6 (低分子化合物（11)の合成） [0191] Example 6 (Synthesis of low molecular compound (11))
10gの化合物（7)を 75gのテトラヒドロフランに溶解し、 3.04gのトリェチルァミンを 加えて室温で 10分攪拌し、 2.97gの 1, 4—ビス（クロロメトキシメチル）シクロへキサ ンを滴下し、室温で 10時間攪拌した。反応終了後、反応液をろ過し、ろ液を濃縮した 後、該濃縮液を水 Z酢酸ェチル (質量比 1： 1)にて抽出し、酢酸ェチル層を減圧濃 縮し、化合物（11)を 2.5g得た。  Dissolve 10 g of compound (7) in 75 g of tetrahydrofuran, add 3.04 g of triethylamine, stir at room temperature for 10 minutes, add 2.97 g of 1,4-bis (chloromethoxymethyl) cyclohexane dropwise, For 10 hours. After completion of the reaction, the reaction mixture was filtered and the filtrate was concentrated. The concentrate was extracted with water Z ethyl acetate (mass ratio 1: 1), and the ethyl acetate layer was concentrated under reduced pressure to give compound (11). 2.5 g was obtained.
[0192] [化 49] [0192] [Chemical 49]
Figure imgf000070_0001
Figure imgf000070_0001
[0193] 化合物（11)について、 — NMR、 IRによる分析を行った。 [0193] Compound (11) was analyzed by NMR and IR.
iH— NMR (重ジメチルスルホキシド（DMSO)、内部標準：テトラメチルシラン、 400 MHz)： δ (ppm)=8.92 s 4H(Ha), 6.87 d 4H(Hb)J =8.4Hz, 6.80 d iH—NMR (deuterated dimethyl sulfoxide (DMSO), internal standard: tetramethylsilane, 400 MHz): δ (ppm) = 8.92 s 4H (H a ), 6.87 d 4H (H b ) J = 8.4 Hz, 6.80 d
be  be
4H(HC)J =8.4Hz, 6.56 s 4H(Hd), 6.31 s 4H(He), 5.35 s 2H(Hf 4H (H C ) J = 8.4Hz, 6.56 s 4H (H d ), 6.31 s 4H (H e ), 5.35 s 2H (H f
cb  cb
), 5.29 s 4H(Hg), 4.75 s 4H(Hh), 3. 15〜3.54 m 4H(H , 1.99 s), 5.29 s 4H (H g ), 4.75 s 4H (H h ), 3.15 to 3.54 m 4H (H, 1.99 s
12H(Hj), 1.94 s 12H(Hk), 0.77〜： L 74 m lOHCH1) 12H (H j ), 1.94 s 12H (H k ), 0.77〜: L 74 m lOHCH 1 )
IR:3365、 2924、 2852、 1748、 1609、 1587、 1509 (cm-1) IR: 3365, 2924, 2852, 1748, 1609, 1587, 1509 (cm -1 )
上記の結果から、化合物（11)が下記に示す構造を有することが確認できた。  From the results shown above, it was confirmed that the compound (11) had a structure shown below.
[0194] [化 50] [0194] [Chemical 50]
Figure imgf000070_0002
実施例 7 (ィ匕合物（11)を用いたポジ型レジスト組成物の製造及び評価）
Figure imgf000070_0002
Example 7 (Production and Evaluation of Positive Resist Composition Using Compound (11))
実施例 6で合成したィ匕合物（11)を 100質量部、トリフエニルスルホ-ゥムノナフルォ ロブタンスルホネートを 10質量部、及びトリー n—ォクチルァミン 1.0質量部を、 PG MEAと ELの混合溶剤（質量比 6 :4) 1370質量部に溶解してレジスト組成物を製造 した。 100 parts by weight of the compound (11) synthesized in Example 6, 10 parts by weight of triphenylsulfo-munonafluorobutane sulfonate, and 1.0 part by weight of tri-n-octylamine are mixed with PG. A mixed solvent of MEA and EL (mass ratio 6: 4) was dissolved in 1370 parts by mass to prepare a resist composition.
