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    • 专利摘要:
    A chemically amplified resist composition comprising: (A) A salt of the formula: wherein Q1 is a C1-C8 perfluoroalkyl group and A + is at least one organic cation selected from the cations of formulas: (B) A salt represented of the formula: in which R22 represents a C1-C30 hydrocarbon group, which may be substituted, Q3 and Q4 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group, and A, + represents an organic cation of the formula: (C) A resin which contains a structural unit having an acid-sensitive group, insoluble or poorly soluble in an aqueous alkaline solution but becoming soluble in an aqueous alkaline solution by the action of an acid.
    公开号:BE1018035A3
    申请号:E2008/0138
    申请日:2008-03-06
    公开日:2010-04-06
    发明作者:Statoshi Yamaguchi；Yoshiyuki Takata；Satoshi Yamamoto
    申请人:Sumitomo Chemical Co；
    IPC主号:
    专利说明:

    CHEMICALLY AMPLIFIED RESIST COMPOSITION
    Field of the invention
    The present invention relates to a chemically amplified resist composition.
    Background of the invention
    A chemically amplified resist composition used for microfabrication of semi-conductors employing a lithographic process, contains a resin which comprises a structural unit having an acid-sensitive moiety and which itself is insoluble or poorly soluble in an aqueous alkaline solution but becomes soluble in an aqueous alkaline solution by the action of an acid, and an acid generator comprising a radiation-generating compound.
    In semiconductor microfabrication, it is desirable to form patterns having high resolution and good line edge roughness and it is expected that a chemically amplified resist composition will provide such patterns.
    US 2006-0194982-A1 discloses a. chemically amplified resist composition containing the salt represented by the following formula:
    wherein E represents a hydrogen atom or a hydroxyl group, and a resin which contains a structural unit having an acid-sensitive group and which is itself insoluble or poorly soluble in an aqueous alkaline solution, but becomes soluble in a solution aqueous alkaline by the action of an acid.
    US 2003/0194639 A1 discloses a chemically amplified resist composition containing the salt represented by the following formula:
    as an acid generator.
    US 2003/0194639 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 and other objects of the present invention will become apparent from the following description.
    The present invention relates to the following: 1. Chemically amplified resist composition comprising:
    (I) (A) A salt represented by the formula (I): wherein Q1 represents a C1-C8 perfluoroalkyl group and A + represents at least one organic cation selected from the cations represented by formula (Ia):
    (la) in which P1, P2 and P3 each independently represent a C1-C30 alkyl group, which may be substituted by at least one group chosen from a hydroxyl group, a C3-C12 cyclic hydrocarbon group and a C1-alkoxy group. -C12, 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):
    (Xb) wherein P4 and P5 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, and a cation represented by the formula (Ic):
    (ie) wherein P10, Pu, P12, P13, P14, P15, P16, P17, P18, P19, P20 and P21 each independently represent a hydrogen atom, a hydroxyl group, a C1-alkyl group. -C12 or'C1-C12 alkoxy group, B represents a sulfur or oxygen atom and m represents 0 or 1, (B) A salt represented by the formula (II):
    / (II) wherein R22 represents a C1-C30 hydrocarbon group, which may be substituted, and at least one -CH2- unit of the hydrocarbon group may be substituted with -CO- or -O-, Q3 and Q4 represent, each independently, a fluorine atom or a C1-C6 perfluoroalkyl group, and A '+ represents an organic cation represented by
    (IIa) the formula (IIa): in which P6 and P7 each independently represent a C1-C12 alkyl group or a C3-C12 cycloalkyl group, or P6 and P7 are joined to form a divalent C3 acyclic hydrocarbon group; -C12 which forms a ring together with the adjacent S + element, and at least one -CH2- unit in the divalent acyclic hydrocarbon group may be substituted with -CO-, -O- or -S-, P8 represents an atom of hydrogen, 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 joined to form a divalent acyclic hydrocarbon group which forms a 2-oxocycloalkyl group together with the adjacent -CHCO- group, and at least one -CH2- unit in 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-sensitive moiety and which is itself insoluble or poorly soluble in an aqueous alkaline solution, but becomes soluble in an aqueous alkaline solution by the action of an acid; 2. A resist composition according to item 1, wherein Q3 and Q4 each independently represent a fluorine atom or a trifluoromethyl group; 3. A resist composition according to item 1, wherein Q3 and Q4 are fluorine atoms; 4. A resist composition according to any one of 1. · to 3, wherein A + is a cation represented by the formula (Id), (le) or (If):
    (Id) (I) (if) wherein P28, P29 and P30 each independently represent a C1-C20 alkyl group or a C3-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 substituted with 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 cyclic hydrocarbon group; -C30 may be substituted with 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, a C1-C12 alkyl group, a C1-C12 alkoxy group or a C3-C12 cyclic hydrocarbon group, and 1, k, j, i, h and g represent each independently an integer of 0 to 5; A resist composition according to any one of 1 to 3, wherein A + is a cation represented by the formula (Ig):
    dg) 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; Resistance composition according to any one of items 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; Resistance composition according to any one of 1. to 6. wherein R22 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 C3-C30 monocyclic or polycyclic hydrocarbon group, in which a hydrogen atom is substituted with a hydroxyl group on the Y1 position when Y1 represents -CH (OH) -, or in which two hydrogen atoms are substituted by = O on the Y1 position when Y1 represents -CO-, and at least one hydrogen atom of the C3-C30 monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, an alkoxy group with C1-C6, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group; Resistance composition according to item 7, wherein the group represented by the formula:
    is a group represented by the formula (1), (m) or (n):
    *

    (1) (m) (n); 9. A resist composition according to any one of 1. to 3. wherein A + is a cation represented by the formula (Ih):
    (Ih) i wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group and R22 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 C3-C30 monocyclic or polycyclic hydrocarbon group, in which a hydrogen atom is substituted with a hydroxyl group on the Y1 position when Y1 represents -CH (OH) -, or in which two hydrogen atoms are substituted by = O at the Y1 position when Y1 is -CO-, and at least one hydrogen atom in the C3-C30 monocyclic or polycyclic hydrocarbon group may be substituted by a C1-C6 alkyl group, an alkoxy group C1-C6, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group; 10. A resist composition according to item 9, wherein the group represented by the formula:
    is a group represented by the formula (1), (m) or (n):

    U) ("O (n).
    J
    A resist composition according to any one of items 1 to 10, wherein P6 and P7 are joined to form a divalent C3-C12 hydrocarbon group which forms a ring together with the adjacent S + element, 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 chosen from a C1-C6 alkoxy group, an acyl group containing C2-C20 and a nitro group; Resistance composition according to any one of items 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 P6 and P7 are joined to form a divalent C3-C12 acyclic hydrocarbon group, which forms a ring together with with the adjacent S + element, 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 chosen from an alkoxy group C1-C6, a C2-C20 acyl group and a nitro group; Resin composition according to item 12, wherein R22 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 C3-C30 monocyclic or polycyclic hydrocarbon group, in which a hydrogen atom is substituted with a hydroxyl group on the Y1 position when Y1 represents -CH (OH) -, or in which two hydrogen atoms are substituted by = O at the Y1 position when Y is -CO-, and at least one hydrogen atom of the C3-C30 monocyclic or polycyclic hydrocarbon group may be substituted by a C1-C6 alkyl group, a C1-alkoxy group -C6, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group; 14. A resist composition according to item 13. wherein the group represented by the formula:
    is a group represented by formula (1), (m) or (n): 15. A resist composition according to any one of items 1 to 14, wherein the quantitative ratio of

