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    • 专利摘要:
    The present invention relates to a chemically enhanced resist composition comprising: (A) a salt represented by the formula (I): wherein R21 represents a C1 to C30 hydrocarbon group which may be substituted, and at least one -CH2 - of the hydrocarbon group can be replaced by -CO or -O-, Q1 and Q2 each independently represent a fluorine atom etc., and A + represents at least one organic cation chosen from a cation represented by the formula (Ia): wherein P1, P2, P3 each independently represent a C1 to C30 alkyl group or the like, a cation represented by formula (lb): wherein P4 and P5 each independently represent each other a hydrogen atom or the like, and a cation represented by the formula (lc)
    公开号:BE1019085A3
    申请号:E2007/0581
    申请日:2007-12-05
    公开日:2012-03-06
    发明作者:Satoshi Yamamoto；Satoshi Yamaguchi；Nobuo Ando
    申请人:Sumitomo Chemical Co；
    IPC主号:
    专利说明:

    "CHEMICAL AMPLIFICATION RESERVE COMPOSITION"
    FIELD OF THE INVENTION
    The present invention relates to a chemical amplification reserve composition.
    BACKGROUND OF THE INVENTION
    A chemically amplified resist composition used for microfabrication of semiconductors using a lithographic process contains a resin which contains a structural unit having an acidolabile group and which is itself insoluble or sparingly soluble in an aqueous alkaline solution but becomes soluble in an aqueous alkaline solution under the action of an acid, and an acid generator comprising a compound generating an acid by irradiation.
    In the microfabrication of semi-conductors, it is desirable to form patterns having a high resolution and a good line edge roughness, and it is expected from a chemically amplified resist composition that it provides such patterns.
    US 2006 - 0194982 A1 discloses a chemically amplified resist composition containing the salt represented by the formula:
    in which E represents a hydrogen atom or a hydroxyl group, and a resin which contains a structural unit having an acidolabile group and which is itself insoluble or poorly soluble in an aqueous alkaline solution, but becomes soluble in an aqueous alkaline solution under the action of an acid.
    US 2007/27336 A1 discloses a chemically amplified resist composition containing the salt represented by the following formula:
    and a resin containing a structural unit having an acid-labile group and which is itself insoluble or poorly soluble in an aqueous alkaline solution but becomes soluble in an aqueous alkaline solution under the action of an acid.
    The document 2003/0194 639 A1 also discloses a chemically amplified resist composition containing the salt represented by the following formula:
    as an acid generator.
    SUMMARY OF THE INVENTION
    An object of the present invention is to provide a chemically amplified resist composition.
    This object of the invention, as well as others according to the present invention, will emerge from the description which follows.
    The present invention relates to the following: <1> A chemically amplified resist composition comprising: (i) (A) a salt represented by the formula (I): wherein R21 represents a C1 to C30 hydrocarbon group which may be substituted, and at least one -CH2- of the hydrocarbon group may be replaced by -CO or -O-, Q1 and Q2 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group and A + represents at least one organic cation selected from a cation represented by formula (Ia):
    wherein P1, P2 and P3 each independently represent a C1-C30 alkyl group which may be substituted by at least one group selected from a hydroxyl group, a C3-C12 cyclic hydrocarbon group; and a C1-C12 alkoxy group, or a C3-C30 cyclic hydrocarbon group which may be substituted by at least one group selected from a hydroxyl group and a C1-C12 alkoxy group a cation represented by the formula (Ib):
    (Ib) wherein P4 and P5 are each independently of one another a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, and a cation represented by formula (the):
    wherein P10, P11, P12, P13, P14, p15, p16, p17, p18 p19 p20 and P21 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, B represents a sulfur or oxygen atom and m is 0 or 1, (B) a salt represented by the formula (II):
    (II) wherein R22 represents a C1 to C30 hydrocarbon group which may be substituted, and at least one -CH2- of the hydrocarbon group may be substituted with -CO- or -O-, Q3 and Q4 each independently represent a on the other a fluorine atom or a C 1 -C 6 perfluoroalkyl group, and A '+ represents an organic cation represented by the formula (IIa):
    (IIa) wherein P6 and P7 each independently represent a C1-C12 alkyl group or a C3-C12 cycloalkyl group, or P and P are bonded to form a divalent C3 acyclic hydrocarbon group C12 which forms a ring with the adjacent S +, and at least one -CH2 of the divalent acyclic hydrocarbon group can be replaced by -CO-, -O- or -S-, P represents a hydrogen atom, P9 represents a group C1-C12alkyl, C3-C12cycloalkyl or an aromatic group which may be substituted, or P8 and P9 are linked to form a divalent acyclic hydrocarbon group which forms a 2-oxocycloalkyl group with the adjacent -CHCO-, and at least one -CH 2 - of the divalent acyclic hydrocarbon group can be replaced by -CO-, -O- or -S-, and (C) a resin which contains a structural unit having an acid-labile group and which is itself insoluble or slightly soluble in an alkaline aqueous solution but becomes soluble in in an alkaline aqueous solution under the action of an acid, <2> The resist composition according to <1>, wherein Q1, Q2, Q3 and Q4 are each independently of one another a fluorine atom or trifluoromethyl, <3> The following resist composition <1>, wherein Q1, Q2, Q3 and Q4 are fluorine atoms, <4> The resist composition of any one of <1> to <3 where A + is a cation represented by the formula (Id), (le) or (If):
    wherein P28, P29 and P30 are each independently C1 to C20 alkyl or a C3 to C30 cyclic hydrocarbon group with the exception of a phenyl group, and at least one hydrogen atom of the C 1 -C 20 alkyl group may be replaced by a hydroxyl group, a C 1 -C 12 alkoxy group or a C 3 -C 12 cyclic hydrocarbon group and at least one hydrogen atom of the C 3 -C 30 cyclic hydrocarbon group may be replaced with a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, and P31, P32, P33, P34, P35 and P36 are each independently of one another a hydroxyl group, a group C1-C12 alkyl, C1-C12 alkoxy or C3-C8 cyclic hydrocarbon group, and I, k, j, i, h and g each independently represent a) integer from 0 to 5, <5> The resist composition according to any one of <1> to <3>, wherein A * is a catio n represented by the formula (Ig):
    (Iff) wherein P41, P42 and P43 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, <6> resist composition according to any one of <1> to <3>, wherein A + is a cation represented by the formula (Ih):
    (Ih) wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group; <7> The resist composition according to any one of <1 > to <6>, wherein R21 represents a group represented by the formula:
    wherein Z1 represents a single bond or - (CH2) r. f represents an integer from 1 to 4, Y1 represents -CH2-, -CO- or -CH (OH), the ring X1 represents a C3-C30 mononuclear or polynuclear hydrocarbon group in which a hydrogen atom is replaced by a hydroxyl group in the Y1 position when Y1 is -CH (OH) - or in which two hydrogen atoms are replaced by = 0 in the Y1 position when Y1 is -CO-, and at least one hydrogen atom of the mononuclear hydrocarbon group or C3-C30 polynuclear may be replaced by C1-C6 alkyl, C1-C6 alkoxy, C1-C4 perfluoroalkyl, C1-C6 hydroxyalkyl, hydroxyl or cyano, <8> The resist composition according to <7>, wherein the group represented by the formula
    is a group represented by the formula (I), (m) or (n):
    <9> The resist composition according to any one of <1> to <3>, wherein A + is a cation represented by the formula (Ih): (Ih)
    wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group, and R represents a group represented by the formula:
    in which Z1 represents a single bond or - (CH2) r, f represents an integer from 1 to 4, Y1 represents -CH2-, -CO- or -CH (OH), the ring X1 represents a mononuclear or polynuclear hydrocarbon group at C3 to C30 in which a hydrogen atom is replaced by a hydroxyl group in the Y1 position when Y1 is -CH (OH) - or in which two hydrogen atoms are replaced by = 0 in the Y1 position when Y1 is -CO - and at least one hydrogen atom of the C3-C30 mononuclear or polynuclear hydrocarbon group may be replaced by a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a hydroxyalkyl group; C1 to C6, a hydroxyl group or a cyano group, <10> The resist composition according to <9>, wherein the group represented by the formula: is a group
    represented by formula (I), (m) or (n)
    <11> the reserve composition according to <1>. <2>. <3>. <7> or <8>, where P6 and P7 are linked to form a C3-C12 acyclic divalent hydrocarbon group which forms a ring with the adjacent S +, P8 represents a hydrogen atom, P9 represents a C1-C8 alkyl group C12, a C3-C12 cycloalkyl group or an aromatic group which may be substituted by at least one group selected from C1-C6 alkoxy, C2-C20 acyl and nitro, <12> The composition of resist according to any one of <1> to <11> where R is a group represented by the formula:
    wherein Z2 represents a single bond or - (Chfejg, g represents an integer from 1 to 4, Y2 represents -CH2-, -CO- or -CH (OH) -, the ring X represents a mononuclear or polynuclear hydrocarbon group in which C3 to C30 in which a hydrogen atom is replaced by a hydroxyl group in the Y2 position when Y2 is -CH (OH) - or in which two hydrogen atoms are replaced by = 0 in the Y2 position is -CO-, and at least one hydrogen atom of the C3-C30 mononuclear or polynuclear hydrocarbon group may be replaced by a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-hydroxyalkyl group; at C6, a hydroxyl group or a cyano group, <13> The resist composition according to <12>, wherein the group represented by the formula:
    is a group represented by the formula (I), (m) or (n):
    <14> The resist composition according to any one of <1> to <10>, wherein P6 and P7 are bonded to form a divalent C3-C12 hydrocarbon group which forms a ring with the adjacent S +, P8 represents a hydrogen atom, P9 represents a C1-C12 alkyl group, a C3-C12 cycloalkyl group or an aromatic group which may be substituted by at least one group selected from a C1-C6 alkoxy group, an acyl group C2 to C20 and a nitro group, and R22 represents a group represented by the formula:
    wherein Z2 represents a single bond or - (Chfejg, g represents an integer from 1 to 4, Y2 represents -CH2-, -CO- or -CH (OH) -, the ring X represents a mononuclear or polynuclear hydrocarbon group in which C3 to C30 wherein a hydrogen atom is replaced by a hydroxyl group in the Y2 position when Y2 is -CH (OH) - or in which two hydrogen atoms are replaced by = 0 in the Y2 position when Y2 is - CO-, and at least one hydrogen atom of the C3-C30 mononuclear or polynuclear hydrocarbon group may be replaced by a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group.
    <15> The resist composition according to <14>, wherein the group represented by the formula:
    is a group represented by the formula (I), (m) or (n):
    <16> The resist composition according to any one of <1> to <3>, wherein A + is a cation represented by the formula (1h):
    (Ih) wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group, R21 represents a group represented by the formula:
    wherein Z1 represents a single bond or - (Chbjf-, f represents an integer from 1 to 4, Y1 represents -CH2-, -CO- or -CH (OH), the ring X1 represents a mononuclear or polynuclear hydrocarbon group in which C3 to C30 in which a hydrogen atom is replaced by a hydroxyl group in the Y1 position when Y1 is -CH (OH) - or in which two hydrogen atoms are replaced by = 0 in the Y1 position when Y1 is -CO- and at least one hydrogen atom of the C3-C30 mononuclear or polynuclear hydrocarbon group may be replaced by a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a hydroxyalkyl group; in Ci to Οβ, a hydroxyl group or a cyano group, and R represents a group represented by the formula:
    wherein Z2 represents a single bond or - (CH2) g, g represents an integer from 1 to 4, Y2 represents -CH2-, -CO- or -CH (OH) -, the ring X represents a mononuclear hydrocarbon group or C3 to C30 polynuclear atom in which a hydrogen atom is replaced by a hydroxyl group at the Y2 position when Y2 is -CH (OH) - or in which two hydrogen atoms are replaced by = 0 in the Y2 position when Y2 is - CO-, and at least one hydrogen atom of the C3-C30 mononuclear or polynuclear hydrocarbon group may be replaced by a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, hydroxyl group or cyano group.
    <17> The resist composition <16>, wherein the group represented by the formula:
    and the group represented by the formula: each independently represents a group represented by the formula (I), (m) or (n):
    <18> The resist composition according to any one of 1> to <17>, wherein the quantitative ratio of the salt represented by formula (I) to the salt represented by formula (II) is 9/1 to 1/9.
    <19> The resist composition according to any one of <1> to <18>, wherein the resin contains a structural unit derived from a monomer having a bulky and acidolabile group.
    <20> The <19> resin composition wherein the bulky and acidolabile group is a 2-alkyl-2-adamantyl ester group or a 1- (1-adamantyl) -1-alkylalkyl ester group.
    <21> The resist composition according to <19>, wherein the monomer having a large and acidolabile group is a 2-alkyl-2-adamantyl acrylate, a 2-alkyl-2-adamantyl methacrylate, a 1-acrylate, 1-adamantyl) -1-alkylalkyl, a 1- (1-adamantyl) -1-alkylalkyl methacrylate, a 2-alkyl-2-adamantyl-5-norbornene 2-carboxylate, a 2-carboxylate of 1- (1-adamantyl) -1-alkylalkyl adamantyl) -1-alkylalkyl-5-norbornene, a 2-alkyl-2-adamantyl α-chloroacrylate or a 1- (1-adamantyl) -21-alkylalkyl α-chloroacrylate.
    <22> The resist composition according to any one of <1> to <21>, wherein the resist composition further contains n basic compound.
    DESCRIPTION OF PREFERRED EMBODIMENTS
    In the salt represented by formula (I) (hereinafter simply referred to as salt (I)), R21 represents a C10-C10 hydrocarbon group which may be substituted, and at least one -CH2- of the hydrocarbon group may be replaced by -CO- or -O-
    The C.sub.1 -C.sub.6 hydrocarbon group may be a straight chain or branched hydrocarbon group. The C1 to C20 hydrocarbon group may have a mononuclear or polynuclear structure, and may have one or more aromatic groups. The C 1 -C 4 hydrocarbon group may have one or more carbon-carbon double bonds.
    It is preferred that the C 1 to C 10 hydrocarbon group has at least one ring structure, it is more preferred that the C 1 -C 4 hydrocarbon group has a ring structure. Examples of the cyclic structure include structures of cyclopropane, cyclohexane, cyclooctane, norbornene, adamantane, cyclohexene, benzene, naphthalene, phenanthene, phenanthrene and fluorene.
    Examples of the substituent include a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C6-C6 hydroxyalkyl group, a hydroxyl group or a cyano group, and the hydroxyl group is preferable as a substituent.
    Examples of C 1-6 alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl and the like. sec-butyl, tert-butyte, n-pentyl and n-hexyte. Examples of the C1-C6 alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy. n-pentyloxy and n-hexyloxy. Examples of the C1-C1 perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl and nonafluorobutyl groups. Examples of the C 1 -C 6 hydroxyalkyl group include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl and 6-hydroxyhexyl groups.
    Q1 and Q2 are each independently of each other a fluorine atom or a C1-C6 perfluoroalkyl group. Examples of the C1-C6 perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, undecafluoropentyl and tridecafluorohexyl groups. and the trifluoromethyl group is preferred.
    It is preferred that Q and Q 2 each independently represent fluorine or trifluoromethyl, and it is more preferable that Q 1 and Q 2 are fluorine atoms.
    Specific examples of the anion portion of salt (I) include the following.