該ポジ型レジスト組成物を、へキサメチルジシラザン処理を施した 8インチシリコン基 板上にスピンナーを用いて均一に塗布し、 110°Cにて 90秒間ベータ処理 (PAB)を 行ってレジスト膜 (膜厚 150nm)を成膜した。  The positive resist composition is uniformly applied on an 8-inch silicon substrate subjected to hexamethyldisilazane treatment using a spinner, and subjected to beta treatment (PAB) at 110 ° C. for 90 seconds to form a resist film. (Film thickness 150 nm) was formed.
該レジスト膜に対し、電子線描画機 HL— 800D (Hitachi社製)を用い、加速電圧 70kVにて大面積描画（1 /z m角）を行い、 110°Cにて 90秒間のベータ処理（PEB) を行い、テトラメチルアンモ-ゥムヒドロキシド (TMAH)の 0. 5質量0 /0水溶液（23°C) を用いて 60秒間の現像を行った。その際、電子線 (EB)の露光量 (EB照射量、 /cm2)の変化による残膜率 (現像後のレジスト膜厚 Z成膜時 (露光前)のレジスト膜 厚)の変化を求め、残膜曲線を作成した (図 1)。 The resist film is drawn on a large area (1 / zm square) at an acceleration voltage of 70 kV using an electron beam lithography machine HL-800D (manufactured by Hitachi), and beta treatment (PEB) at 110 ° C for 90 seconds. ) performed, tetramethylammonium - Umuhidorokishido developed for 60 seconds using a (0.5 mass 0/0 aqueous solution of TMAH) (23 ° C) was carried out. At that time, find the change in the remaining film ratio (resist film thickness after development, Z film thickness (before exposure) resist film thickness) due to the change in the electron beam (EB) exposure dose (EB irradiation dose, / cm 2 ). A residual film curve was created (Fig. 1).
上記結果より、本願発明の化合物を用いて得られる低分子化合物を含有するポジ 型レジスト組成物は良好なコントラストが得られることが確認された。  From the above results, it was confirmed that the positive resist composition containing the low molecular weight compound obtained by using the compound of the present invention can obtain a good contrast.
[0196] 実施例 8 (化合物（3) 'の合成） [0196] Example 8 (Synthesis of Compound (3) ')
17gの 4—カルボキシベンズアルデヒド（1)，を 40gのメタノールに溶かし、 30. 43g の 2, 5—ジメチルフエノール（2) 'をカ卩え、そこへ 35gの 35質量％塩化水素水溶液（ HClaq. )を加え、 60°Cで 3日間反応させた。  Dissolve 17 g of 4-carboxybenzaldehyde (1), in 40 g of methanol, and prepare 30.43 g of 2,5-dimethylphenol (2) ', in which 35 g of 35 mass% aqueous hydrogen chloride (HClaq.) And reacted at 60 ° C for 3 days.
反応終了後、反応液を室温に戻し、次いで水酸ィ匕カリウム水溶液を添加して反応 液をアルカリ性にして 10時間撹拌を行った。  After completion of the reaction, the reaction solution was returned to room temperature, and then an aqueous potassium hydroxide solution was added to make the reaction solution alkaline, followed by stirring for 10 hours.
その後、反応液を塩ィ匕水素水溶液にて中和 (pH試験紙で中性を確認)し、沈殿物 を得た。この沈殿物をろ過し、水洗浄を行い、乾燥させることにより、 31gの化合物（3 )，を得た。  Thereafter, the reaction solution was neutralized with a saline-hydrogen aqueous solution (neutrality was confirmed with a pH test paper) to obtain a precipitate. This precipitate was filtered, washed with water, and dried to obtain 31 g of compound (3).
[0197] [化 51] [0197] [Chemical 51]
Figure imgf000072_0001
Figure imgf000072_0001
Figure imgf000072_0002
化合物（3) 'について、 ipi— NMI^ IR、 LCZMS (液体クロマトグラフィ 質量 分析法）による分析を行った。その結果を以下に示した。
Figure imgf000072_0002
Compound (3) ′ was analyzed by ipi—NMI ^ IR and LCZMS (liquid chromatography mass spectrometry). The results are shown below.