    (L M n)
    .
    salt represented by formula (I) to the salt represented by formula (II) is from 9/1 to 1/9; Resin composition according to any of items 1 to 15, wherein the resin contains a structural unit derived from a monomer having a bulky acid-sensitive moiety; 17. A resist composition according to item 16, wherein the bulky and acid-sensitive moiety is a 2-alkyl-2-adamantyl ester moiety or a 1- (1-adamantyl) -1-alkylalkyl ester moiety; 18. A resist composition according to item 16, wherein the monomer having a bulky and acid-sensitive moiety is 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate, acrylate 1- (1-adamantyl) -1-alkylalkyl, 1- (1-adamantyl) -1-alkylalkyl methacrylate, 2-alkyl-2-adamantyl 5-norbornene-2-carboxylate, 5-norbornene 1- (1-adamantyl) -1-alkylalkyl 2-carboxylate, 2-alkyl-2-adamantyl α-chloroacrylate or 1- (1-adamantyl) -1-alkylalkyl α-chloroacrylate; 19. A resist composition according to any one of 1. to 18. wherein the resist composition also comprises a basic compound.
    Description of Preferred Embodiments
    In the salt represented by formula (I) (hereinafter simply referred to as salt (I)), Q1 represents a C1-C8 perfluoroalkyl group. Examples of a C1-C8 perfluoroalkyl group include the trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, heptadecafluorooctyl, perfluorocyclohexyl and perfluoro-4-ethylcyclohexyl groups, of which a linear chain C1-C8 perfluoroalkyl group is preferred. branched.
    A + represents at least one organic cation chosen from the cations represented by the formula (la):
    (la) in which P1, P2 and P3 each independently represent a C1-C30 alkyl group, which may be substituted by at least one group chosen from a hydroxyl group, a C3-C12 cyclic hydrocarbon group and a C1-alkoxy group. -C12, or a C3-C30 cyclic hydrocarbon group which may be substituted with at least one group chosen from a hydroxyl group and a C1-C12 alkoxy group (hereinafter simply referred to as cation (Ia)), a cation represented by the formula (Ib):
    (Ib) wherein P4 and P5 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group (hereinafter referred to simply as cation (Ib)), and
    t (le) a cation represented by formula (Ic): 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 represents 0 or 1 (hereinafter simply referred to as cation (Ie)).
    Examples of the C1-C12 alkoxy group present 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 present in the cation (Ia) include cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, phenyl, 2-methylphenyl, 4-methylphenyl, 1-naphthyl and 2-naphthyl.
    Examples of the C1-C30 alkyl group which may be substituted by at least one group selected from the hydroxyl group, the C3-C12 cyclic hydrocarbon group and the C1-C12 alkoxy group present in the cation (Ia) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl and benzyl groups.
    Examples of the C 3 -C 30 cyclic hydrocarbon group, which may be substituted by at least one of the groups chosen from the hydroxyl group and the C 1 -C 12 alkoxy group present in the cation (Ia), include cyclopentyl groups, cyclohexyl, 1-adamantyl, 2-adamantyl, bicyclohexyl, phenyl, 2-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 2,4-dimethylphenyl, 2,4,6-dimethylphenyl, trimethylphenyl, 4-n-hexylphenyl, 4-n-octylphenyl, 1-naphthyl, 2-naphthyl, fluorenyl, 4-phenylphenyl, 4-hydroxyphenyl, 4-methoxyphenyl, 4-tert-butoxyphenyl and 4-n-butylphenyl. hexyloxyphényle.
    Examples of the C1-C12 alkyl group present in cations (Ib) and (Ic) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl groups. , n-hexyl, n-octyl and 2-ethylhexyl.
    Examples of the cation (la) include the following cations:
    Examples of the cation (Ib) include the following cations:
    Examples of the cation (Ic) include the following cations:


    As the cation represented by A +, the cation (Ia) is preferable.
    As the cation represented by A +, the cations represented by the following formulas (Id), (Ic) and (If) are also preferred:
    (Id) (1e) (If) * in which P28, P29 and P30 each independently represent a C1-C20 alkyl group or a C3-C30 cyclic hydrocarbon group, with the exception of a phenyl group, and at least one a hydrogen atom of the C 1 -C 20 alkyl group may be substituted 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 cyclic hydrocarbon group in C3-C30 may be substituted 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 or C1-C12, a C1-C12 alkoxy group or a C3-C12 cyclic hydrocarbon group, and 1, k, j, i, h and g each independently represent an integer of 0 to 5.
    Examples of the C 1 -C 20 alkyl group include a methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, n-octyl, n-decyl and n-icosyl group.
    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 +, a cation represented by the formula (Ig) is clearly preferred:
    dg) in which P4; P42 and P43 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, and in particular 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.
    Examples of the alkyl group and the alkoxy group include the same groups as mentioned above.
    As salt (I), the salt represented by the following formula is preferred:
    in which P22, P23, P24 and Q1 have the same meanings as those defined above.
    In the salt represented by formula (II) (hereinafter simply referred to as salt (II)), R22 represents a C1-C30 hydrocarbon group which may be substituted and at least one -CH2- unit of the hydrocarbon group may be substituted by -CO- or -0-.
    The C1-C30 hydrocarbon group may be a linear or branched chain hydrocarbon group. The C1-C30 hydrocarbon group may have a monocyclic or polycyclic structure and may have one or more aromatic groups. The C1-C30 hydrocarbon group can have one or more carbon-carbon double bonds.
    It is preferred that the C1-C30 hydrocarbon group contain at least one ring structure and it is most preferred that the C1-C30 hydrocarbon group has a ring structure. Examples of the cyclic structure include cyclopropane, cyclohexane, cyclooctane, and the like structures. norbornane, adamantane, cyclohexene, benzene, naphthalene, anthracene, phenanthrene and fluorene.
    Examples of the substituent of the C1-C30 hydrocarbon group are 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, the hydroxyl group being preferred as a substituent.
    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 C1-C6 hydroxyalkyl group include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl and 6-hydroxyhexyl.
    Q3 and Q4 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group.
    Examples of the C1-C6 perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl undecafluoropentyl and tridecafluorohexyl, with trifluoromethyl being preferred.
    It is preferred that Q 3 and Q 4 are each independently fluorine atom or trifluoromethyl group and it is more preferred that Q 3 and Q 4 are fluorine atoms.
    >
    Specific examples of the anionic portion of salt (II) include the following forms:








    It is preferred that R22 represents a group having the formula:
    in which 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 C3-C30 monocyclic or polycyclic hydrocarbon group, in which a hydrogen atom is substituted with a hydroxyl group on the Y1 position when Y1 represents -CH (OH) -, or in which two hydrogen atoms are substituted by = O on the Y1 position when Y1 represents -CO-, and at least one hydrogen atom of the C3-C30 monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, an alkoxy group with C1-C6, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a 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 C1-C6 hydroxyalkyl moiety include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl and 6-hydroxyhexyl groups.
    Examples of the X1 ring include a C4-C8 cycloalkyl group, such as a cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl group, an adamantyl group and a norbornyl group, in which a hydrogen atom may be substituted with a hydroxyl group or in which two hydrogen atoms may be substituted with = 0, and in which at least one hydrogen atom may be substituted by the C1-C6 alkyl group, the C1-C6 alkoxy group, the perfluoroalkyl group; C1-C4, the hydroxy-C1-C6 group, the hydroxyl group or the cyano group.
    As specific examples of the ring X1, mention may be made of a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, a 3-oxocyclopentyl group, a 3-oxocyclohexyl group, a 4-oxocyclohexyl group, a 2-hydroxy-cyclopentyl group and a 2-hydroxycyclopentyl group. -hydroxycyclohexyl, a 3-hydroxycyclopentyl group, a 3-hydroxycyclohexyl group, a 4-hydroxycyclohexyl group, a 4-oxo-2-adamantyl group, a 3-hydroxy-1-adamantyl group, a 4-hydroxy-1-adamantyl group a 5-oxonorbornan-2-ÿle group, a 1,7,7-trimethyl-2-oxonorbornan-2-yl group, a 3,6,6-trimethyl-2-oxo-bicyclo [3.1.1] heptan group; -3-yl, a 2-hydroxy-norbornan-2-yl group, a 1,7,7-trimethyl-2-hydroxynorbornan-3-yl group, a 3,6,6-trimethyl-2-hydroxybicyclo group [3.1 .1] hepta-3-yl, t
    t and related groupings
    In the above formulas, a continuous drawn with an open end represents a link extending from an adjacent group.
    As cycle X1, the adamantane ring is preferred.
    The group represented by the following formulas (1), (m) or (n) is preferred:

    (1) {") <*) as group R22. In formulas (1), (m) and (n) above, a continuous drawn with an open end represents a bond extending from an adjacent group.
    Q3 and Q4 each independently represent 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 each independently represent the fluorine atom or the trifluoromethyl group and it is more preferred that Q 3 and Q 4 are the fluorine atoms.
    A '+ represents an organic cation corresponding to formula (IIa):
    (IIa) wherein P6 and P7 each independently represent a C1-C12 alkyl group or a C3-C12 cycloalkyl group, or P6 and P7 are joined to form a divalent C3-C12 acyclic hydrocarbon group which forms a ring together with the adjacent S + element, and at least one -CH2- unit of the divalent acyclic hydrocarbon group may be substituted with -CO-, -O- or -S-, P8 represents a hydrogen atom, P9 represents a C1-alkyl group -C12, a C3-C12 cycloalkyl group or an aromatic group which may be substituted, or P8 and P9 are joined to form a divalent acyclic hydrocarbon group which forms a 2-oxocycloalkyl moiety together with the adjacent -CHCO- radical, and at least one -CH2- unit of the divalent acyclic hydrocarbon group may be replaced by -CO-, -O- or -S- (hereinafter referred to simply as cation (Ha)).
    Examples of the C1-C12 alkyl group include the same groups as mentioned above.
    Examples of the C 3 -C 12 cycloalkyl group present in the cation (IIa) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl. Examples of the divalent C3-C12 acyclic hydrocarbon group formed by linking P6 and P7 include trimethylene, tetramethylene and pentamethylene.
    Examples of the cyclic group formed together with the adjacent S + element and the divalent acyclic hydrocarbon group include a tetramethylenesulphonio, pentamethylenesulphonio and oxybisethylenesulphonio group.
    Examples of the aromatic group present in the cation (IIa) include phenyl, tolyl, xylyl, 4-n-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-cyclohexylphenyl, 4-phenylphenyl and naphthyl. The aromatic group may be substituted and, as examples of substituents, there may be mentioned a C1-C6 alkoxy group, such as a methoxy, ethoxy, n-propoxy, n-butoxy, tert-butoxy and n-hexyloxy group; an acyloxy group, such as an acetyloxy group and a 1-adamantylcarbonyloxy group; and a nitro group.
    Examples of the divalent acyclic hydrocarbon group formed by linking P8 and P9 include methylene, ethylene, trimethylene, tetramethylene and pentamethylene moieties, and examples of the 2-oxocycloalkyl moiety formed together with the adjacent -CHCO- radical and the acyclic hydrocarbon moiety. divalent, include 2-oxocyclopentyl and 2-oxocyclohexyl groups.
    As the cation (IIa), the cation is preferred in which P6 and P7 are joined to form the divalent C3-C12 acyclic hydrocarbon group which forms the ring together with the adjacent S + element, P8 represents the hydrogen atom, P9 represents the C1-C12 alkyl group, the C3-C12 cycloalkyl group or the aromatic group which may be substituted by at least one group chosen from C1-C6 alkoxy group, C2-C20 acyl group and nitro group, and the cation, wherein P6 and P7 are joined together to form the trimethylene, tetramethylene or pentamethylene group which forms the ring together with the adjacent S + element, P8 represents the hydrogen atom, P9 represents the C1 alkyl group, is most preferred. -C12 or the aromatic group which may be substituted by at least one group selected from the C1-C6 alkoxy group and the nitro group.
    Examples of the cation (IIa) include the following cations:

    As salt (II), the salt represented by the following formula is clearly preferred:
    wherein P6, P7, P8, P9, Q3, Q4, X1, Y1 and Z1 are the same as defined above, and the salts represented by the following formulas are particularly preferred:
    where P6, P7, P8, P9, Q3 and Q4 are the same as defined above, from the point of view of resolution.
    The salt (I) can be produced by a process comprising reacting a salt of formula (V):
    (V) wherein M represents Li, Na, K or Ag and Q1 has the same meaning as defined above (hereinafter referred to simply as salt (V)), with a compound of formula (VI):
    (VI) wherein A + has the same meaning as defined above, and G is F, Cl, Br, I, BF4, AsF0, SbFg, PFβ or C104 (hereinafter referred to simply as the compound; (vi)) .
    The reaction of the salt (V) and the compound (VI) 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 (VI) is usually 0.5 to 2 moles per mole of the salt (V). The salt (I) obtained by the above process can be isolated by recrystallization and can be purified by washing with water.
    The salt (II) can be produced by a process comprising reacting a salt of formula (VII):
    (VII) in which M 'represents Li, Na, K or Ag, and Q3, Q4 and R22 have the same meanings as defined above (hereinafter, it will simply be designated by salt (VII)), with a compound of formula (VIII): A '+ G' (VIII) wherein A + has the same meaning as defined above and G- 'represents F, Cl, Br, I, BF4, AsF6, SbF6, PFe or CIO4 (hereinafter simply referred to as Compound (VIII)).
    The reaction of salt (VII) and compound (VIII) 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 (VIII) is usually from 0.5 to 2 moles per mole of the salt (VII). The salt (II) obtained by the above process can be isolated by recrystallization and can be purified by washing with water.
    The salt (VII) used for the production of the salt (II) can be obtained by a process comprising the esterification of an alcoholic compound represented by the H0 ~ * 22 (IX) formula (IX): in which R22 has the same meaning as defined above (hereinafter simply referred to as an alcoholic compound (IX)), with a carboxylic acid represented by the formula (X):
    (X) wherein M ', Q3 and Q4 have the same meanings as defined above (hereinafter simply referred to as carboxylic acid (X)).
    The esterification reaction of the alcoholic compound (IX) 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 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 are 1,1-carbonyldiimidazole and N, N'-dicyclohexylcarbodiimide.
    The esterification reaction may preferably be carried out with dehydration as long as this tends to shorten the reaction time. Examples of the dehydration process include the Dean and Stark process.
    The amount of carboxylic acid (X) is usually 0.2 to 3 moles, preferably 0.5 to 2 moles per mole of the alcoholic compound (IX).
    The amount of acid catalyst may be a catalytic amount or the amount equivalent to the solvent and is usually 0.001 to 5 moles per mole of the alcoholic compound (IX). The amount of the dehydrating agent is usually 0.2 to 5 moles, preferably 0.5 to 3 moles per mole of the alcoholic compound (IX).
    The carboxylic acid (X) can be produced, for example, by a process comprising reacting an ester compound represented by the following formula:
    in which Q3 and Q4 have the same meanings as defined above and R30 represents a C1-C6 alkyl group, with a compound represented by the following formula:
    M '-OH
    in which M 'has the same meaning as that defined above, in water.
    The present resist composition comprises (A) salt (I), (B) salt (II) and (C) a resin which contains a structural unit having an acid-sensitive group and which is itself insoluble or poorly soluble in an aqueous alkaline solution, but becomes soluble in an aqueous alkaline solution by 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 the salt (II) acts catalytically with respect to the groups sensitive to In the case of the resin acids, cleavages the acid-sensitive groups, so that the resin becomes soluble in an aqueous alkaline solution.
    /
    The resin used for the present composition contains a structural unit having the acid-sensitive moiety and itself insoluble or poorly soluble in an aqueous alkaline solution, but the acid-sensitive moiety is cleaved with an acid.
    In this specification, an "acid-sensitive group" refers to a group capable of being removed by the action of an acid.
    In the present specification, the term "-COOR" may be described as "a structure having a carboxylic acid ester", and may also be abbreviated as "ester group". In particular, the term "-COOC (CH 3) 3" may be described as "a structure having a tert-butyl carboxylic acid ester" or may be referred to in abbreviated form as "tert-butyl ester moiety".
    As examples of the acid-sensitive group, there may be mentioned a structure having a carboxylic acid ester, such as an alkyl ester group, wherein a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, an alicyclic ester group, wherein a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, and a lactone ester group, wherein a carbon atom adjacent to. the oxygen atom is a quaternary carbon atom. The expression "quaternary carbon atom" denotes a "carbon atom connected to four substituents different from the hydrogen atom". As an acid-sensitive group, there may be mentioned as an example a group having a quaternary carbon atom connected to three carbon atoms and a group -OR ', R' representing an alkyl group.
    Examples of the acid-sensitive moiety include an alkyl ester moiety, wherein a carne atom adjacent to the oxygen atom is a quaternary carbon atom, such as a tert-butyl ester moiety; an ester group of the acetal type, such as the methoxymethyl ester, ethoxymethyl ester, 1-ethoxy-ethyl ester, 1-isobutoxyethyl ester, 1-isopropoxyethyl ester, 1-ethoxypropoxy ester, 1-ester ester ( 2-methoxyethoxy) ethyl, 1- (2-acetoxyethoxy) ethyl ester, 1- [2- (1-adamantyloxy) -ethoxy] ethyl ester, 1- [2- (1-adamantanecarbonyloxy) ethoxy] -ethyl ester 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 present in the adamantyl group may be substituted by a hydroxyl group.
    As examples of structural unit, there may be mentioned 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-acid ester. carboxylic acid, a structural unit. derived from a tricyclodecenecarboxylic acid ester and a structural unit derived from a tetracyclodecenecarboxylic acid ester. The structural units derived from the acrylic acid ester and the methacrylic acid ester are preferable.
    The resin used for the present composition can be obtained by carrying out a polymerization reaction of one or more monomers having the acid-sensitive group and an olefinic double bond.
    Of these monomers, those having a bulky acid-sensitive moiety, such as an alicyclic ester moiety (for example, a 2-alkyl-2-adamantyl ester group and a 1- (1-adamantyl) ester) are preferred. -alkylalkyl), since an excellent resolution is obtained when using the resin obtained in the present composition.
    Examples of such monomers containing the acid-sensitive and bulky group include 2-alkyl-2-adamantyl-2-acrylate groups, 2-alkyl-2-adamantyl methacrylate, 1- (1-adamantyl) acrylate, and the like. -alkylalkyl, 1- (1-adamantyl) -1-alkylalkyl methacrylate, 2-alkyl-2-adamantyl 5-norbornene-2-carboxylate, 1- (1-adamantyl) -5-norbornene-2-carboxylate -alkylalkyl, 2-alkyl-2-adamantyl α-chloroacrylate and 1- (1-adamantyl) -1-alkylalkyl α-chloroacrylate.
    Particularly when using 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate or 2-alkyl-2-adamantyl α-chloroacrylate as monomer for the component in the present composition, which tends to provide a resist composition having excellent resolution. Typical examples thereof include 2-methyl-2-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl acrylate, 2-ethyl methacrylate and the like. 2-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-ethyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-isopropyl-2-adamantyl acrylate or 2-isopropyl-2 methacrylate adamantyl for the present composition, there is a tendency to obtain a resist composition having excellent sensitivity and resistance to heat. In the present invention, two or more types of monomers, whose group or groups are dissociated by the action of the acid, can be used 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-methacrylate. 2-Adamantyl can usually be produced by reacting a 2-alkyl-2-adamantanol or a metal salt thereof with a methacrylic halide.
    The resin used for the present composition may also contain one or more other structural units derived from an acid-stable monomer in addition to the aforementioned structural units having the acid-sensitive moiety. In the present application, the term "structural unit derived from an acid-stable monomer" refers to a structural unit which is not dissociated by an acid generated by salt (I) and salt (II). .
    Examples of another structural unit 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 unsaturated aliphatic dicarboxylic anhydride, 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 alkyl methacrylate wherein 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 with 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 the quaternary carbon atom, and the 1-adamantyloxycarbonyl group can 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 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-methacryloyloxy-γ-butyrolactone; i a structural unit represented by the formula (1):
    (1) wherein R1 represents a hydrogen atom or a methyl group, R3 represents a methyl group, a trifluoromethyl group or a halogen atom, e represents an integer of 0 to 3 and, when ft represents 2 or 3 the R3 groups may be the same or different from each other; a structural unit represented by formula (II):