    It is preferred that R21 represents a group represented by the formula:
    wherein Z1 represents a single bond or - (CH2) f-, f represents an integer from 1 to 4, Y1 represents -CH2-, -CO- or -CH (OH), the ring X1 represents a mononuclear hydrocarbon group or C3 to C30 polynuclear ring in which a hydrogen atom is replaced by a hydroxyl group in the Y1 position when Y1 is -CH (OH) - or in which two hydrogen atoms are replaced by = 0 in the Y1 position when Y1 is - CO-, and at least one hydrogen atom of the C3-C30 mononuclear or polynuclear hydrocarbon group may be replaced by a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, hydroxyl group or cyano group
    Examples of the C1-C6 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and n-hexyl. Examples of the C1-C6 alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy and n-hexyloxy. Examples of the C1-C4 perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl and nonafluorobutyl groups. Examples of the C 1 -C 6 hydroxyalkyl group include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl and 6-hydroxyhexyl groups.
    Examples of the X1 ring include a C4-C6 cycloalkyl group such as cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl, an adamantyl group and a norbornyl group, where a hydrogen atom may be replaced by a hydroxyl group or in which two atoms of hydrogen can be replaced by = 0, and wherein at least one hydrogen atom can be replaced by a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1 to C6 hydroxyalkyl, a hydroxyl group or a cyano group.
    Specific examples of the X1 ring include a 2-oxycyclopentyl group, a 2-oxocyclohexyl group, a 3-oxocyclopentyl group, a 3-oxocyclohexyl group, a 4-oxocyclohexyl group, a 2-hydroxycyclopentyl group, a 2-hydroxycyclohexyl group, a 3-hydroxycyclopentyl group, 3-hydroxycyclohexyl group, 4-hydroxycyclohexyl group, 4-oxo-2-adamantyl group, 3-hydroxy-1-adamantyl group, 4-hydroxy-1-adamantyl group, 5-hydroxycyclohexyl group, -oxonorbornan-2-yl, 1,7,7-trimethyl-2-oxonorbornan-2-yl, 3,6,6-trimethyl-2-oxo-bicyclo [3.1.1] heptan-3 2-hydroxynorbornan-3-yl, 1,7-trimethyl-2-hydroxynorbornan-3-yl, 3,6,6-trimethyl-2-hydroxybicyclo [3.1.1] ] heptan-3-yl,
    and the like.
    In the foregoing formulas, an open-ended straight line shows a bond that is extended from an adjacent group.
    Preferred as the X1 ring is the adamantane ring. The group represented by the following formulas (I), (m) or (n)
    are more preferable.
    In the foregoing formulas, an open-ended straight line shows a bond that is extended from an adjacent group.
    A + represents at least one organic cation chosen from a cation represented by formula (Ia):
    wherein P1, P2 and P3 each independently represent a C1 to C30 alkyl group which may be substituted by at least one group selected from a hydroxyl group, a C3 to C12 cyclic hydrocarbon group; and a C1-C12 alkoxy group or a cyclic hydrocarbon group which may be substituted by at least one group selected from a hydroxyl group and a C1-C12 alkoxy group (hereinafter simply referred to as cation (Ia)), a cation represented by the formula (Ib):
    wherein each of P4 and P5 is, independently of one another, a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, hereinafter referred to simply as a cation (Ib), and a cation represented by the formula (le):
    wherein P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20 and P21 each independently of one another is a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, B represents a sulfur or oxygen atom and m is 0 or 1 (and hereinafter simply called cation (Ic)).
    Examples of C 1 -C 12 alkoxy in cations (Ia), (Ib) and (Ic) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec.-butoxy, tert. butoxy, n-pentyloxy, n-hexyloxy, n-octyloxy and 2-ethylhexyloxy.
    Examples of the C3-C12 cyclic hydrocarbon group in the cation (Ia) include cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, phenyl, 2-methylphenyl, 4-methylphenyl, 1-naphthyl and 2-naphthyl.
    Examples for the C 1 -C 30 alkyl group which may be substituted by at least one group selected from hydroxyl group, a C 1 -C 12 cyclic hydrocarbon group and a C 1 -C 12 alkoxy group in the cation (1a) include groups methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl and benzyl.
    Examples of the C3-C30 cyclic hydrocarbon group which may be substituted by at least one of a hydroxyl group and a C1-C12 alkoxy group in the cation (1a) include cyclopentyl, cyclohexyl, 1-adamantyl, 2- adamantyl, bicyclohexyl, phenyl, 2-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert.-butylphenyl, 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 4-n-hexylphenyl, 4 n-octyl-phenyl, 1-naphthyl, 2-naphthyl, fluorenyl, 4-phenylphenyl, 4-hydroxyphenyl, 4-methoxyphenyl, 4-tert.-butoxyphenyl, 4-n-hexyloxyphenyl.
    Examples of C 1 -C 12 alkyl in cations (1b) and (1c) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-butyl, pentyl, n-hexyl, n-octyl and 2-ethylhexyl.
    Examples of the cation (1a) include the following:

    Examples of the cation (1b) include the following:
    examples of the cation (1c) include the following:


    The cation (Ia) is preferable as the cation represented by A +.
    Cations represented by the following formulas (Id), (Ic) and (If) are preferable as cations represented by A +:
    Wherein P28, P29 and P30 each independently represent a C1 to C20 alkyl group, or a C3 to C30 cyclic hydrocarbon group with the exception of a phenyl group, and at least one atom. of hydrogen in the group C 1 to C 20 may be replaced by a hydroxyl group, a C 1 -C 12 alkoxy group or a C 3 to C 12 cyclic hydrocarbon group and at least one hydrogen atom in the C 3 to C 30 cyclic hydrocarbon group. may be replaced by a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, and P31, P32, P33, P34, P35 and P36 each independently represent a hydroxyl group, an alkyl group C1 to C12, a C1 to C12 alkoxy group or a C3 to C12 cyclic hydrocarbon group, and I, k, j, i, h and g each independently represent an integer of 0 to 5, also preferable.
    Examples of the C 1 -C 20 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, n-octyl, n-decyl and n-icosyl groups.
    Examples of the C1-C12 alkoxy group and the C3-C30 cyclic hydrocarbon group include the same groups as mentioned above.
    As the cation represented by A +, it is particularly preferred that represented by the formula (Ig):
    (ig) wherein P41, P42 and P43 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group) and a particularly preferable cation is that represented by the formula (Ih):
    (Ih) wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group.
    Examples of the alkyl group and the alkoxy group include the same groups as mentioned above.
    A preferable salt as salt (I) is that represented by the following formula:
    wherein A +, Q1, Q2, X1, Y1 and Z1 are as defined above, and the salt represented by the following formula
    wherein P22, P23, P24, Q1, Q2, X1, Y1 and Z1 are as defined above, is more preferable, and the salts represented by the following formulas:
    wherein P22, P23, P24, Q1 and Q2 are as defined above are particularly preferable.
    In the salt represented by formula (II) (hereinafter simply referred to as salt (II)), R22 represents a C1 to C30 hydrocarbon group which may be substituted, and at least one -CH2- of the hydrocarbon group may be replaced by -CO- or -0-. As the C1-C30 hydrocarbon group which may be substituted, and wherein at least one -CH2- of the hydrocarbon group may be replaced by -CO- or -O-, examples are the same groups as mentioned for R21 in the salt (I).
    Q3 and Q4 are each independently of each other a fluorine atom or a C1-C6 perfluoroalkyl group. Examples of the C1-C6 perfluoroalkyl group include the same groups as mentioned in Q1 and Q2, and the trifluoromethyl group is preferable.
    It is preferred that Q 3 and Q 4 are each independently of each other fluorine atom or trifluoromethyl group. and it is more preferable that Q3 and Q4 are fluorine atoms.
    Specific examples of the anion portion of salt (II) include the same anion moieties as mentioned for the anion moieties of salt (I).
    AA
    It is preferred that R represents a group represented by the formula: R22 represents a group represented by the formula:
    wherein Z2 represents a single bond or - (CH2) g, g represents an integer from 1 to 4, Y2 represents -CH2-, -CO- or -CH (OH) -, the ring X2 represents a mononuclear hydrocarbon group or C3-C30 polynuclear ring in which a hydrogen atom is replaced by a hydroxyl group at the Y2 position when Y2 is -CH (OH) - or in which two hydrogen atoms are replaced by = 0 in the Y2 position is -CO- and at least one hydrogen atom of the C3-C30 mononuclear or polynuclear hydrocarbon group may be replaced by a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a hydroxyalkyl group. C1 to C6, a hydroxyl group or a cyano group.
    Examples of C1-C6 alkyl, C1-C6 alkoxy, C1-C4 perfluoroalkyl and C1-C6 hydroxyalkyl include the same groups as mentioned above, respectively.
    Examples of the X2 ring include the same ring groups as those mentioned for the X1 ring.
    The adamantane nucleus is preferable as the X2 nucleus. The group represented by the following formulas (I), (m) or (n):
    is preferable as R22.
    In formulas (I), (m) and (n) above, an open-ended straight line shows a bond that is extended from an adjacent group.
    A '+ represents an organic cation represented by the formula (IIa): (IIa) wherein P6 and P7 each independently represent a C1-C12 alkyl group or a C3-C12 cycloalkyl group, or although P6 and P7 are linked to form a C3-C12 divalent acyclic hydrocarbon group which forms a ring with the adjacent S +, and at least one -CH2- of the divalent acyclic hydrocarbon group can be replaced by -CO-, -O- or -S.
    P8 represents a hydrogen atom, P9 represents a C1-C12 alkyl group, a C3-C12 cycloalkyl group or an aromatic group which may be substituted, or P8 and P9 are linked to form a divalent acyclic hydrocarbon group which forms a 2-oxocycloalkyl group with the adjacent -CHCO-, and at least one -CH2- of the divalent acyclic hydrocarbon group can be replaced by -CO-, -O- or -S- (hereinafter simply called cation (IIa)) .
    Examples of the C1-C12 alkyl group include the same groups as mentioned above.
    Examples of the C 3 -C 12 cycloalkyl group in the (IIa) cation include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl. Examples of the C3-C12 divalent acyclic hydrocarbon group formed by the bonding of P6 and P7 include trimethylene, tetramethylene, pentamethylene groups. Examples of the cyclic group formed together with the adjacent S + and the divalent acyclic hydrocarbon group include tetramethylene sulfonio, pentamethylene sulfonio and oxybisethylene sulphonio groups.
    Examples of the aromatic group in the cation (IIa) include phenyl, tolyl, xylyl, 4-b-butylphenyl, 4-isobutylphenyl, 4-tert.-butylphenyl, 4-cyclohexylphenyl, 4-phenylphenyl, and naphthyl. The aromatic group may be substituted, and the exemplary substituents include a C1-C6 alkoxy group such as methoxy, ethoxy, n-propoxy, n-butoxy, tert-butoxy and n-hexyloxy, acyloxy group. C2 to C12 as an acetyloxy group and a 1-adamantylcarbonyloxy group, and a nitro group.
    Examples of the divalent acyclic hydrocarbon group formed by the bonding of P6 and P9 include methylene, ethylene, trimethylene, tetramethylene and pentamethylene groups, and examples of the 2-oxocycloalkyl group formed together with the -CHCO-adjacent and the divalent acyclic hydrocarbon group include a 2-oxocyclopentyl group and a 2-oxocyclohexyl group.
    For the cation (IIa), a preferable cation is the cation in which P and P are bonded to form the divalent C3-C12 acyclic hydrocarbon group which forms the ring with the adjacent S +, P6 represents the hydrogen atom, P9 is a C1-C12 alkyl group, a C3-C12 cycloalkyl group or an aromatic group which may be substituted by at least one group selected from C1-C6 alkoxy, C2-C20 acyl and nitro group and a more preferable cation is one in which P6 and P7 are linked to form a trimethylene, tetramethylene or pentamethylene group which forms the ring with the adjacent S +, P8 represents the hydrogen atom, P9 represents a C1 to C8 alkyl group, C12 or an aromatic group which may be substituted by at least one group selected from a C1-C6 alkoxy group and a nitro group.
    Examples of the cation (IIa) include the following:

    A more preferred salt as salt (II) is that represented by the following formula:
    wherein P6, P7, P8, P9, Q3, Q4, X2, Y2 and Z2 are as defined above, and the salts represented by the following formulas:
    wherein P6, P7, P8, P9, Q3 and Q4 are as defined above are particularly preferable.
    The salt (I) can be produced by a process comprising reacting a salt of the formula (L1):
    <LI) in which M represents Li, Na, K or Ag, and Q1, Q2 and R21 have the same meanings as defined above (hereinafter simply called salt (Ll)), with a compound of the formula (XI ): A + G (XI) wherein A + has the same meaning as defined above and G represents F, Cl, Br, I, BF4, AsF6, PF6 or ClO4 (and hereinafter simply referred to as compound (XI)).
    The reaction of salt (L1) and of compound (XI) is usually carried out in an inert solvent such as acetonitrile, water, methanol and dichloromethane, at a temperature of about 0 to 150 ° C, preferably from 0 to 100 ° C, with stirring.
    The amount of the compound (XI) is usually 0.5 to 2 moles per 1 mole of the salt (L1). The salt (I) obtained by the above process can be isolated by recrystallization and can be purified by washing with water.
    The salt (L1) used for the production of the salt (I) can be produced by a process comprising an esterification of an alcohol compound represented by the formula (II): HO-R21 (LII) wherein R has the same meaning than that defined above, and hereinafter simply called alcohol compound (LII), with a carboxylic acid represented by formula (IX):
    (IX) in which M, Q1 and Q2 have the same meanings as those defined above (and simply hereinafter referred to as carboxylic acid (IX)).
    The esterification reaction of the alcohol compound (LII) and the carboxylic acid (IX) can generally be carried out by mixing the materials in an aprotic solvent such as dichloroethane, toluene, ethylbenzene, monochlorobenzene, acetonitrile and N, N-dimethylformamide at a temperature of 20 to 200 ° C, preferably 50 to 150 ° C. In the esterification reaction, an acid catalyst or a dehydrating agent is usually added, and examples of acidic catalysts include organic acids such as p-toluenesulfonic acid, and inorganic acids such as sulfuric acid. Examples of the dehydrating agent include 1,1'-carbonyldiimidazole and N, N'-dicyclohexylcarbodiimide.
    The esterification reaction can preferably be carried out with dehydration as this tends to shorten the reaction time. Examples of a dehydration process include the Dean and Stark process.
    The amount of the carboxylic acid (IX) is usually 0.2 to 3 moles, preferably 0.5 to 2 moles per 1 mole of the alcohol compound (LII).
    The amount of the acid catalyst may be a catalytic amount or the amount equivalent to the solvent, and is usually from 0.001 to 5 moles per 1 mole of the alcohol compound (LU). The amount of the dehydrating agent is usually 0.2 to 5 moles, preferably 0.5 to 3 moles per 1 mole of the alcohol compound (LM).
    The salt (II) can be produced by a process comprising the reaction of a salt of the formula (III):
    In which M 'represents Li, Na, K or Ag, and Q3, Q4 and R22 have the same meanings as defined above (and hereinafter simply called salt (III)), with a compound of the formula (XII): A '+' G '(XII) wherein A' + has the same meaning as defined above, and G 'represents F, Cl, Br, I, BF4, AsFe, SbF6, PFe or ClO4 ( and hereinafter simply called compound (XII)).
    The reaction of the salt (III) and the compound (XII) is usually carried out in an inert solvent such as acetonitrile, water, methanol and dichloromethane, at a temperature of about 0 to 150 ° C, preferably from 0 to 100 ° C, with stirring.
    The amount of the compound (XII) is usually 0.5 to 2 moles per 1 mole of the salt (LUI). The salt (II) obtained by the above process can be isolated by recrystallization, and can be purified by washing with water.
    The salt (III) used for the production of salt (II) can be produced by a process comprising an esterification of an alcohol compound represented by the formula (LIV): HO-R22 (LIV) in which R22 has the same meaning as that defined above (and hereinafter simply called alcohol compound (LIV)), with a carboxylic acid represented by the formula (X):
    (X) wherein M ', Q3 and Q4 have the same meanings as defined above (and hereinafter simply called carboxylic acid (X))
    The esterification reaction of the alcohol compound (LIV) and the carboxylic acid (X) can generally be carried out by mixing the materials in an aprotic solvent such as dichloroethane, toluene, ethylbenzene, monochlorobenzene, acetonitrile and N, N-dimethylformamide at a temperature of 20 to 200 ° C, preferably 50 to 150 ° C. In the esterification reaction, an acid catalyst or a dehydrating agent is usually added, and examples of the acid catalyst include organic acids such as p-toluenesulfonic acid, and inorganic acids such as sulfuric acid. Examples of the dehydrating agent include 1,1'-carbonyldiimidazole and N, N'-dicyclohexylcarbodiimide.
    The esterification reaction may preferably be carried out with dehydration as this tends to reduce the reaction time. Examples of a dehydration process include the Dean and Stark process.
    The amount of carboxylic acid (X) is usually from 0.2 to 3 moles, preferably from 0.5 to 2 moles per 1 mole of the alcohol compound (LIV).
    The amount of the acid catalyst may be a catalytic amount or the amount equivalent to the solvent, and is usually from 0.001 to 5 moles per 1 mole of the alcohol compound (LIV). The amount of the dehydrating agent is usually 0.2 to 5 moles, preferably 0.5 to 3 moles per 1 mole of the alcohol compound (LIV).
    The present resist composition comprises (A) a salt (I), (B) a salt (II) and (C) a resin containing a structural unit having an acidolabile group and which is itself insoluble or slightly soluble in a solution aqueous alkaline, but becomes soluble in an aqueous alkaline solution under the action of an acid.
    The salt (I) and the salt (II) are usually used as an acid generator, and the acid generated by irradiation of the salt (I) and salt (II) acts as a catalyst with respect to the acidolabile groups of the resin, cleaves the acidolabile groups and the resin becomes soluble in an aqueous alkaline solution.
    In the present resist composition, the anion portion of the salt (II) may be the same as that of the salt (I), and the anion portion of the salt (II) may be different from that of the salt (I).
    The resin used for the present composition contains a structural unit having the acidolabile group and which is itself insoluble or poorly soluble in an alkaline aqueous solution, but the acidolabile group is cleaved with an acid.
    In the present description, "-COOR" can be described as a structure having a carboxylic acid ester ", and can also be shortened to" ester group. "Specifically," -COOR (CH 3) 3 "can be described as a "structure having a tert-butyl carboxylic acid ester" or be abbreviated to "tert-butyl ester group".
    Examples of the acidolabile group include a structure having a carboxylic acid ester such as an alkyl ester group in which a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, an alicyclic ester group in which an atom of carbon adjacent to the oxygen atom is a quaternary carbon atom and a lactone ester group in which a carbon atom adjacent to the oxygen atom is a quaternary carbon atom. A "quaternary carbon atom" refers to a "carbon atom bound to four substituents other than hydrogen atoms". For the acidolabile group, an example is a group having a quaternary carbon atom bonded to three carbon atoms and -OR ', where R' is an alkyl group.
    Examples of the acidolabile group include an alkyl ester group wherein a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, such as a tert-butyl ester group, an acetal ester group such as a methoxymethyl ester group ethoxymethyl ester, 1-ethoxyethyl ester, 1-isobutoxyethyl ester, 1-isopropoxyethyl ester, 1-ethoxypropoxylic ester, 1- (2-methoxyethoxy) ethyl ester, 1- (2-acethoxyethoxy) ethyl ester, 1- [2- (1-adamantyloxy) ethoxy] -ethyl, 1- [2- (1-adamantan-carbonyloxy) ethoxy] ethyl, tetrahydro-2-furyl ester and tetrahydro-2-pyranyl ester, an alicyclic ester group in which a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, such as an isobornyl ester group, 1-alkylcycloalkyl ester, 2-alkyl-2-adamantyl ester and 1- (1-adamantyl) -1-alkylalkyl ester. At least one hydrogen atom of the adamantyl group may be replaced by a hydroxyl group.
    Examples of the structural unit include a structural unit derived from an acrylic acid ester, a structural unit derived from a methacrylic acid ester, a structural unit derived from a norbornene carboxylic acid ester, a structural unit derived from a tricyclodecenecarboxylic acid ester and a structural unit derived from a tetracyclodecene carboxylic acid ester. Structural units derived from acrylic acid esters and methacrylic acid esters are preferable.
    The resin used for the present composition can be obtained by carrying out the polymerization reaction of one or more monomers having the acidolabile group and an olefinic double bond.
    Among the monomers, those having a large and acid-labile group such as an alicyclic ester group (for example a 2-alkyl-2-adamantyl ester group and a 1- (1-adamantyl) -1-alkylalkyl ester) are preferred, since an excellent resolution when the resin obtained is used in the present composition.
    Examples of such monomers containing the bulky and acidolabile group include 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate, 1- (1-adamantyl) acrylate -alkylalkyl, (1-adamantyl) -1-alkylalkyl methacrylate, 2-alkyl-2-adamantyl-5-norbornene 2-carboxylate, 1- (1-adamantyl) -1-alkylalkyl 2-carboxylate, 2-alkyl-2-adamantyl Γα-chloroacrylate and 1- (1-adamantyl) -1-alkylalkyl α-chloroacrylate.
    Especially when using 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate or 2-alkyl-2-adamantyl Γα-chloroacrylate as monomers for the component In the present composition, there is a tendency to obtain a resist composition with excellent resolution. Typical examples in this regard include 2-methyl-2-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl acrylate, 2-ethyl-2-methacrylate, and the like. adamantyl, 2-n-butyl-2-adamantyl acrylate, 2-methyl-2-adamantyl α-chloroacrylate and 2-ethyl-2-adamantyl α-chloroacrylate. When using in particular 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-isopropyl-2-adamantyl acrylate or 2-isopropyl methacrylate -2-adamantyl for the present composition there is a tendency to obtain a resist composition with excellent sensitivity and high heat resistance. In the present invention, two or more types of monomers having one or more groups dissociated by the action of the acid can be used together, if necessary.
    The 2-alkyl-2-adamantyl acrylate can usually be produced by reacting a 2-alkyl-2-adamantanol or a metal salt thereof with an acrylic halide, and 2-alkyl-2-methacrylate. Adamantyl can usually be produced by reaction of a 2-alkyl-2-adamantanol or a metal salt thereof with a methacrylic halide.
    The resin used for the present composition may also contain other structural units derived from an acid-stable monomer, in addition to the aforementioned structural units having the acidolabile group. Here, the "structural unit derived from an acid-stable monomer" refers to a structural unit that is not dissociated by an acid generated by salt (I) and salt (II).
    Examples of such other structural units derived from the acid-stable monomer include a structural unit derived from a monomer having a free carboxyl group such as acrylic acid and methacrylic acid, a structural unit derived from an aliphatic dicarboxylic anhydride unsaturated such as maleic anhydride and itaconic anhydride, a structural unit derived from 2-norbornene, a structural unit derived from acrylonitrile or methacrylonitrile, a structural unit derived from an alkyl acrylate or a methacrylate d alkyl in which a carbon atom adjacent to the oxygen atom is a secondary or tertiary carbon atom, a structural unit derived from 1-adamantyl acrylate or 1-adamantyl methacrylate, a structural unit derived from a styrene monomer such as p-hydroxystyrene and m-hydroxystyrene, a structural unit derived from acryloyloxy-γ-butyrolactone or methacryloyloxy-γ-butyrolactone having a lactone ring which may be substituted by an alkyl group, and the like. Here, the 1-adamantyloxycarbonyl group is the acid stable group although the carbon atom adjacent to the oxygen atom is a quaternary carbon atom, and the 1-adamantyloxycarbonyl group may be substituted by at least one hydroxyl group .
    Specific examples of the structural unit derived from the acid-stable monomer include a structural unit derived from 3-hydroxy-1-adamantyl acrylate, a structural unit derived from 3-hydroxy-1-adamantyl methacrylate, a structural unit derived from of 3,5-dihydroxy-1-adamantyl acrylate, a structural unit derived from 3,5-dihydroxy-1-adamantyl methacrylate, a structural unit derived from α-acryloyloxy-γ-butyrolactone, a structural unit derived from α-methacryoloyloxy-γ-butyrolactone, a structural unit derived from β-acryloyloxy-γ-butyrolactone, a structural unit derived from β-methacryloyloxy-γ-butyrolactone, a structural unit represented by the formula (1):
    in which R 1 represents a hydrogen atom or a methyl group, R represents a methyl group, a trifluoromethyl group or a halogen atom, e represents an integer from 0 to 3, and when f is 2 or 3, the R 3 may be the same or different, a structural unit represented by formula (2):
    wherein R2 is hydrogen or methyl, R4 is methyl, trifluoromethyl or halogen, d is an integer of 0 to 3, and when e is 2 or 3, R3 is may be the same or different, a structural unit derived from p-hydroxystyrene, a structural unit derived from m-hydroxystyrene, a structural unit derived from an alicyclic compound having an olefinic double bond, as a structural unit represented by formula (3) :
    (3) wherein R5 and R6 each independently represent a hydrogen atom, a C1-C3 alkyl group, a C1-C3 hydroxyalkyl group, a carboxyl group, a cyano group, a group hydroxyl or a -COOU group in which U represents an alcohol residue, or R5 and R6 may be bonded together to form a carboxylic anhydride residue represented by -C (= O) 0C (= O) -, a unit structural derivative of an aliphatic unsaturated dicarboxylic anhydride, such as a structural unit represented by formula (4):
    (4) a structural unit represented by] formula (5): and the like.
    (5)