— NMRデータ（重ジメチルスルホキシド（DMSO)、内部標準：テトラメチルシラ ン、 400MHz): δ (ppm)=9.02 brs(Ha), 7.88 d 2H J =8.4Hz(Hb)， 7 be — NMR data (deuterated dimethyl sulfoxide (DMSO), internal standard: tetramethylsilane, 400 MHz): δ (ppm) = 9.02 brs (H a ), 7.88 d 2H J = 8.4 Hz (H b ), 7 be
. 11 d J =8.4Hz(Hc), 6.60 s 2H(Hd), 6.31 s 2H(He), 5.51 s 1 cb 11 d J = 8.4Hz (H c ), 6.60 s 2H (H d ), 6.31 s 2H (H e ), 5.51 s 1 cb
H(Hf), 1.99 s 6H(He), 1.92 s 6H(Hh)。 IRデータ： 3359、 2977、 1691、 1609、 1509、 1285cm H (H f ), 1.99 s 6H (H e ), 1.92 s 6H (H h ). IR data: 3359, 2977, 1691, 1609, 1509, 1285cm
LC/MSデータ： m/z (— H+) 375. 2 (Exact Mass : 376. 2)。  LC / MS data: m / z (—H +) 375.2 (Exact Mass: 376.2).
この結果から、化合物（3) 'が下記に示す構造を有することが確認できた。  From this result, it was confirmed that the compound (3) ′ had the structure shown below.
[化 52]  [Chemical 52]
Figure imgf000073_0001
Figure imgf000073_0001
[0200] 実施例 9 (化合物（5) 'の合成） [0200] Example 9 (Synthesis of Compound (5) ')
7. 51gの 4—カルボキシベンズアルデヒド（1)，を 20gのメタノールに溶かし、 20gの 2—シクロへキシル—5—メチルフエノール（4)，をカ卩え、そこへ 17gの 35質量0 /0塩化 水素水溶液 (HClaq. )を加え、 60°Cで 3日間反応させた。 7. 4-carboxybenzaldehyde in 51 g (1), was dissolved in methanol 20 g, 20 g of 2-cyclohexyl-5-methyl-phenol (4), the Ka卩E, 35 mass 0/0 chloride 17g thereto Aqueous hydrogen solution (HClaq.) Was added and reacted at 60 ° C for 3 days.
反応終了後、反応液を室温に戻し、次いで水酸ィ匕カリウム水溶液を添加して反応 液をアルカリ性にして 10時間撹拌を行った。  After completion of the reaction, the reaction solution was returned to room temperature, and then an aqueous potassium hydroxide solution was added to make the reaction solution alkaline, followed by stirring for 10 hours.
その後、反応液を塩ィ匕水素水溶液にて中和 (pH試験紙で中性を確認)し、沈殿物 を得た。この沈殿物をろ過し、水洗浄を行い、乾燥させることにより、 15gの化合物（5 )，を得た。  Thereafter, the reaction solution was neutralized with a saline-hydrogen aqueous solution (neutrality was confirmed with a pH test paper) to obtain a precipitate. The precipitate was filtered, washed with water, and dried to obtain 15 g of compound (5).
[0201] [化 53] [0201] [Chemical 53]
Figure imgf000074_0001
Figure imgf000074_0001
+  +
Figure imgf000074_0002
Figure imgf000074_0002
化合物（5)，について、 H— NMR、 IR、 LCZMSによる分析を行った。その結果 を以下に示した。  Compound (5) was analyzed by 1 H-NMR, IR, and LCZMS. The results are shown below.
iH— NMRデータ（重ジメチルスルホキシド（DMSO)、内部標準：テトラメチルシラ 400MHz)： δ (ppm) =12.80 brs lH(Ha), 8. 91 s 2H(Hb), 7. 85 d 2H J =8. lHz(Hc), 7.06 d 2H J =8. lHz(Hd), 6. 58 s 2H(He), 6 cd dc iH—NMR data (deuterated dimethyl sulfoxide (DMSO), internal standard: tetramethylsila 400MHz): δ (ppm) = 12.80 brs lH (H a ), 8. 91 s 2H (H b ), 7. 85 d 2H J = 8. LHz (H c ), 7.06 d 2H J = 8. LHz (H d ), 6. 58 s 2H (H e ), 6 cd dc
.46 s 2H(Hf), 5. 55 s lH(Hg), 2.65— 2. 78 m 2H(Hh), 2.01 s 6 H CH1) , O. 96- 1. 78 m 20H (Hj)。 .46 s 2H (H f ), 5.55 s lH (H g ), 2.65— 2.78 m 2H (H h ), 2.01 s 6 H CH 1 ), O. 96- 1.78 m 20H (H j ).