    (2) wherein R 2 is hydrogen or methyl, R 4 is methyl, t is trifluoromethyl or halogen, d is an integer of 0 to 3 and when e is 2 or 3, the groups R4 may be the same or different from each other; 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, especially a structural unit represented by the formula (3):
    t (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 hydroxyl group or a -COO2 group. wherein U represents an alcohol residue, or R5 and R6 can be joined to each other to form a carboxylic anhydride residue represented by -C (= O) 00 (= O) -; .
    a structural unit derived from an unsaturated aliphatic dicarboxylic anhydride, such as a structural unit t represented by formula (4):
    (4) * f a structural unit represented by formula (5):
    (5) 9 and the like.
    Particularly preferred is the resin additionally containing at least one structural unit selected from the structural unit derived from p-hydroxystyrene, the structural unit derived from m-hydroxystyrene, the structural unit derived from the 3-hydroxy acrylate. 1-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 of 3, 5-dihydroxy-1-adamantyl, the structural unit represented by the formula (1) and the derived structural unit represented by the formula (2), in addition to the structural unit having the acid-sensitive group, the the adhesion of the resist to 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 methacrylate can be produced. adamantyl, for example, by reacting the corresponding hydroxyadamantane with acrylic acid, methacrylic acid or its acid halide, and they are also available commercially.
    In addition, ori may produce acryloyloxy-γ-butyrolactone and methacryloyloxy-γ-butyrolactone, wherein the lactone ring may be substituted with an alkyl group by reacting α- or β-bromo-γ-butyrolactone. corresponding with acrylic acid or methacrylic acid, or by reacting the corresponding α- or β-hydroxy-γ-butyrolactone with the acrylic halide or methacrylic halide.
    As monomers 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 above, and mixtures thereof. These esters may be produced, for example, by reacting the corresponding alicyclic lactone having the hydroxyl group with acrylic acid or methacrylic acid and its production method is described, for example, in JP 2000-26446. AT.
    /
    Examples of acryloyloxy-γ-butyrolactone and methacryloyloxy-γ-butyrolactone having the lactone ring which may be substituted by the alkyl group include the compounds α-acryloyloxy-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, α-acryloyloxy-β, β-dimethyl-γ-butyrolactone, α-methacryloyloxy-β, β-dimethyl-γ-butyrolactone, α-acryloyloxy-α-methyl-γ-butyrolactone, α-methacryloyloxy-α-methyl-γ- butyro-lactone, β-acryloyloxy-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone and β-methacryloyloxy-α-methyl-γ-butyrolactone. ,
    The resin containing a structural unit derived from 2-norbornene has a resistant structure, because the alicyclic group is directly present on its main chain, and has a property resulting in excellent resistance to dry etching. 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 2-norbornene. The structural unit derived from 2-norbornene is formed by opening the 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 unit derived from an unsaturated aliphatic dicarboxylic anhydride, are formed by opening their double bonds and can be represented by the above-mentioned formula (4) and formula (5), respectively.
    As regards R 5 and R 6, examples of the C 1 -C 3 alkyl group are a methyl, ethyl and n-propyl group, and examples of the hydroxyalkyl / C 1 -C 3 group include the hydroxymethyl and 2-hydroxyethyl groups.
    In R 5 and R 6, the group -COO 2 represents an ester formed from the carboxyl group, and an alcoholic residue corresponding to ü, for example, an optionally substituted C 1 -C 8 alkyl group, a 2-oxooxolan-3 group will be mentioned. yl, a 2-oxooxolan-4-yl group and the like and, as a substituent on the C1-C8 alkyl group, there will be mentioned a hydroxyl group, an alicyclic hydrocarbon residue and the like.
    Specific examples of the monomer used to generate the structural unit represented by the above-mentioned formula (3) may include 2-norbornene, 2-hydroxy-5-norbornene, 5-norbornene-2- carboxylic acid, methyl 5-norbornene-2-carboxylate, 2-hydroxyethyl 5-norbornene-2-carboxylate, 5-norbornene-2-methanol and 5-norbornene-2,3-dicarboxylic anhydride.
    When the term U represents, in the grouping. In the acid-sensitive group, the structural unit represented by formula (3) is a structural unit having the acid-sensitive group even though it has the structure of norbornane.
    Examples of structural unit-generating monomers having the acid-sensitive moiety include tert-butyl 5-norbornene-2-carboxylate, 1-cyclohexyl-1-methylethyl 5-norbornene-2-carboxylate, 5-norbornene, and 1-methylcyclohexyl 2-carboxylate, 2-methyl-2-adamantyl 5-norbornene-2-carboxylate, 2-ethyl-2-adamantyl 5-norbornene-2-carboxylate, 5-norbornene-2 1- (4-methylcyclohexyl) -1-methylethylcarboxylate, 1- (4-hydroxycyclohexyl) -1-methylethyl 5-norbornene-2-carboxylate, 1-methyl-1-5-norbornene-2-carboxylate - (4-oxocyclohexyl) ethyl, 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) having the acid-sensitive group, generally in a ratio of 10 to 80 mol% in all structural units of the resin, although the ratio varies in depending on the type of radiation used for the exposure to form the pattern, the type of group sensitive to acids, etc.
    When using the derived structural units, in particular, 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate, 1- (1-adamantyl) acrylate, 1-alkylalkyl or 1- (1-adamantyl) -1-alkylalkyl methacrylate, as a structural unit having an acid-sensitive group, it is advantageous, in terms of resistance to dry etching of the resist, that the ratio of the units 15 mol% or more, based on all the structural units of the resin.
    When, in addition to the structural units having the acid-sensitive group, other structural units having the acid-stable group are contained in the resin, it is preferable that the sum of these structural units is in the range of 20 to 90 % mole based on all structural units of the resin.
    In the case of KrF lithography, even if a structural unit derived from hydroxystyrene, in particular p-hydroxystyrene and m-hydroxystyrene, is used as one of the components of the resin, a composition can be obtained. resist having sufficient transparency. To obtain these resins, the corresponding acrylic or methacrylic ester monomer can be radically polymerized with acetoxystyrene and styrene, and then the acetoxy group of the structural unit derived from acetoxystyrene can be removed by a reaction. deacetylation with an acid.
    Specific examples of the structural unit derived from hydroxystyrene include the following structural units, represented by formulas (6) and (7):
    (6)
    (7)
    The resin used for the present resist composition can be produced by carrying out the polymerization reaction of the corresponding monomer (s). The resin may also be produced by performing the oligomerization reaction of the corresponding monomer (s), followed by polymerization of the resulting oligomer.
    The polymerization reaction is usually carried out in the presence of a radical initiator.
    The radical initiator is not limited and examples thereof include an azo compound, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methyl-butyronitrile), 1, 1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2 azobis (2-methylpropionate) and 2,2'-azobis (2-hydroxymethylpropionitrile); an organic hydroperoxide, such as lauroyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-peroxydicarbonate, propyl, 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, more preferably, 2,2'-t azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile ), 2,2'-azobis (2,4-dimethylvaleronitrile) and dimethyl-2,2'-azobis (2-methylpropionate), more preferably 2,2'-azobisisobutyronitrile and 2,2 ' azobis (2,4-dimethylvaleronitrile).
    These radical initiators may be used alone or in the form of a mixture of two or more types of them. When the 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 from 0 to 150 ° C, preferably from 40 to 100 ° C.
    The polymerization reaction is usually carried out in the presence of a solvent and it is preferred to use a solvent in an amount sufficient to dissolve the monomer, the radical initiator and the resulting resin. Examples of these are a hydrocarbon solvent, such as toluene; an ether solvent, such as 1,4-dioxane and tetrahydrofuran; a ketonic solvent, such as methyl isobutyl ketone; an alcoholic solvent, such as isopropyl alcohol; a cyclic ester solvent, such as γ-butyrolactone; an ester and glycol ether solvent, such as propylene glycol monomethyl ether acetate; and an acyclic ester solvent, such as ethyl lactate. It is possible to use these solvents alone or as a mixture.
    The amount of solvent is not limited and will preferably be from 1 to 5 parts by weight based on 1 part of all the monomers or oligomers.
    When an alicyclic compound having an olefinic double bond and an aliphatic dicarboxylic anhydride are used as the monomers, it is preferable to use them in excess amount because of their tendency not to polymerize easily.
    At the end of the polymerization reaction, the resin produced can be isolated, for example, by adding a solvent in which the present resin is insoluble or poorly soluble, to the resulting reaction mixture and filtering 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 80 to 99.9% by weight of the resin component and 0.1 to 20% by weight of the sum of salt (I) and salt (II) on the basis of total amount of the resin component, salt (I) and salt (II).