    In particular, the resin furthermore having at least one structural unit chosen from the structural unit derived from p-hydroxystyrene, the structural unit derived from m-hydroxystyrene, the structural unit derived from 3-hydroxy-1 acrylate adamantyl, the structural unit derived from 3-hydroxy-1-adamantyl methacrylate, the structural unit derived from 3,5-dihydroxy-1-adamantyl acrylate, the structural unit derived from methacrylate 3,5 1-dihydroxy-1-adamantyl, the structural unit represented by the formula (1) and the structural unit represented by the formula (2) in addition to the structural unit having the acidolabile group is preferable from the point of view of the adhesiveness of the resist on a substrate and the resolution of the resist.
    3-hydroxy-1-adamantyl acrylate, 3-hydroxy-1-adamantyl methacrylate, 3,5-dihydroxy-1-adamantyl acrylate and 3,5-dihydroxy-1-adamantyl methacrylate may for example, by reaction of the corresponding hydroxyadamantane with acrylic acid, methacrylic acid or its acid halide, and are also available commercially.
    In addition, acryloyloxy-γ-butyrolactone and methacryloyloxy-γ-butyrolactone having the lactone ring which may be substituted by the alkyl group may be produced by reaction of the corresponding α- or β-bromo-γ-butyrolactone. with acrylic acid or methacrylic acid, or by reaction of the corresponding α- or β-bromo-γ-butyrolactone with the acrylic halide or methacrylic halide.
    As monomers intended to give structural units represented by the formulas (1) and (2), there will be specifically mentioned, for example, an alicyclic lactone acrylate and a methacrylate of alicyclic lactones having the hydroxyl group, described below, and their mixtures. These esters may be produced, for example, by reaction of the corresponding alicyclic lactone having the hydroxyl group with acrylic acid or methacrylic acid, and their production method is for example described in JP 2000-26444. AT.
    Examples of acryloyloxy-γ-butyrolactone and methacryloyloxy-γ-butyrolactone having the lactone ring which may be substituted by the alkyl group include Γα-acryloyloxy-γ-butyrolactone, Γα-methacryloyloxy-γ-butyrolactone, -acryloyloxy-β, β-dimethyl-γ-butyrolactone, α-methacryloyloxy-β.β-methyl-γ-butyrolactone, Γα-acryloyloxy-α-methyl-γ-butyrolactone, Γα-methacryloyloxy-α-methyl-y butyrolactone, β-acryloyloxy-γ-butyrolactone, β-methacryloyoloxy-γ-butyrolactone and β-methacryloyloxy-α-methyl-γ-butyrolactone.
    The resin containing a structural unit derived from 2-nornornene has a solid structure, since the alicyclic group is directly present on its main chain and exhibits properties from which the resistance in dry etching is excellent. The structural unit derived from 2-norbornene can be introduced into the main chain by radical polymerization using, for example, an unsaturated aliphatic dicarboxylic anhydride such as maleic anhydride and itaconic anhydride together with the corresponding 2-norbornene. The structural unit derived from 2-norbornene is formed by opening its double bond, and may be represented by the above-mentioned formula (3). The structural unit derived from maleic anhydride and itaconic anhydride, which are the structural units derived from unsaturated aliphatic dicarboxylic anhydrides, are formed by opening their double bond and can be represented by formula (4) and formula (5) above.
    In R 5 and R 6 examples of the C 1 -C 3 alkyl group include methyl, ethyl and n-propyl groups, and examples of the C 1 -C 3 hydroxyalkyl group include hydroxymethyl and 2-hydroxyethyl groups.
    In R 5 and R 6, the group -COO 2 is an ester formed from the carboxyl group, and the alcohol residue corresponding to U, for example, is an optionally substituted C 1 -C 8 alkyl group, a 2-oxooxolan-3-yl group. , 2-oxooxolan-4-yl and the like, and as a substituent on the C1-C8 alkyl group, a hydroxyl group, an alicyclic hydrocarbon residue and the like.
    Specific examples of the monomer used to give the structural unit represented by the above-mentioned formula (3) may include 2-norbornene, 2-hydroxy-5-norbornene, 5-norbornene-2-carboxylic acid, 2-norbornene, 2-hydroxy-5-norbornene, methyl-5-norbornene carboxylate, 2-hydroxyethyl-5-norbornene 2-carboxylate, 5-norbornene-2-methanol and 5-norbornene-2,3-dicarboxylic anhydride.
    In the group -COOU, when U is the acidolabile group, the structural unit represented by the formula (3) is a structural unit having the acidolabile group, even having the norbornane structure. Examples of monomers yielding a structural unit having the acidolabile group include tert.-butyl-5-norbornene 2-carboxylate, 1-cyclohexyl-1-methylethyl-5-norbornene 2-carboxylate, 2-carboxylate 5-methylcyclohexyl-5-norbornene, 2-methyl-2-adamantyl-5-norbornene 2-carboxylate, 2-ethyl-2-adamantyl-5-norbornene 2-carboxylate, 1- (4-methoxy) -2-carboxylate Methylcyclohexyl) -1-methylethyl-5-norbornene, 1- (4-hydroxycyclohexyl) -1-methylhexyl-5-norbornene-2-carboxylate, 1-methyl-1- (4-oxocyclohexyl-ethyl) -2-carboxylate 5-norbornene, 1- (1-adamantyl) -1-methylethyl-5-norbornene-2-carboxylate, and the like.
    The resin used in the present composition preferably contains the structural unit (s) possessing the acidolabile group, generally in a proportion of 10 to 80 mol% in all the structural units of the resin, although the proportion varies according to the type of radiation. for pattern formation exposure, acidolabile group type, and the like.
    When the structural units in particular derived from 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate, 1- (1-adamantyl) -1-alkyl alkyl acrylate or 1-methacrylate - (1-adamantyl) -1-alkylalkyl are used as structural units possessing the acidolabile group, it is advantageous for the resistance of the resist in dry etching that the proportion of the structural units is 15 mol% or more in all the structural units of the resin.
    When, in addition to structural units having the acid-labile group, the resin contains other structural units having the acid-stable group, it is preferable that the sum of these structural units is on the order of 20 to 90 mol%, based on of all the structural units of the resin.
    In the case of KrF lithography, even if a structural unit derived from hydroxystyrene such as p-hydroxystyrene and m-hydroxystyrene is used, as one of the components of the resin, can obtain a reserve composition with sufficient transparency. To obtain such resins, the corresponding acrylic or methacrylic ester monomer can be polymerized radically with acetoxystyrene and styrene, and the acetoxy group of the structural unit derived from acetoxystyrene can then be deacetylated by an acid.
    Specific examples of the structural unit derived from hydroxystyrene include the following structural units represented by formulas (6) and (7).
    The resin used for the present resist composition can be produced in that the polymerization reaction of the corresponding monomer (s) is carried out. The resin may also be produced in that the oligomerization reaction of the corresponding monomer (s) is carried out followed by polymerization of the oligomer obtained.
    The polymerization reaction is usually carried out in the presence of a radical initiator.
    The radical initiator is not limited, and examples of this initiator include an azo compound such as 2,2'-azobis-isobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1 ' azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4-dimethyl-valeronitrile), 2,2-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis dimethyl azobis (2-methylpropionate) and 2,2'-azobis (2-hydroxymethylpropionitrile), an organic hydroperoxide such as lauroyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-peroxybenzoate n-butyl, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, tert-butyl peroxneodecanoate, tert-butyl peroxypivalate and 3,5,5-trimethylhexanoyl peroxide; , and an inorganic peroxide such as potassium peroxodisulfate, ammonium peroxodisulfate and hydrogen peroxide. Among them, the azo compound is preferable and 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2 ' -azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate) are more preferable, and 2,2'-azobis-isobutyronitrile and 2,2'-azobis (2 , 4-dimethyl-valeronitrile) are particularly preferable.
    These radical initiators can be used alone or in the form of a mixture of two or more types of them. When a mixture of two or more types of them is used, the mixing ratio is not particularly limited.
    The amount of the radical initiator is preferably 1 to 20 mol%, based on the molar amount of all monomers or oligomers.
    The polymerization temperature is usually 0 to 150 ° C, preferably 40 to 100 ° C.
    The polymerization reaction is usually conducted in the presence of a solvent, and the use of a solvent sufficient to dissolve the monomer, the radical initiator and the resulting resin is preferred. Examples include a hydrocarbon solvent such as toluene, an ether solvent such as 1,4-dioxane and tetrahydrofuran, a ketone solvent such as methyl isobutyl ketone, an alcohol solvent such as isopropyl alcohol, a cyclic ester solvent such as γ-butyrolactone, a glycolic ester-ether solvent such as propylene glycol monomethyl ether acetate, and an acyclic ester solvent such as ethyl lactate. These solvents can be used alone, or a mixture of them can be used.
    The amount of solvent is not limited and in practice is preferably 1 to 5 parts by weight based on 1 part of all monomers or oligomers.
    When an alicyclic compound having an olefinic double bond and an unsaturated aliphatic dicarboxylic anhydride are used as the monomers, it is preferable to use them in excess, since they tend not to be readily polymerized.
    At the end of the polymerization reaction, the resin produced can be isolated, for example, by adding to the reaction mixture obtained a solvent in which the present resin is insoluble or poorly soluble and filtration of the precipitated resin. If necessary, the isolated resin can be purified, for example by washing with a suitable solvent.
    The present resist composition preferably comprises from 80 to 99.9% by weight of the resin component and from 0.1 to 20% by weight of the sum of the salt (I) and the salt (II), based on the total amount of the resin component, salt (I) and salt (II).
    The quantitative proportion of salt (I) and salt (II) is usually 9/1 to 1/9.
    In the present resist composition, deterioration in performance caused by acid inactivation that occurs as a result of post-exposure delay can be reduced by addition of an organic base compound, particularly an organic base compound containing nitrogen, as a deactivator.
    Specific examples of the nitrogenous organic base compound include an amino compound represented by the following formulas:
    wherein R 11 and R 12 independently of one another are hydrogen, alkyl, cycloalkyl or aryl, and alkyl, cycloalkyl and aryl may be substituted by at least one a hydroxyl group, an amino group which may be substituted by a C 1 -C 4 alkyl group and a C 1 -C 6 alkoxy group which may be substituted by a C 1 -C 4 alkoxy group, R 13 and R 14 independently represent one of other a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, and the alkyl, cycloalkyl, aryl and alkoxy group may be substituted by at least one group selected from a hydroxyl group, a group amino which may be substituted by C 1 -C 4 alkyl and C 1 -C 6 alkoxy, or R 13 and R 14 bond together with the carbon atoms to which they are attached to form an aromatic ring, R 15 represents a Hyd atom hydrogen, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or a nitro group, and the alkyl, cycloalkyl, aryl and alkoxy group may be substituted by at least one group selected from a hydroxyl group, an amino group which may be substituted by C1-C4alkyl and C1-C6alkoxy, R16 is alkyl or cycloalkyl, and the alkyl and cycloalkyl group may be substituted by at least one group selected from a hydroxyl group, a group amino which may be substituted by C 1 -C 4 alkyl and C 1 -C 6 alkoxy, and W represents -CO-, -NH-, -S-, -S-, an alkylene group has at least one group methylene may be replaced by -O-, or an alkenylene group of which at least one methylene group may be replaced by -O-, and a quaternary ammonium hydroxide represented by the following formula:
    wherein R17, R18, R19 and R20 independently of one another are an alkyl group, a cycloalkyl group or an aryl group, and the alkyl, cycloalkyl and aryl group may be substituted by at least one group selected from a group hydroxyl, an amino group which may be substituted by a C1-C4 alkyl group and a C1-C6 alkoxy group.
    The alkyl group in R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 preferably has from 1 to 10 carbon atoms, and more preferably from 1 to 6 carbon atoms.
    Examples of amino groups which may be substituted by the C1-C4 alkyl group include amino, methylamino, ethylamino, n-butylamino, dimethylamino and diethylamino groups. Examples of the C1-C6 alkoxy group which may be substituted by the C1-C6 alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy groups. and 2-methoxyethoxy.
    Specific examples of the alkyl group which may be substituted by at least one group selected from a hydroxyl group, an amino group which may be substituted by a C 1 -C 4 alkyl group and a C 1 -C 6 alkoxy group, which may be substituted by a C1-C6 alkoxy group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, 2- (2-methoxyethoxy) ethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-aminoethyl, 4-aminobutyl and 6-aminohexyl.
    The cycloalkyl group in R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19 and R 20 preferably has from 5 to 10 carbon atoms. Specific examples of the cycloalkyl group which may be substituted by at least one group selected from hydroxyl group, an amino group which may be substituted by a C 1 -C 4 alkyl group and a C 1 -C 6 alkoxy group include cyclopentyl, cyclohexyl groups. cycloheptyl and cyclooctyl.
    The aryl group in R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19 and R 20 preferably has from 6 to 10 carbon atoms. Specific examples of the aryl group which may be substituted by at least one group selected from a hydroxyl group, an amino group which may be substituted by a C 1 -C 4 alkyl group and a C 1 -C 6 alkoxy group include phenyl and naphthyl groups. .
    The alkoxy group in R13, R14 and R15 preferably has from 1 to 6 carbon atoms, and specific examples of this group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy. , n-pentyloxy and n-hexyloxy.