IRデータ： 3357、 2926、 2852、 1692、 1609、 1416、 1283cm_1。 IR data: 3357, 2926, 2852, 1692 , 1609, 1416, 1283cm _1.
LC/MSデータ： m/z (— H+) 511. 4 (Exact Mass : 512. 3)。  LC / MS data: m / z (—H +) 511.4 (Exact Mass: 512.3).
この結果から、化合物（5) 'が下記に示す構造を有することが確認できた。  From this result, it was confirmed that the compound (5) ′ had the structure shown below.
[化 54] [Chemical 54]
Figure imgf000075_0001
Figure imgf000075_0001
産業上の利用可能性 Industrial applicability
本発明は、レジスト組成物用としての利用が可能な低分子化合物の製造に好適に 使用できる化合物、および該化合物の製造方法、前記化合物を用いて得られる低分 子化合物、該低分子化合物を含有するポジ型レジスト組成物、該ポジ型レジスト組成 物を用いるレジストパターン形成方法を提供できる。  The present invention relates to a compound that can be suitably used for the production of a low-molecular compound that can be used as a resist composition, a method for producing the compound, a low-molecular compound obtained using the compound, and the low-molecular compound. A positive resist composition can be provided, and a resist pattern forming method using the positive resist composition can be provided.

Claims

請求の範囲 The scope of the claims
下記一般式 (I 0)で表される化合物。  A compound represented by the following general formula (I 0).
Figure imgf000076_0001
Figure imgf000076_0001
[式 (I— O)中、 RU〜R13はそれぞれ炭素数 1〜： LOのアルキル基であり； sは 1〜2の整 数であり； tは 1〜3の整数であり； uは 1〜3の整数であり； s+t+uは 3〜5の整数であ り； qは 0〜2の整数であり； Qは酸素原子又は単結合であり、； rは 0〜3の整数であり； pは 1又は 2である。 ] [In the formula (I—O), R U to R 13 are each an alkyl group having 1 to C: LO; s is an integer of 1 to 2; t is an integer of 1 to 3; u Is an integer from 1 to 3; s + t + u is an integer from 3 to 5; q is an integer from 0 to 2; Q is an oxygen atom or a single bond; r is 0 to 3 P is 1 or 2. ]
[2] 下記一般式 (A— 1 -0)または (A— 2— 0)で表される低分子化合物。  [2] A low-molecular compound represented by the following general formula (A— 1-0) or (A— 2-0).
[化 2]  [Chemical 2]
1 ~ 0： 1 to 0:
Figure imgf000076_0002
Figure imgf000076_0002
[式中、！^〜 ， 〜 はそれぞれ独立して水素原子、ハロゲン原子、アルキル基ま たはハロゲンィ匕アルキル基であり； R3"〜R4", R9 -〜 R1G"はそれぞれ独立して下記一 般式 (I— 11— 0)で表される基であり； 1, m, 1' , m，はそれぞれ独立して 1〜3の整数 であり； n, n，は 1〜3の整数であり； Yは（n+ 1)価の有機基であり； Zは（n， + 1)価の 有機基である。 ] [In the formula! ^ ~ And ~ are each independently a hydrogen atom, a halogen atom, an alkyl group, or a halogenoalkyl group; R 3 "to R 4 ", R 9-to R 1G "are each independently Is a group represented by the general formula (I—11—0); 1, m, 1 ′ and m are each independently an integer of 1 to 3; n, n are integers of 1 to 3 Yes; Y is an (n + 1) -valent organic group; Z is an (n, + 1) -valent organic group. ]
[化 3] [Chemical 3]
Figure imgf000077_0001
Figure imgf000077_0001
[式中、 RU〜R はそれぞれ炭素数 1〜10のアルキル基であり； sは 1〜2の整数であ り； tは 1〜3の整数であり； uは 1〜3の整数であり； s + t + uは 3〜5の整数であり； qは 0〜2の整数であり； Qは酸素原子又は単結合であり； rは 0〜3の整数である。 ] 酸の作用によりアルカリ可溶性が増大する基材成分 (A—0)、および放射線の照射 により酸を発生する酸発生剤成分 (B)を含有するポジ型レジスト組成物であって、 前記基材成分 (A— 0)が、下記一般式 (A— 1— 0)または (A— 2— 0)で表される 低分子化合物 (A1— 0)を含有するポジ型レジスト組成物。 [Wherein RU to R are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3] S + t + u is an integer of 3-5; q is an integer of 0-2; Q is an oxygen atom or a single bond; r is an integer of 0-3. A positive resist composition comprising a base component (A-0) whose alkali solubility is increased by the action of an acid, and an acid generator component (B) that generates an acid upon irradiation with radiation. A positive resist composition in which the component (A-0) contains a low molecular compound (A1-0) represented by the following general formula (A-1-0) or (A-2-0).