    The quantitative ratio of salt (I) and salt (II) is usually from 9/1 to 1/9, preferably from 8/2 to 2/8, more preferably from 7/3 to 3/7 .
    In the present resist composition, performance degradation due to inactivation of the acid that occurs due to a delay following exposure, can be reduced by adding an organic base compound, particularly an organic base compound containing nitrogen as a neutralizing agent. Specific examples of the nitrogen-containing organic base compound include an amine compound represented by the following formulas:
    in which R11 and R12 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and the alkyl, cycloalkyl and aryl groups may be substituted by at least one group chosen from a hydroxyl group, an amino group which may be substituted with a C 1 -C 4 alkyl group, and a C 1 -C 6 alkoxy group which may be substituted by a C 1 -C 6 alkoxy group, R 13 and R 14 independently represent a hydrogen atom, an alkyl group, a group / cycloalkyl group, an aryl group or an alkoxy group, and the alkyl, cycloalkyl, aryl and alkoxy groups may be substituted by at least one group selected from a hydroxyl group, an amino group which may be substituted by a C1-C6 alkyl group. C4 and a C1-C6 alkoxy group, or R13 and R14 are joined together with the carbon atoms to which they are bound to form a ring aromatic, R15 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or a nitro group and the alkyl, cycloalkyl, aryl and alkoxy groups, which may be substituted by at least one group chosen. from among a hydroxyl group, an amino group which may be substituted by a C1-C4 alkyl group, and a C1-C6 alkoxy group, R16 represents an alkyl or cycloalkyl group and the alkyl and cycloalkyl groups may be substituted by at least a group selected from a hydroxyl group, an amino group which may be substituted by a C1-C4 alkyl group, and a C1-C6 alkoxy group, and W represents -CO-, -NH-, -S-, - SS-, an alkylene group. at least one methylene unit may be replaced by -O-, or an alkenylene group, at least one methylene unit may be replaced by -O-, and a quaternary ammonium hydroxide represented by the following formula:
    in which R 17, R 18, R 19 and R 20 independently represent an alkyl group, a cycloalkyl group or an aryl group, and the alkyl, cycloalkyl and aryl groups may be substituted by at least one group chosen from a hydroxyl group, an amino group which may be substituted by a C1-C4 alkyl group, and a C1-C6 alkoxy group.
    The alkyl group present in the radicals R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 preferably contains about 1 to 10 carbon atoms, more preferably about 1 to 6 carbon atoms.
    Examples of the amino group 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 and 2-methoxy groups. -mé.thoxyéthoxy.
    Specific examples of the alkyl group may be substituted by at least one group selected from a hydroxyl group, an amino group which may be substituted by a C1-C4 alkyl group, and a C1-C6 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 present in the radicals R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 preferably contains about 5 to 10 carbon atoms. Specific examples of the cycloalkyl group which may be substituted by at least one group selected from a hydroxyl group, an amino group which may be substituted by a C1-C4 alkyl group, and a C1-C6 alkoxy group include cyclopentyl groups. cyclohexyl, cycloheptyl and cyclooctyl.
    The aryl group present in the radicals R 11, R 12, R 13, R 14, R 15, R 17, R 18, R 19 and R 20 preferably contains about 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 a phenyl group and naphthyl.
    The alkoxy group present in the radicals R13, R14 and R15 preferably contains about 1 to 6 carbon atoms and will be mentioned as specific examples thereof, a methoxy, ethoxy, n-propoxy, isopropoxy or n-butoxy group. , tert-butoxy, n-pentyloxy and n-hexyloxy.
    The alkylene and alkenylene groups present in the term W contain, preferably, 2 to 6 carbon atoms. Specific examples of the alkylene moiety include ethylene, trimethylene, tetramethylene, methylenedioxy and ethylene-1,2-dioxy, and specific examples of the alkenylene moiety include ethane-1,2-diyl, 1-propene-1,3 -diyl and 2-butene-1,4-diyl.
    Specific examples of the amine compound include the compounds 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, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine , methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, eth yldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, N, N-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-pyridyl) ethane, 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'- dipyridylsulfide, 4,4'-dipyridyldisulfide, 1,2-bis (4-pyridyl) ethylene, 2,2'-dipicolylamine and 3,3'-dipicolylamine.
    Examples of the quaternary ammonium hydroxide group include tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, (3-trifluoromethylphenyl) trimethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (so-called "choline").
    A hindered amine compound having a piperidine backbone as disclosed in JP 11-52575 A1 can also be used as a neutralizing agent.
    As regards the formation of higher resolution units, it is preferred to use quaternary ammonium hydroxide as the neutralizing agent.
    When the base compound is used as a neutralizing agent, the present resist composition preferably comprises 0.01 to 1% by weight of the base compound based on the total amount of the resin component, ) and salt (II).
    The present resist composition may contain, if necessary, a small amount of various additives, such as a sensitizer, a dissolution inhibitor, other polymers, a surfactant, a stabilizer and a dye, as long as the of the present invention is not inhibited.
    The present resist composition is usually in the form of a liquid resist 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, such as spin coating. The solvent is used in an amount sufficient to dissolve the aforementioned ingredients, has a suitable drying rate and gives a uniform and smooth coating after evaporation of the solvent. Solvents generally used in the art may be employed.
    Examples of the solvent include monomethyl ether acetate; an acyclic ester, 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 ester, such as γ-butyrolactone. These solvents can be used alone or two or more of them can be mixed for use.
    A resist film applied to the substrate, then dried, is exposed to pattern formation, then heat-treated to facilitate the deblocking reaction, and then developed with an alkaline developer.
    . The alkaline developer used may be any of the various aqueous alkaline solutions used in the art. In general, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly known as "choline") is often used.
    It should be borne in mind that the embodiments disclosed herein are examples in all respects and are not restrictive. The scope of the invention is intended to be determined not by the foregoing descriptions, but by the appended claims, and includes all variants of equivalent meaning which fall within the scope of the claims.
    The present invention will be more specifically described by examples, which are not intended to limit the scope of the present invention. The symbol "%" and the terms "the part (s)" used to represent the content of any component and the amount of any material used in the following Examples and Comparative Examples are on a weight basis unless otherwise indicated. The weight average molecular weight of. any material used in the following examples is a value determined by gel permeation chromatography [HLC-8120GPC Type, Column (three columns): TSKgel multipore HXL-M, solvent: tetrahydrofuran, manufactured by TOSO CORPORATION] using styrene as the material standard reference.
    Structures of compounds were determined by NMR (type GX-270 or type EX-270, manufactured by JEOL LTD) and mass spectrometry (liquid chromatography: type 1100, manufactured by AGILENT TECHNOLOGIES LTD., Mass spectrometry: type LC / MSD or LC / MSD TOF type, manufactured by AGILENT TECHNOLOGIES LTD.).
    Example of salt synthesis I
    (1) 460 parts of a 30% aqueous sodium hydroxide solution are added to a mixture of 200 parts of methyl difluoro (fluorosulfonyl) acetate and 300 parts of deionized water in an ice bath. . The resulting mixture is refluxed at 100 ° C for 2.5 hours. After cooling, the cooled mixture is neutralized with 175 parts of concentrated hydrochloric acid and the resulting solution is concentrated to obtain 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-adamantanemethanol and 600 parts of dichloroethane are mixed, followed by addition of 75.1 parts of p-toluenesulfonic acid. The mixture obtained is refluxed for 12 hours. The resulting solution is concentrated to remove the dichloroethane. The residue obtained is mixed with 400 parts of tert-butyl methyl ether and the mixture obtained is stirred. The mixture is filtered to obtain a solid. The solid is mixed with 400 parts of acetonitrile and the mixture obtained is filtered to obtain the filtrate and the solid. The solid obtained is mixed with 400 parts of acetonitrile and the mixture obtained is filtered to obtain the filtrate and the solid. The filtrates obtained are mixed and concentrated to obtain 99.5 parts of the salt represented by formula (a) above. NMR (dimethylsulfoxide-d6: 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 are dissolved in 375 parts of acetone and 66.5 parts of tetrahydrothiophene are 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 obtain 207.9 parts of 1- (2-oxo-2-phenylethyl) tetrahydro-thiophenium bromide as white crystals. .