    The alkylene and alkenylene groups of W preferably have from 2 to 6 carbon atoms. Specific examples of the alkylene group include ethylene, trimethylene, tetramethylene, methylenedioxy and ethylene-1,2-dioxy groups, and specific examples of the alkenylene group include ethane-1,2-diyl groups, 1-propene-1,3 -diyl and 2-butene-1,4-diyl.
    Specific examples of the amine compound include n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline 4-nitroaniline, 1-naphthylamine, 2-naphthylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3 , 3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, N-methylaniline, piperidine , diphenylamine, triethylamine, trimethylamine, tripyopylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, méthyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2-2-methoxyethoxy) ethyl] amine, triisopropanolamine, Ν, Ν-dimethylaniline, 2,6-diisopropylaniline, imidazole, benzimidazole, pyridine, 4-methylpyridine, 4-methylimidazole, bipyridine, 2,2'-dipyridylamine, di- 2-pyridylketone, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridylethane, 1,3-di (4-pyridyl) propane, 1,2-bis ( 2-pyridyl) ethylene, 1,2-bis (4-pyridyl) ethylene, 1,2-bis (4-pyridyloxy) ethane, 4,4-dipyridyl sulfide, 4,4'-dipyridyl disulfide 1,2-bis (4-pyridyl) ethylene, 2,2'-dipicolylamine and 3,3'-dipicolylamine.
    Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, hydroxide, and the like. (3-trifluoromethylphenyl) trimethylammonium and (2-hydroxyethyl) trimethylammonium hydroxide (called "choline").
    A hindered amine having a piperidine backbone as disclosed in JP 11-52575 A1 can also be used as a quencher.
    From the point of view of pattern formation with higher resolution, quaternary ammonium hydroxide is preferably used as a quencher.
    When the basic compound is used as deactivator, the present resist composition preferably comprises from 0.01 to 1% by weight of the basic compound, based on the total amount of the resin component, salt (I) and salt ( II).
    The present resist composition may contain, if necessary, a small amount of various additives such as a sensitizer, a solution-suppressing agent, other polymers, a surfactant, a stabilizer and a dye, as long as the effect of the present invention is not inhibited.
    The present resist composition is generally in the form of a liquid reserve composition wherein the aforementioned ingredients are dissolved in a solvent, and the liquid resist composition is applied to a substrate such as a silicon wafer, by a conventional method as a spin coating. The solvent used is sufficient to dissolve the aforementioned ingredients, have a suitable drying rate and give a uniform and smooth coating after evaporation of the solvent. Solvents generally used in the art can be used.
    Examples of the solvent include a glycol ether ester such as ethyl glycol acetate, methyl glycol acetate and propylene glycol monopropyl ether acetate, and acyclic esters such as ethyl lactate, butyl acetate amyl acetate and ethyl pyruvate, a ketone such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone, and a cyclic ether such as γ-butyrolactone. These solvents can be used alone, and two or more can be mixed for use.
    A resist film applied to the substrate and then dried is subjected to patterning exposure, then heat treated to facilitate a deblocking reaction, and then developed using an alkaline developer. The alkaline developer used may be any of various alkaline solutions used in the art. In general, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly called "choline") is often used.
    It should be understood that the embodiments disclosed herein are examples in all respects and are not limiting. The idea is that the scope of the present invention is determined, not by the foregoing descriptions, but by the appended claims, and covers all variants of the meanings and scope of the claims.
    The present invention will be more specifically described by way of examples, which are not to be construed as limiting the scope of the present invention. The "%" and "parts" used to represent the content of any compound and the amount of any material used in the Examples and Comparative Examples which follow are on a weight basis, unless otherwise expressly stated. The weight average molecular weight of any material used in the examples which follow is a value found by gel permeation chromatography (type HLC-8120GPC, column (three columns): TSK Multipore HXL-M gel, solvent, tetrahydrofuran, TOSOH CORPORATION] using styrene as the standard reference material. The structures of compounds were determined by NMR (type GX-270 or type EX-270, manufacture of JEOL LTD) and mass spectrometry (liquid chromatography: type 1100, manufacture of AGILENT TECHNOLOGIES LTD., Mass spectrometry: type LC / MSD or LC / MSD TOF, manufacture of AGILENT TECHNOLOGIES LTD.).
    EXAMPLE 1.- Synthetic salt
    1,230 parts of 30% aqueous sodium hydroxide solution were added to a mixture of 100 parts of methyldifluoro (fluorosulfonyl) acetate and 250 parts of ion-treated water in an ice bath. . The resulting mixture was heated and refluxed at 100 ° C for 3 hours. After cooling, the cooled mixture was neutralized with 88 parts of concentrated hydrochloric acid and the resulting solution was concentrated to obtain 164.8 parts of sodium salt of difluorosulfoacetic acid (containing an inorganic salt, purity). 62.8%).
    (2) 5.0 parts of sodium difluorosulfoacetate (purity: 62.8%), 2.6 parts of 4-oxo-1-adamantanol and 100 parts of ethylbenzene were mixed and 0.8 part was added concentrated sulfuric acid. The resulting mixture was refluxed for 30 hours. After cooling, the mixture was filtered to give solids, and the solids were washed with tert.-butyl methyl ether to give 5.5 parts of the salt represented by the above formula (a). Its purity was 35.6%, calculated by the result of a 1 H NMR analysis.
    1 H NMR (dimethyl sulfoxide - d6, internal standard tetramethylsilane): d (ppm) 1.84 (d, 2H, J = 13.0 Hz), 2.00 (d, 2H, J = 11.9 Hz) 2.29 - 2.32 (m, 7H), 2.54 (s, 2H).
    (3) To 5.4 parts of the salt represented by the formula (a), and obtained in (2) (purity: 35.6%), a mixed solvent of 16 parts of acetonitrile and 16 parts of water treated with ion exchange. A solution prepared by mixing 1.7 parts of triphenylsulfonium chloride, 5 parts of acetonitrile and 5 parts of ion-treated water was added to the resulting mixture. After 15 hours of stirring, the mixture obtained was concentrated and extracted with 142 parts of chloroform. The organic layer obtained was washed with water treated with ion exchange and concentrated. The resulting concentrate was washed with 24 parts of tert.-butyl methyl ether and the solvent was decanted to give 1.7 part of the salt represented by the above-mentioned formula (b) as a white solid which the we called B1.
    1 H NMR (dimethyl sulfoxide - d6, internal standard: tetramethylsilane): d (ppm) 1.83 (d, 2H, J = 12.7 Hz), 2.00 (d, 2H, J = 12 Hz), 2.29 - 2.32 (m, 7H), 2.53 (s, 2H), 7.75-7.91 (m, 15H).
    MS (ESI (+) spectrum): M + 263.2 (C18H15S + = 263.09) MS (ESI (-) spectrum): M-323.0 (C12H13F2O6S '= 323.04).
    EXAMPLE 2 Synthetic Salt (1) 230 parts of 30% aqueous sodium hydroxide solution were added to a mixture of 100 parts of methyldifluoro (fluorosulfonyl acetate) and 250 parts of water treated with sodium hydroxide. ions, in an ice bath. The resulting mixture was heated and refluxed at 100 ° C for 3 hours. After cooling, the cooled mixture was neutralized with 88 parts of concentrated hydrochloric acid and the resulting solution was concentrated to obtain 164.8 parts of sodium salt of difluorosulfoacetic acid (containing an inorganic salt, purity). 62.8%).
    (2) 30 parts sodium salt of sodium difluorosulfoacetic acid (purity: 62.8%), 14.7 parts of the compound represented by the above-mentioned formula (c) and 300 parts of toluene were mixed and there was added 18.1 parts of p-toluenesulfonic acid. The resulting mixture was heated and refluxed for 12 hours. The resulting solution was filtered to give the solids. The solids obtained were mixed with 100 parts of acetonitrile and the resulting mixture was filtered. The resulting filtrate was concentrated to give 26.7 parts of the salt represented by formula (d) above.
    1 H NMR (Dimethyl sulfoxide, internal standard tetramethylsilane): d (ppm) 1.57 -1.67 (m, 2H), 1.91 - 2.06 (m, 2H), 2.53 (dd) , 1H), 3.21 (td, 1H), 4.51 (d, 1H), 4.62 (s, 1H).
    (3) 26.7 parts of the salt represented by the formula (d), and obtained in (2) above were dissolved in 267 parts of acetonitrile. 23.9 parts of triphenylsulfonium chloride and 239 parts of ion-treated water were added to the resulting solution. The resulting mixture was stirred for 15 hours and then concentrated. The residue obtained was extracted twice with 200 parts of chloroform. The organic layers obtained were mixed, washed with water treated with ion exchange and concentrated. The resulting concentrate was mixed with 200 parts of tert.-butyl methyl ether and the resulting mixture was filtered to give 37.7 parts of the salt represented by the formula (e) as a pale yellow oil, which we called B2.
    1 H NMR (dimethyl sulfoxide - d6, tetramethylsilane internal standard): d (ppm) 1.57 -1.67 (m, 2H), 1.91 - 2.06 (m, 2H), 3.21 (td) , 1H), 4.51 (d, 1H), 4.62 (s, 1H), 7.76 - 7.91 (m, 15H).
    MS (ESI (+) spectrum): M + 263.2 (C 18 H 15 S + = 263.09) MS (ESI (-) spectrum): M-311.0 (C 10 H 9 F 2 O 7 S '= 311.00).
    EXAMPLE 3 Synthetic salt
    (1) 460 parts of 30% aqueous sodium hydroxide solution was added to a mixture of 200 parts of methyldifluoro (fluorosulfonyl) acetate and 300 parts of ion-treated water in a bath of ice cream. The resulting mixture was heated and refluxed at 100 ° C for 2.5 hours. After cooling, the cooled mixture was neutralized with 175 parts of concentrated hydrochloric acid, so that 328.19 parts of sodium salt of difluorosulfoacetic acid (containing an inorganic salt, purity: 62.8%) were obtained. .
    (2) 5.0 parts of sodium difluorosulfoacetate (purity: 62.8%), obtained in (1), 2.6 parts of 4-oxo-1-adamantanol and 100 parts of ethylbenzene were mixed and added 0.8 part of concentrated sulfuric acid. The resulting mixture was refluxed for 30 hours. After cooling, the mixture was filtered to give solids, and the solids were washed with tert.-butyl methyl ether to give 5.5 parts of the salt represented by the above formula (a). Its purity was 57.6%, calculated by the result of a 1 H NMR analysis.
    1H NMR (dimethylsulfoxide - d6, internal standard tetramethylsilane): d (ppm) 1.84 (d, 2H), 2.00 (d, 2H), 2.29 - 2.32 (m, 7H), 2.54 (s, 2H).
    (3) To 4.3 parts of the salt represented by formula (a), and obtained in (2) above (purity: 57.6%), 43.0 parts of chloroform were added. 2.2 parts of the sulfonium salt represented by the above-mentioned formula (f) and 11.7 parts of ion-treated water were added to the resulting mixture. After stirring for 15 hours, the mixture obtained was separated into an organic layer and an aqueous layer. The organic layer was washed several times with ion-exchange treated water until the resulting aqueous layer was neutralized and then concentrated. The resulting concentrate was mixed with 15.0 parts of tert.-methylbutyl ether and the supernatant was decanted off. The resulting residue was dried to give 2.3 parts of the salt represented by the above formula (g) as a white solid, which was named B3.
    1H NMR (dimethylsulfoxide - d6, internal standard tetramethylsilane): d (ppm) 1.82 (d, 2H), 1.98 (d, 2H), 2.27 - 2.35 (m, 7H), 2.51 (s, 2H), 7.52 (d, 4H), 7.74-7.89 (m, 20H), 7.91 (d, 4H).
    EXAMPLE 4 Synthetic Salt
    (1) 460 parts of 30% aqueous sodium hydroxide solution was added to a mixture of 200 parts of methyldifluoro (fluorosulfonyl) acetate and 300 parts of ion-treated water in a bath of ice cream. The resulting mixture was heated and refluxed at 100 ° C for 2.5 hours. After cooling, the cooled mixture was neutralized with 175 parts of concentrated hydrochloric acid and the resulting solution was concentrated so that 328.19 parts of sodium salt of difluorosulfoacetic acid (containing an inorganic salt, purity 62.8%).
    (2) 75.1 parts of p-toluenesulfonic acid were added to a mixture of 123.3 parts of the sodium salt of sodium difluorosulphoacetic acid (purity: 62.8%), 65.1 parts of 1-adamantane-methanol and 600 parts of dichloroethane, and the resulting mixture was heated and refluxed for 12 hours. The mixture was concentrated to remove dichloroethane and 400 parts of tert.-butyl methyl ether were added to the resulting residue. The resulting mixture was stirred and filtered to give the solid. 400 parts of acetonitrile were added to the solid and the resulting mixture was stirred and filtered, and this operation was repeated. The resulting filtrates were mixed and the resulting solution was concentrated to give 99.5 parts of the salt represented by the above-mentioned formula (h).
    1 H NMR (dimethyl sulfoxide, internal standard tetramethylsilane): d (ppm) 1.51 (d, 6H), 1.62 (dd, 6H), 1.92 (s, 3H), 3.80 ( s, 2H).
    (3) 5.0 parts of thioanisole were dissolved in 15.0 parts of acetonitrile. To this was added 8.35 parts of silver perchlorate (I) and then 11.4 parts of acetonitrile solution containing 5.71 parts of methyl iodide were added. The resulting mixture was stirred for 24 hours. The precipitate was filtered for removal and the filtrate was concentrated. The concentrate was mixed with 36.8 parts of tert.-butyl methyl ether and the resulting mixture was stirred and filtered to give 8.22 parts of dimethylphenylsulfonium perchlorate as a white solid.
    (4) 5.98 parts of the salt represented by the above-mentioned formula (h), obtained in (2) above, were mixed with 35.9 parts of chloroform. To the resulting mixture was added a solution obtained by mixing 4.23 parts of dimethylphenylsulfonium perchlorate obtained in (3) and 12.7 parts of ion-treated water. The resulting mixture was stirred for 4 hours, and separated into an organic layer and an aqueous layer. The aqueous layer was extracted with 23.9 parts of chloroform to give a layer in chloroform. The organic layer and the chloroform layer were mixed and washed several times with ion-treated water until the resulting aqueous layer was neutralized and then concentrated. The resulting concentrate was mixed with 31.8 parts of tert.-butyl methyl ether and the resulting mixture was filtered to give 5.38 parts of the salt represented by the above-mentioned formula (i) as a white solid, which we called B4.
    1 H NMR (dimethylsulfoxide - d6, internal standard tetramethylsilane): d (ppm) 1.51 (d, 6H), 1.62 (dd, 6H), 1.92 (s, 3H), 3.26 ( s, 6H), 3.80 (s, 2H), 7.68-7.80 (m, 3H), 8.03-8.06 (m, 2H).