[化 4] [Chemical 4]
1 - 0； Ten;
Figure imgf000077_0002
Figure imgf000077_0002
[式中、！^〜 ， 〜 はそれぞれ独立して水素原子、ハロゲン原子、アルキル基ま たはハロゲンィ匕アルキル基であり； R3"〜R4 , R9〜R1Gはそれぞれ独立して下記一 般式 (1—11—0)で表される基であり； 1, m, Ι' , m，はそれぞれ独立して 1〜3の整数 であり； n, n，は 1〜3の整数であり； Yは（n+ 1)価の有機基であり； Zは（n， + 1)価の 有機基である。 ] [In the formula! ^ ~ And ~ are each independently a hydrogen atom, a halogen atom or an alkyl group. R 3 ″ to R 4 , R 9 to R 1G are each independently a group represented by the following general formula (1-11-0); 1, m, Ι 'and m are each independently an integer of 1 to 3; n and n are integers of 1 to 3; Y is an (n + 1) -valent organic group; Z is (n, + 1 ) Valent organic group.]
[化 5]  [Chemical 5]
Figure imgf000078_0001
(卜 1 1 - 0 )
Figure imgf000078_0001
(卜 1 1-0)
[式中、 R 〜R はそれぞれ炭素数 1〜10のアルキル基であり； sは 1〜2の整数であ り； tは 1〜3の整数であり； uは 1〜3の整数であり； s + t + uは 3〜5の整数であり； qは 0〜2の整数であり； Qは酸素原子又は単結合であり； rは 0〜3の整数である。 ] [Wherein R to R are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3] S + t + u is an integer of 3-5; q is an integer of 0-2; Q is an oxygen atom or a single bond; r is an integer of 0-3. ]
[4] 下記一般式 (I)で表される請求項 1記載の化合物。  [4] The compound according to claim 1, which is represented by the following general formula (I):
[化 6]  [Chemical 6]
Figure imgf000078_0002
Figure imgf000078_0002
[式 (I)中、 R"〜R "はそれぞれ炭素数 1〜10のアルキル基であり； sは 1〜2の整数 であり； tは 1〜3の整数であり； uは 1〜3の整数であり； s+t+uは 3〜5の整数であり； qは 0〜2の整数であり； rは 1〜3の整数であり； pは 1又は 2である。 ] [In the formula (I), R "to R" are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is 1 to 3 S + t + u is an integer from 3 to 5; q is an integer from 0 to 2; r is an integer from 1 to 3; p is 1 or 2. ]
下記一般式 (Π)で表される請求項 4記載の化合物。 The compound according to claim 4, which is represented by the following general formula (Π).
[化 7][Chemical 7]
Figure imgf000079_0001
Figure imgf000079_0001
[式 (Π)中、 R"〜R "はそれぞれ炭素数 1〜10のアルキル基であり； rは 1〜3の整数 であり； ρは 1又は 2である。 ] [In the formula (Π), R ″ to R ″ are each an alkyl group having 1 to 10 carbon atoms; r is an integer of 1 to 3; ρ is 1 or 2. ]
下記一般式（1)で表される化合物（1)と下記一般式 (2)で表される化合物（2)とを 反応させて下記一般式 (3)で表される化合物（3)を得る工程と、  The compound (1) represented by the following general formula (1) and the compound (2) represented by the following general formula (2) are reacted to obtain the compound (3) represented by the following general formula (3). Process,
前記化合物 (3)と下記一般式 (4)で表される化合物 (4)とを酸性条件下で反応させ て下記一般式 (I)で表される化合物 (I)を得る工程とを有する、下記一般式 (I)で表さ れる化合物 (I)の製造方法。  Reacting the compound (3) with a compound (4) represented by the following general formula (4) under acidic conditions to obtain a compound (I) represented by the following general formula (I). The manufacturing method of compound (I) represented by the following general formula (I).