    1H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (ppm) 2.13 to 2.36 (m, 4H), 3.50 to / 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 (a) which was obtained above in step (2) are dissolved in 298 parts of acetonitrile. 79.5 parts of 1- (2-oxo-2-phenylethyl) tetrahydro-thiophenium bromide obtained above are added to the resulting solution. step (3) and 159 parts of deionized water. The resulting mixture is stirred for 15 hours and concentrated. The resulting concentrate is extracted twice with 500 parts of chloroform. The organic layers obtained are mixed, washed with deionized water and concentrated. 250 parts of tert-butylmethyl ether are added to the concentrate and the mixture obtained is stirred and filtered. The solid obtained is dried under reduced pressure to give 116.9 parts of the salt represented by the above formula (b) in the form of a white solid, which is called Cl.
    1H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): d (ppm) 1.50 (d, 6H), 1.62 (dd, 6H), 1.92 (s, 3H), 2.13 at 2.32 (m, 4H), 3.45 to 3.63 (m, 4H), 3.80 (s, 2H),. 5.30 (s, 2H), 7.62 (t, 2H), 7.76 (t, 1H), 8.00 (d, 2H) MS (spectrum in ESI (+) mode): M + 207.0 (C12H15OS + = 207.08) MS (spectrum in ESI (-) mode): M-323.0 (C13H17, F205S- = 323-08)
    Example of salt synthesis 2
    (c) "(1) 230 parts of a 30% aqueous solution of sodium hydroxide are added to a mixture of 100 parts of methyl difluoro- (fluorosulfonyl) acetate and 250 parts of deionized water in an ice bath. The mixture obtained is refluxed at 100 ° C. for 3 hours.
    After cooling, the cooled mixture is neutralized with 88 parts of concentrated hydrochloric acid and the resulting solution is concentrated to obtain 164.8 parts of sodium salt of difluoroisulfoacetic acid (containing an inorganic salt, purity: 62.8.degree. %).
    (2) 5.0 parts of sodium difluorosulfoacetate (purity: 62.8%), 2.6 parts of 4-oxo-1-adamantanol and 100 parts of ethylbenzene are mixed, and 0.8 parts of concentrated sulfuric acid. The resulting mixture is refluxed for 30 hours. After cooling, the mixture is filtered to obtain solids and the solids are washed with diethyl ether. tert-butylmethyl to obtain 5.5 parts of the salt represented by the above formula (c). Its purity is 35.6%, which has been calculated by the result of 1H-NMR analysis.
    ¹H-NMR (dimethylsulfoxide-ds, internal standard: tetramethylsilane): d (ppm) 1.84 (d, 2H, J = 13.0 Hz), 2.00 (d, 2H, J = 11.9). Hz), 2.29 to 2.32 (m, 7H), 2.54 (s, 2H).
    (3) 10.0 parts of the salt represented by the formula (c) (purity: 55.2%), which was obtained by a similar method described in this salt synthesis example 2, are mixed with the steps ( 1) and (2), to a mixed solvent of 30 parts of acetonitrile and 20 parts of deionized water. To the resulting mixture is added the solution prepared by mixing 5.0 parts of 1- (2-oxo-2-phenylethyl) tetrahydrothiophenium bromide, 10 parts of acetonitrile and 5 parts of deionized water. After stirring for 15 hours, the stirred mixture is concentrated and extracted with 98 parts of chloroform. The organic layer is washed with deionized water. The organic layer obtained is concentrated. The concentrate is mixed with 70 parts of ethyl acetate and the resulting mixture is filtered to obtain 5.2 parts of the salt represented by the above formula (d) as a white solid, which is designated C2.
    . 1H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): d (ppm) 1.83 (d, 2H, J = 12.5 Hz), 2.00 (d, 2H, J = 12.0 Hz) ), 2.21 to 2.37 (m, 11H), 2.53 (s, 2H), 3.47 to 3.62 (m, 4H), 5.31 (s, 2H), 7.63 (m.p. 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 (spectrum in ESI (+) mode): M + 207.1 (C12H15SO + = 207.08) MS (spectrum in ESI (-) mode): M-323.0 (C12H13F2O6S ~ = 323.04)
    Example of resin synthesis 1
    The monomers used in this resin synthesis example are the following monomers M1, M2 and M3: ·
    /
    Ml M2 M3
    The monomer M1, the monomer M2 and the monomer M3 are dissolved in an amount of methyl isobutyl ketone representing twice the amount of all the monomers to be used (molar ratio of the monomers: monomer
    M1: M2 monomer: M3 monomer = 5: 2.5: 2.5). 2,2'-azobisisobutyronitrile is added to the solution as an initiator in a ratio of 2 mol% based on the total molar amount of the monomers and the resulting mixture is heated at 80 ° C for about 8 hours. The reaction solution is poured into a large amount of heptane to cause precipitation. The precipitate is 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 is obtained. This copolymer has the following structural units. It is called Al resin:
    Example of resin synthesis 2
    The monomers used in this resin synthesis example are the monomers M1, M2 and M4
    Ml M2 M4 following:
    The monomer M1, the monomer M2 and the monomer M4 are dissolved in an amount of 1,4-dioxane which represents 1.28 times the amount of all the monomers to be used (molar ratio of the monomers: monomer
    M2 monomer: M4 monomer = 50:25:25). 2,2'-Azobisisobutyronitrile is added to the solution as an initiator in a ratio of 3 mol% to the molar amount of all the monomers. The solution obtained is added to a quantity of 1,4-dioxane representing 0.72 times the amount of all the monomers to be used, at 88 ° C. for 2 hours. The resulting mixture is stirred at the same temperature for 5 hours. The reaction solution is cooled, then poured into a large amount of a mixed solvent of methanol and water to cause precipitation. The precipitate is 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 is obtained.
    This copolymer has the following structural units. It is called resin A2.
    i
    Examples 1 to 4 and Comparative Examples 1 to 3 Acid Generator B1 Acid Generator
    B2 Acid Generator
    Cl acid generator
    C2 acid generator: /
    Resin, Resins Al to A2
    Neutralizing agent
    Q1 2,6-diisopropylaniline
    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 are mixed and dissolved, and then filtered on a fluororesin filter having a pore diameter of 0.2 μm to prepare a resist liquid.
    Resin (type and amount are described in Table I) Acid Generator (type and quantity are described in Table I)
    Neutralizing agent (type and quantity are described in Table I)
    Solvent (the type is described in Table I)
    Silicon wafers are each coated with the material "ÄRC-29A", which is an antireflective organic coating composition available from Nissan Chemical Industries, Ltd., and then fired under the following conditions: 205 ° C and 60 seconds, to form an organic anti-reflective coating of 780Å thick. Each of the resist liquids prepared as indicated above is applied by centrifugal coating on. the anti-reflective coating, so that the thickness of the obtained film reaches 0.15 μm after drying.
    The silicon wafers thus coated with the respective resist liquids are each precooked directly on a plate heated to a temperature shown in FIG. column "PB" of Table I for 60 seconds. Using an ArF stepper system ("FPA-5000AS3" manufactured by CANON INC., NA = 0.75, 2/3 annular), each slice thus formed with the respective resist film is subjected to exposure according to a pattern of lines and spaces, the amount of exposure being gradually changed.
    After exposure, each slice is subjected to post-exposure firing on a plate heated to a temperature shown in the "PEB" column of Table I for 60 seconds, followed by development by a 60 second attack with 2.38% by weight aqueous solution of tetramethylammonium hydroxide.
    Each of the dark field patterns developed on the organic antireflective coating substrate after the development phase is examined under a scanning electron microscope, the results of the observation being shown in Table II. The term "dark field pattern" as used herein refers to a pattern obtained by exposing and developing through a reticle comprising a chromium-based surface (light-protecting portion) and linear glass layers (light transmitting portion) formed in the chromium surface and aligned with each other. As a result, the dark field pattern is such that after the exposure and development steps, the resist layer surrounding the pattern of lines and spaces remains on the substrate.
    Effective Sensitivity (ES): It is expressed as the amount of exposure, such as the line pattern and the space pattern becomes 1: 1, after exposure through a line pattern mask and i spaces of 100 nm and development process.
    Line Edge Roughness (LER): Each of a patterned wall surface developed on the organic anti-reflective coating substrate after development was observed with a scanning electron microscope. When the surface of the wall is smoother than that of Comparative Example 3, its evaluation is marked by the symbol "O", when the surface of the wall is smooth as that of Comparative Example 3, its evaluation is marked. by the symbol "Δ" and when the surface of the wall is rougher than that of Comparative Example 3, its evaluation is marked by the symbol "X".
    /
    Table I
    t
    Table II
    As is apparent from Table II, the resist compositions of the examples, which are in accordance with the present invention, provide a good resist configuration for resolution and smoothing of the wall surface.
    The present composition provides a good resistance pattern in terms of resolution and roughness of line edges and is particularly suitable for ArF excimer laser lithography, KrF excimer laser lithography and ArF dip lithography.
    权利要求:
    Claims (19)
    [1]
    A chemically amplified resist composition comprising: (A) A salt represented by the formula (I): wherein: Q1 is a C1-C8 perfluoroalkyl group and A + is at least one organic cation selected from the cations represented by formula (la):