    MS (ESI (+) spectrum): M + 193.0 (C8H11S + = 139.06) MS (ESI (-) spectrum): M-323.0 (C18 H28 OsS '= 323.08).
    EXAMPLE 5 Synthetic Salt
    (1) 32.8 parts of the salt represented by the above-mentioned formula (h), obtained by a process similar to that described for the synthetic salt of Example 4 above (1) and (2), were dissolved in 100 parts of water treated with ion exchange. To the resulting solution was added a mixture of 28.3 parts of triphenylsulfonium chloride and 140 parts of methanol, and stirred for 5 hours. The resulting mixture was concentrated. The resulting residue was extracted twice with 200 parts of chloroform. The organic layers obtained were mixed and washed repeatedly with ion-exchange treated water until the resulting aqueous layer was neutralized. The resulting solution was concentrated. 300 parts of tert.-butyl methyl ether were added to the concentrate and stirred. The resulting mixture was filtered and the resulting solid was dried to give 39.7 parts of the salt represented by the above-mentioned formula G) as a white solid which was named B5.
    1H NMR (dimethyl sulfoxide - d6, internal standard: tetramethylsilane): δ (ppm) 1.52 (d, 6H), 1.63 (dd, 6H), 1.93 (s, 3H), 3.81 (s, 2H), 7.76 - 7.90 (m, 15H).
    MS (ESI (+) spectrum): M + 263.2 (C18H25S + = 263.09) MS (ESI (-) spectrum): M-323.0 (C13H17F2O5S '= 323.08).
    EXAMPLE 6.- Synthetic salt
    (1) 460 parts of 30% aqueous sodium hydroxide solution was added to a mixture of 200 parts of methyldifluoro (fluorosulfonyl) acetate and 300 parts of ion-treated water in a bath of ice cream. The resulting mixture was heated and refluxed at 100 ° C for 2.5 hours. After cooling, the cooled mixture was neutralized with 175 parts of concentrated hydrochloric acid and the resulting solution was concentrated so that 328.19 parts of sodium salt of difluorosulfoacetic acid (containing an inorganic salt, purity 62.8%).
    (2) 123.3 parts of sodium salt of difluorosulfoacetic acid (purity: 62.8%), 65.7 parts of 1-adamantane-methanol and 600 parts of dichloroethane were mixed and added to 75, 1 parts of p-toluenesulfonic acid. The resulting mixture was heated and refluxed for 12 hours. The resulting solution was concentrated for removal of dichloroethane. The resulting residue was mixed with 400 parts of tert.-butyl methyl ether and the resulting mixture was stirred. The mixture was filtered to give the solid. The solid was mixed with 400 parts of acetonitrile and the resulting mixture was filtered to give the filtrate and the solid. The resulting solid was mixed with 400 parts of acetonitrile and the resulting mixture was filtered to give the filtrate and the solid. The resulting filtrates were mixed and concentrated to give 99.5 parts of the salt represented by the above formula (h).
    1 H NMR (dimethylsulfoxide-dβ, internal standard: tetramethylsilane): d (ppm) 1.51 (d, 6H), 1.62 (dd, 6H), 1.92 (s, 3H), 3.80 (s, 2H).
    (3) 150 parts of 2-bromoacetophenone were dissolved in 375 parts of acetone, and 66.5 parts of tetrahydrothiophene were added dropwise to the resulting solution. The resulting mixture was stirred at room temperature for 24 hours and the white precipitates were filtered, washed and dried to give 207.9 parts of 1- (2-oxo-2-phenylethyl) tetrahydrothiophenium bromide as crystals. white.
    1H NMR (dimethylsulfoxide - d6, internal standard: tetramethylsilane): d (ppm) 2.13 - 2.36 (m, 4H), 3.50 - 3.67 (m, 4H), 5.41 ( s, 2H), 7.63 (t, 2H), 7.78 (t, 1H), 8.02 (d, 2H).
    (4) 99.5 parts of the salt represented by formula (h), obtained in step (2) above, were dissolved in 298 parts of acetonitrile. 79.5 parts of 1- (2-oxo-2-phenylethyl) tetrahydrothiophenium bromide obtained in (3) above and 159 parts of ion-treated water were added to the resulting solution. The resulting mixture was stirred for 15 hours and concentrated. The resulting concentrate was extracted twice with 500 parts of chloroform. The organic layers obtained were mixed, washed with water treated with ion exchange and concentrated. To the concentrate was added 250 parts of tert.-butyl methyl ether and the resulting mixture was stirred and filtered. The resulting solid was dried under reduced pressure to give 116.9 parts of the salt represented by the above-mentioned formula (k) as a white solid which was named C1.
    1H NMR (dimethylsulfoxide - d6, internal standard tetramethylsilane): d (ppm) 1.50 (d, 6H), 1.62 (dd, 6H), 1.92 (s, 3H), 2.13 - 2.32 (m, 4H), 3.45 - 3.63 (m, 4H), 3.80 (s, 2H), 5.30 (s, 2H) 7.62 (t, 2H), 7, 76 (t, 1H), 8.88 (s, 2H).
    MS (ESI (+) spectrum): M + 207.0 (C12H15OS + = 207.08) MS (ESI (-) spectrum): M-323.0 (C13H17F2O5S '= 323.08).
    EXAMPLE 7 Synthetic Salt
    (1) 10.0 parts of the salt represented by the formula (a) (purity: 55.2%), obtained by a process similar to that described in the example of synthetic salt 1, (1) and (2), were mixed with a mixed solvent composed of 30 parts of acetonitrile and 20 parts of ion-treated water. The resulting solution was added to the resulting mixture by mixing 5.0 parts of 1- (2-oxo-2-phenylethyl) tetrahydrothiophenium bromide, 10 parts of acetonitrile and 5 parts of ion-exchanged water. After stirring for 15 hours; the stirred mixture was concentrated and extracted with 98 parts of chloroform. The organic layer was washed with ion-treated water. The organic layer obtained was concentrated. The concentrate was mixed with 70 parts of ethyl acetate and the resulting mixture was filtered to give 5.2 parts of the salt represented by the above-mentioned formula (o) as a white solid which was called C2.
    1 H NMR (dimethyl sulfoxide, internal standard tetramethylsilane): d (ppm) 1.83 (d, 2H, J = 12.5 Hz), 2.00 (d, 2H, J = 12.0 Hz) , 2.21 - 2.37 (m, 11H), 2.53 (s, 2H), 3.47 - 3.62 (m, 4H), 5.31 (s, 2H), 7.63 ( t, 2H, J = 7.3 Hz), 7.78 (t, 1H, J = 7.6 Hz), 8.01 (dd, 2H, J = 1.5 Hz, 7.3 Hz).
    MS (ESI (+) spectrum): M + 207.1 (C12H15OS + = 207.08) MS (ESI (-) spectrum): M-323.0 (C18H18 FsOeS '= 323.04).
    EXAMPLE 8 Synthetic Salt
    (1) 50 parts of 2-bromo-4'-methoxyacetophenone were dissolved in 150 parts of acetone and 19 parts of tetrahydrothiophene were added dropwise thereto. The resulting mixture was stirred for 24 hours at room temperature and then filtered to give a white precipitate. The precipitate was washed with acetone and dried to give 63 parts of 1- [2-oxo-2- (4'-methoxyphenylethyl)] tetrahydrothiophenium bromide as a white solid.
    1 H NMR (dimethyl sulfoxide - d6, internal tetramethylsilane standard): d (ppm) 2.14 - 2.34 (m, 4H), 3.48 - 3.65 (m, 4H), 3.89 (s) , 3H), 5.39 (s, 2H), 7.15 (d, 2H, J = 8.9 Hz), 8.00 (d, 2H, j = 8.9 Hz).
    (2) 3.05 parts of the salt represented by the above-mentioned formula (h) obtained by a process similar to that described in (1) and (2) for Example 6 of synthetic salt were dissolved in 15.3 parts of acetonitrile. To the resulting solution was added a solution prepared by mixing 2.6 parts of 1- [2-oxo-2- (4'-methoxyphenylethyl)] tetrahydrothiophenium bromide, obtained in (1) above, and 13, 1 part of water treated with ion exchange. The resulting mixture was stirred for 15 hours and concentrated. The residue obtained was extracted twice with 50 parts of chloroform and the extracts obtained were washed with water treated with ion exchange and concentrated. The concentrate was mixed with 30 parts of tert.-butyl methyl ether and the resulting mixture was filtered to give the solid. The solid was dried to give 3.44 parts of the salt represented by the above-mentioned formula (p) as a white solid, which was named C3.
    1H NMR (dimethyl sulfoxide - d6, internal standard: tetramethylsilane): d (ppm) 1.52 (d, 6H), 1.6 (dd, 6H), 1.93 (s, 3H), 2.12 -2.30 (m, 4H), 3.43 - 3.60 (m, 4H), 3.81 (s, 2H), 3.88 (s, 3H), 5.26 (s, 2H), 7.15 (d, 2H), 7.98 (d, 2H).
    MS (ESI (+) spectrum): M + 237.2 (C 13 H 15 O 2 S + = 237.09) MS (ESI (-) spectrum): M-323.0 (O 2 H 2 O 5 S = 323.08).
    EXAMPLE 1 Synthetic resin
    The monomers used in this example of synthetic resin are the following monomers M1, M2 and M3.
    The monomer M1, the monomer M2 and the monomer M3 were dissolved in an amount of methylisobutylketone twice the amount of all the monomers to be used (molar proportion of the monomers: monomer 1: monomer 2: monomer 3 = 5: 2.5: 2.5). To the solution was added 2,2'-azobisisobutyronitrile as initiator, in a proportion of 2 mol% based on the total molar amount of the monomers, and the resulting mixture was heated at 80 ° C for 8 hours. . The reaction solution was poured into a large amount of heptane to precipitate. The precipitate was isolated and washed twice with a large amount of heptane for purification. As a result, a copolymer having a weight average molecular weight of about 9200 was obtained. This copolymer had the following structural units. It is designated as A1 resin.
    EXAMPLE 2. Synthetic resin
    The monomers used in this example of synthetic resin are the monomers M1, M2 and M4 below.
    The monomer M1, the monomer M2 and the monomer M4 were dissolved in a quantity of 1,4-dioxane equal to 1.28 times the amount of all the monomers to be used (molar proportion of the monomers: monomer M1: monomer M2: monomer M4 = 50: 25:25). To the solution was added 2,2'-azobisisobutyronitrile as initiator in a proportion of 3 mol% based on the total molar amount of the monomers. The resulting solution was added to 0.72 times the amount of 1,4-dioxane corresponding to the amount of all the monomers to be used at 88 ° C for 2 hours. The resulting mixture was stirred at the same temperature for 5 hours. The reaction solution was cooled and then poured into a large amount of a mixed solvent of methanol and water to precipitate. The precipitate was isolated and washed twice with a large amount of methanol for purification. As a result, a copolymer having a weight average molecular weight of about 8500 was obtained. This copolymer had the following structural units. It is designated as A2 resin.
    EXAMPLE 3 Synthetic resin
    The monomers used in this example of synthetic resin are the monomers M1, M2, M3, M4 and M5 below.
    The monomer M1, the monomer M2, the monomer M3, the monomer M4 and the monomer M5 were dissolved in a quantity of 1,4-dioxane equal to 1.3 times the amount of all the monomers to be used (molar proportion of the monomers : monomer M1: monomer M2: monomer M3: monomer M4: monomer M5 = 25: 5: 30: 20: 20). To the solution was added 2,2'-azobisisobutyronitrile as initiator in a proportion of 2.5 mol% based on the total molar amount of the monomers. The resulting solution was added to 1.3 times the amount of 1,4-dioxane corresponding to the amount of all the monomers to be used at 87 ° C for 2 hours. The resulting mixture was stirred at the same temperature for 6 hours. The reaction solution was cooled and then poured into a large amount of methanol to precipitate. The precipitate was isolated and washed twice with a large amount of methanol for purification. As a result, a copolymer having a weight average molecular weight of about 9100 was obtained. This copolymer had the following structural units. It is designated as resin A3.
    EXAMPLES 1 TO 10 AND COMPARATIVE EXAMPLES 1 TO 7 .- <Acid generator) Acid generator B1:
    B2 acid generator:
    B3 acid generator:
    B4 acid generator:
    B5 acid generator:
    C1 acid generator:
    C2 acid generator:
    C3 acid generator:
    <Resin> Resins A1 to A3.
    <Deactivator> Q1: 2,6-diisopropylamine.
    <Solvent> Y1: propylene glycol monomethyl ether acetate 145 parts 2-heptanone 20.0 parts propylene glycol monomethyl ether 20.0 parts γ-butyrolactone 3.5 parts
    The following components were mixed and dissolved, and then filtered on a fluororesin filter having a pore diameter of 0.2 μm, to prepare the liquid reserve.
    Resin (type and quantity as described in Table 1) Acid generator (type and quantity as described in Table 1) Deactivator (type and quantity as described in Table 1) Solvent (type as described in Table 1)
    Silicon wafers were coated with "ARC-29A", which is an organic antireflective coating composition available from Nissan Chemical Industries, Ltd., and then baked under the following conditions: 205 ° C, 60 ° C .; seconds, to form an organic anti-reflective coating with a thickness of 780 A. Each of the liquid reserves prepared as above was deposited by centrifugation on the anti-reflective coating, so that the thickness of the resulting film becomes 0.15 μm after drying. The silicon wafers thus coated with the respective liquid reserves were each precooked on a direct hot plate at a temperature indicated in column "PB" of Table 1 for 60 seconds. Using an ArF progressive excimer ("FPA-5000AS3" manufactured by Canon Inc., NA = 0.75, annular 2/3), each slab thus formed with the respective resist film was subjected to pattern with lines and spaces, the amount of exposure being varied gradually.
    After exposure, each slab was subjected to post-exposure cooking on a hot plate at a temperature indicated in the "PEB" column of Table 1 for 60 seconds, followed by 60 seconds paddle development with a solution. 2.38% by weight aqueous solution of tetramethylammonium hydroxide.
    Each dark zone pattern grown on the organic anti-reflective coating substrate was observed, after development, with a scanning electron microscope, and the results are shown in Table 2. The term "dark area pattern" as used in FIG. 'used herein' means a pattern obtained by exposure and development with a reticle comprising a chromium base surface (light-arresting portion) and linear layers of glass (light-transmitting portion) formed on the chromium surface and aligned with each other . Therefore, the dark area pattern is such that after exposure and development, the resist layer surrounding the line and space pattern remains on the substrate.
    Effective Sensitivity (ES): It is expressed as the amount of exposure such that the line pattern and space pattern are 1: 1 after exposure by a 100 nm mask to lines and spaces and development.
    Line Edge Roughness (LER): Each pattern wall surface developed on the anti-reflective coating substrate after development was observed using a scanning electron microscope. When the wall surface is smoother than that of Comparative Example 1, its evaluation is marked with an "O", when the wall surface is as smooth as that of Comparative Example 1, its evaluation is marked by a "Δ", and when the wall surface is rougher than that of Comparative Example 1, its evaluation is marked with an "X".