[化 8][Chemical 8]
Figure imgf000079_0002
Figure imgf000079_0002
[式中、 R は炭素数 1〜10のアルキル基であり； qは 0〜2の整数であり； pは 1又は 2 であり；Xはハロゲン原子であり； rは 1〜3の整数であり； Rは保護基である。 ] [Wherein R is an alkyl group having 1 to 10 carbon atoms; q is an integer of 0 to 2; p is 1 or 2; X is a halogen atom; r is an integer of 1 to 3] Yes; R is a protecting group. ]
[化 9]
Figure imgf000080_0001
[Chemical 9]
Figure imgf000080_0001
[式中、 R 〜R はそれぞれ炭素数 1〜10のアルキル基であり； sは 1〜2の整数であ り； tは 1〜3の整数であり； uは 1〜3の整数であり； s + t + uは 3〜5の整数であり； qは 0〜2の整数であり； rは 1〜3の整数であり； pは 1又は 2であり； Rは保護基である。 ] 下記一般式 (A— 1)または (A— 2)で表される請求項 2記載の低分子化合物。 [Wherein R to R are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3] S + t + u is an integer of 3-5; q is an integer of 0-2; r is an integer of 1-3; p is 1 or 2; R is a protecting group; The low molecular compound according to claim 2, represented by the following general formula (A-1) or (A-2).
[化 10] [Chemical 10]
Figure imgf000080_0002
Figure imgf000080_0002
[式中、 〜 ， R5〜R8はそれぞれ独立して水素原子、ハロゲン原子、アルキル基 またはハロゲンィ匕アルキル基であり； R3〜R4, R9〜R1C)はそれぞれ独立して下記一般 式 (1—11)で表される基であり； 1, m, Ι' , m，はそれぞれ独立して 1〜3の整数であり ； n, n は 1〜3の整数であり； Yは（η+ 1)価の有機基であり； Ζは（η， + 1)価の有機 基である。 ] [Wherein, R 5 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group or a halogenated alkyl group; R 3 to R 4 , R 9 to R 1C) are each independently A group represented by the general formula (1-11); 1, m, Ι 'and m are each independently an integer of 1 to 3; N and n are integers of 1 to 3; Y is an (η + 1) valent organic group; Ζ is an (η, +1) valent organic group; ]
[化 11] [Chemical 11]
Figure imgf000081_0001
Figure imgf000081_0001
[式中、 R 〜R はそれぞれ炭素数 1〜10のアルキル基であり； sは 1〜2の整数であ り； tは 1〜3の整数であり； uは 1〜3の整数であり； s + t + uは 3〜5の整数であり； qは 0〜2の整数であり； rは 1〜3の整数である。 ] [Wherein R to R are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3] S + t + u is an integer of 3-5; q is an integer of 0-2; r is an integer of 1-3. ]
酸の作用によりアルカリ可溶性が増大する基材成分 (A)、および放射線の照射に より酸を発生する酸発生剤成分 (B)を含有するポジ型レジスト組成物であって、 前記基材成分 (A)が、下記一般式 (A— 1)または (A— 2)で表される低分子化合 物 (A1)を含有するポジ型レジスト組成物。  A positive resist composition comprising a base component (A) whose alkali solubility is increased by the action of an acid, and an acid generator component (B) that generates an acid upon irradiation with radiation, the base component ( A positive resist composition in which A) contains a low molecular weight compound (A1) represented by the following general formula (A-1) or (A-2).