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

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

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

    [7]
    Resistance composition according to claim 1, wherein R22 is a group represented by the formula:

    [8]
    Resistance composition according to claim 7, wherein the group represented by the formula:

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

    [10]
    Resistance composition according to claim 9, wherein the group represented by the formula:

    [11]
    The resist composition of claim 1, wherein P6 and P7 are joined to form a divalent C3-C12 acyclic hydrocarbon group which forms a ring together with the adjacent S + element, 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 chosen from a C1-C6 alkoxy group, a C2-C20 acyl group and a nitro group.
    [12]
    The resist composition of claim 1, wherein A + is an organic cation represented by the formula (Ih):

    [13]
    The resist composition of claim 12, wherein R22 is a group represented by the formula:

    [14]
    Resistance composition according to claim 13, wherein the group represented by the formula:

    [15]
    Resistance composition according to claim 1, wherein the quantitative ratio of the salt represented by the formula (I) to the salt represented by the formula (II) is 9/1 to 1/9.
    [16]
    The resist composition of claim 1, wherein the resin contains a structural unit. derived from a monomer having a bulky group sensitive to acids.
    [17]
    The resist composition of claim 16, wherein the bulky and acid-sensitive moiety is a 2-alkyl-2-adamantyl ester group or a 1- (1-adamantyl) -1-alkylalkyl ester.
    [18]
    The resist composition of claim 16, wherein the monomer having a bulky, acid-sensitive moiety is 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate, 1- (1-adamantyl) -1-alkylalkyl, 1- (1-adamantyl) -1-alkylalkyl methacrylate, 2-alkyl-2-adamantyl 5-norbornene-2-carboxylate, 5-norbornene-2 1 - (.1-adamantyl) -1-alkylalkylcarboxylate, 2-alkyl-2-adamantyl α-chloroacrylate or 1- (1-adamantyl) -1-alkylalkyl α-chloroacrylate
    [19]
    The resist composition of claim 1, wherein the resist composition further comprises a basic compound.
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    法律状态:
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    JP2007056890|2007-03-07|
    JP2007056890A|JP4844436B2|2007-03-07|2007-03-07|Chemically amplified resist composition|
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