    As can be seen from Table 2, the resist compositions of the examples according to the present invention give a good reserve pattern for the resolution and smoothness of the wall surface.
    The present composition provides good resist pattern resolution and good line edge roughness, and is particularly suitable for ArF excimer laser lithography, KrF excimer laser lithography and ArF immersion lithography.
    权利要求:
    Claims (22)
    [1]
    A chemical amplification resist composition comprising: (A) a salt represented by formula (I):

    [2]
    2. A resist composition according to claim 1, wherein Q1, Q2, Q3 and Q4 are each independently of one another a fluorine atom or a trifluoromethyl group.
    [3]
    The resist composition of claim 1, wherein Q1, Q2, Q3 and Q4 are fluorine atoms.
    [4]
    The resist composition according to claim 1, wherein A + is a cation represented by the formula (Id), (Ic) or (If):

    [5]
    The resist composition of claim 1, wherein A is a cation represented by the formula (Ig):

    [6]
    The resist composition of claim 1, wherein A + is a cation represented by the formula (Ih):

    [7]
    The resist composition of claim 1, wherein R21 represents a group represented by the formula:

    [8]
    The resist composition of claim 7, wherein the group represented by the formula

    [9]
    The resist composition of claim 1, wherein A + is a cation represented by the formula (Ih):

    [10]
    The resist composition of claim 9, wherein the group represented by the formula: is a group

    [11]
    The resist composition of claim 1, wherein P6 and P7 are linked to form a C3-C12 acyclic divalent hydrocarbon group which forms a ring with the adjacent S +, P8 is a hydrogen atom, P9 is an alkyl group C1 to C12, a C3 to C12 cycloalkyl group or an aromatic group which may be substituted by at least one group selected from a C1 to C6 alkoxy group, a C2 to C20 acyl group and a nitro group.
    [12]
    The resist composition of claim 1, wherein R22 represents a group represented by the formula:

    [13]
    The resist composition of claim 12, wherein the group represented by the formula:

    [14]
    The resist composition of claim 1, wherein P6 and P7 are bonded to form a divalent C3-C12 acyclic hydrocarbon group which forms a ring with the adjacent S +, P8 is hydrogen, P9 is alkyl. C1 to C12, a C3 to C12 cycloalkyl group or an aromatic group which may be substituted by at least one group selected from C1 to C6 alkoxy, C2 to C20 acyl and nitro, and R22 is group represented by the formula:

    [15]
    The resist composition of claim 14, wherein the group represented by the formula:

    [16]
    The resist composition of claim 1, wherein A + is a cation represented by the formula (1h):

    [17]
    The resist composition of claim 16 wherein the group represented by the formula:

    [18]
    The resist composition of claim 1, wherein the quantitative ratio of the salt represented by the formula (I) to the salt represented by the formula (II) is from 9/1 to 1/9.
    [19]
    The resist composition of claim 1, wherein the resin contains a structural unit derived from a monomer having a bulky and acidolabile group.
    [20]
    The resist composition of claim 19, wherein the bulky and acidolabile group is a 2-alkyl-2-adamantyl ester group or a 1- (1-adamantyl) -1-alkylalkyl ester group.
    [21]
    The resist composition of claim 19, wherein the monomer having a bulky and acidolabile group is a 2-alkyl-2-adamantyl acrylate, a 2-alkyl-2-adamantyl methacrylate, a 1- (1- adamantyl) -1-alkylalkyl, 1- (1-adamantyl) -1-alkylalkyl methacrylate, 2-alkyl-2-adamantyl-5-norbornene 2-carboxylate, 1 (1-adamantyl) carboxylate 1-alkylalkyl-5-norbornene, a 2-alkyl-2-adamantyl α-chloroacrylate or a 1- (1-adamantyl) -21-alkylalkyl α-chloroacrylate.
    [22]
    The resist composition of claim 1, wherein the resist composition further comprises a basic compound.
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    法律状态:
    2014-06-30| RE| Patent lapsed|Effective date: 20131231 |
    优先权:
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    JP2006329132|2006-12-06|
    JP2006329132|2006-12-06|
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