[化 12] [Chemical 12]
Figure imgf000081_0002
Figure imgf000081_0002
[式中、 〜 ， R5〜R8はそれぞれ独立して水素原子、ハロゲン原子、アルキル基 またはハロゲンィ匕アルキル基であり； R3〜R4, R9〜R1C)はそれぞれ独立して下記一般 式 (I 11)で表される基であり； 1, m, Ι' , m，はそれぞれ独立して 1〜3の整数であり ； n, n，は 1〜3の整数であり； Yは（n+ 1)価の有機基であり； Zは（n， + 1)価の有機 基である。 ] [Wherein, R 5 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group or a halogenated alkyl group; R 3 to R 4 , R 9 to R 1C) are each independently General Is a group represented by the formula (I 11); 1, m, Ι ′ and m are each independently an integer of 1 to 3; n, n are an integer of 1 to 3; Y is (N + 1) -valent organic group; Z is an (n, + 1) -valent organic group. ]
[化 13]  [Chemical 13]
Figure imgf000082_0001
Figure imgf000082_0001
[式中、 R 〜R はそれぞれ炭素数 1〜10のアルキル基であり； sは 1〜2の整数であ り； tは 1〜3の整数であり； uは 1〜3の整数であり； s + t + uは 3〜5の整数であり； qは 0〜2の整数であり； rは 1〜3の整数である。 ] [Wherein R to R are each an alkyl group having 1 to 10 carbon atoms; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer of 1 to 3] S + t + u is an integer of 3-5; q is an integer of 0-2; r is an integer of 1-3. ]
[9] さらに、含窒素有機化合物（D)を含有する請求項 8記載のポジ型レジスト組成物。  9. The positive resist composition according to claim 8, further comprising a nitrogen-containing organic compound (D).
[10] 請求項 8記載のポジ型レジスト組成物を用いて基板上にレジスト膜を形成する工程 、前記レジスト膜を露光する工程、および前記レジスト膜を現像してレジストパターン を形成する工程を含むレジストパターン形成方法。 [10] A step of forming a resist film on a substrate using the positive resist composition according to claim 8, a step of exposing the resist film, and a step of developing the resist film to form a resist pattern Resist pattern forming method.
[11] 請求項 9記載のポジ型レジスト組成物を用いて基板上にレジスト膜を形成する工程 、前記レジスト膜を露光する工程、および前記レジスト膜を現像してレジストパターン を形成する工程を含むレジストパターン形成方法。  [11] A step of forming a resist film on a substrate using the positive resist composition according to claim 9, a step of exposing the resist film, and a step of developing the resist film to form a resist pattern Resist pattern forming method.
[12] 下記一般式 (I) 'で表される請求項 1記載の化合物。  [12] The compound according to claim 1, which is represented by the following general formula (I) ′.
[化 14]
Figure imgf000083_0001
[Chemical 14]
Figure imgf000083_0001
[式 (I)，中、 R"〜R "はそれぞれ独立して炭素数 1〜： LOのアルキル基であり； sは 1 〜2の整数であり； tは 1〜3の整数であり； uは 1〜3の整数であり； s+t+uは 3〜5の 整数であり； qは 0〜2の整数であり； pは 1または 2である。 ] [In the formula (I), R "to R" are each independently an alkyl group having 1 to carbon atoms: LO; s is an integer of 1 to 2; t is an integer of 1 to 3; u is an integer from 1 to 3; s + t + u is an integer from 3 to 5; q is an integer from 0 to 2; p is 1 or 2. ]
[13] 下記一般式 (Π) 'で表される請求項 12記載の化合物。  [13] The compound according to claim 12, which is represented by the following general formula (Π) ′.
[化 15]  [Chemical 15]
Figure imgf000083_0002
Figure imgf000083_0002
[式 (Π)，中、 R"〜R "はそれぞれ独立して炭素数 1〜： L0のアルキル基であり； pは 1 または 2である。 ] [In the formula (Π), R "to R" each independently represents an alkyl group having 1 to carbon atoms: L0; p is 1 or 2. ]
下記一般式（1) 'で表される化合物（1) 'と下記一般式 (2) 'で表される化合物（2) ' とを酸性条件下で反応させて下記一般式 (I) 'で表される化合物を得る工程を有する 化合物の製造方法。 A compound (1) 'represented by the following general formula (1)' and a compound (2) 'represented by the following general formula (2)' are reacted under acidic conditions to give the following general formula (I) ' A step of obtaining a compound represented by Compound production method.
[化 16]  [Chemical 16]
Figure imgf000084_0001
Figure imgf000084_0001
[式中、 R11〜R 3はそれぞれ独立して炭素数 1〜 10のアルキル基であり； sは:!〜 2の 整数であり； tは 1〜3の整数であり； uは 1〜3の整数であり； s+t+uは 3〜5の整数で あり； qは 0〜2の整数であり； pは 1または 2である。 ] [Wherein R 11 to R 3 are each independently an alkyl group having 1 to 10 carbon atoms; s is an integer of:! To 2; t is an integer of 1 to 3; u is 1 to S + t + u is an integer from 3 to 5; q is an integer from 0 to 2; p is 1 or 2. ]
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