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    公开号:BE1018146A3
    申请号:E2008/0055
    申请日:2008-01-29
    公开日:2010-06-01
    发明作者:Yoshiyuki Takata；Satoshi Yamamoto；Satoshi Yamaguchi
    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 semiconductors using a lithographic process, contains 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:
    and the resin that contains the following structural units:
    Summary of the invention
    The objects of the invention are to provide a chemically amplified resist composition, giving patterns having better resolution and roughness of the line edges.
    This and other objects of the present invention will be apparent from the following description.
    The present invention relates to the following: 1. A chemically amplified resist composition comprising: a resin that comprises a structural unit having an acid-sensitive moiety and a structural unit represented by formula (I):
    (I) wherein R1 represents a hydrogen atom or a methyl group, the ring X represents a C3-C30 cyclic hydrocarbon group, in which one -CH2- unit is substituted with a -COO- function, and at least one hydrogen atom in the C3-C30 cyclic hydrocarbon group may be substituted, and p represents an integer of 1 to 4, and which is itself insoluble or poorly soluble in an aqueous alkaline solution, but becomes soluble in a solution aqueous alkali under the action of an acid, and at least two salts selected from a salt represented by the formula (II):
    (II) wherein Y1 and Y2 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group, A + represents an organic counterion and R21 represents a C1-C30 hydrocarbon group which may be substituted and at least a -CH2- unit of the C1-C30 hydrocarbon group may be substituted with a -CO- or -O- group, and a salt represented by the formula (III): (III) wherein R23 represents a linear-chain perfluoroalkyl group or branched C1-C8 and A '+ represents an organic counterion; 2. The chemically amplified resist composition according to item 1, wherein the structural unit having an acid-sensitive moiety is a structural unit represented by formula (IVa):
    (IVa) wherein R2 represents a hydrogen atom or a methyl group, R3 represents a C1-C8 hydrocarbon group, R4 represents a methyl group, n represents an integer from 0 to 14, ZI represents a single bond or - (CH2) r-COO- and r represents an integer of 1 to 4, or a structural unit represented by the formula (TVb):
    (ivb) wherein R5 represents a hydrogen atom or a methyl group, R6 represents a C1-C8 hydrocarbon group, R7 and R8 represent, each independently, a hydrogen atom or a monovalent C1-C8 hydrocarbon group, which can have at least one heteroatom, and R7 and R8 can be joined to form a C1-C8 divalent hydrocarbon group which can have at least one heteroatom and which forms a ring together with the adjacent carbon atoms to which R7 and R8 are bound , and R7 and R8 may be joined to form a carbon-carbon double bond between the carbon atom to which R7 is bonded and the carbon atom to which R8 is bonded, q represents an integer of 1 to 3, Z2 represents a single bond or - (CH2) s-COO-, and s represents an integer of 1 to 4; 3. The chemically amplified resist composition according to item 1 or 2, wherein the resin further comprises a structural unit represented by formula (V):
    (V) wherein R9 represents a hydrogen atom or a methyl group, R10 and R11 represent, each independently, a hydrogen atom, a methyl group or a hydroxyl group, R12 represents a methyl group, t represents a whole number from 0 to 12, Z3 represents a single bond or - (CH2) u-COO- and u represents an integer from 1 to 4; 4. The chemically amplified resist composition according to items 1, 2 or 3, wherein the structural unit represented by formula (I) is a structural unit represented by formulas (Via), (VIb) or (Life):
    in which R1 represents a hydrogen atom or a methyl group, p represents an integer from 1 to 4, RI3 represents a methyl group, x represents an integer from 0 to 5, RI4 represents a C1-C4 hydrocarbon group, a carboxyl group or a cyano group, y represents an integer from 0 to 3, R 5 represents a C 1 -C 4 hydrocarbon group, a carboxyl group or a cyano group, z represents an integer from 0 to 3 and, when there is 2 or 3, the RI4 groups may be the same or different and when z is 2 or 3, the groups RI 5 may be the same or different; 5. The chemically amplified resist composition according to any one of 1 to 4, wherein the salt represented by formula (II) is a salt represented by formula (VII):
    (VII) wherein Y1 and Y2 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group, A + represents an organic counterion and R22 represents a linear or branched C1-C20 hydrocarbon group which may be substituted, or a C3-C30 cyclic hydrocarbon group which may be substituted, and at least one -CH2- unit of the C1-C20 straight or branched chain hydrocarbon group or the C3-C30 cyclic hydrocarbon group may be substituted by -CO- or -O-; The chemically amplified resist composition according to any one of items 1 to 4, wherein the salt represented by formula (II) is a salt represented by the following formula (XII):
    (XII) wherein Y1 and Y2 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group, A + represents an organic counterion, Z4 represents a single bond or a C1-C4 alkylene group, Q represents -CH2-, -CO- or -CH (OH) - and ring XI represents a C3-C30 monocyclic or polycyclic hydrocarbon group, in which two hydrogen atoms are substituted with = 0 in the Q position when Q is -CO -, or in which a hydrogen atom is substituted by a hydroxyl group at the Q position when Q is -CH (OH) -, and at least one hydrogen atom in the monocyclic or polycyclic C3-C30 hydrocarbon group may be substituted 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; 7. The chemically amplified resist composition according to any one of 1 to 6, wherein A + and A '+ are the same or different and each independently represents at least one cation selected from the group represented by the formula (Villa):
    (Villa) wherein PI, P2 and P3 each independently represent a C1-C30 linear or branched chain alkyl group, which may be substituted by at least one group selected from a hydroxyl group, a C3 cyclic hydrocarbon group, C12 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 (VUIb):
    (vxiib) wherein P4 and P5 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, a cation represented by the formula (City):
    (City) 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 in the divalent acyclic hydrocarbon group may be substituted with -CO-, -O- or -S-, P8 represents a hydrogen atom, P9 represents a grouping C1-C12 alkyl, 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- moiety and at least one -CH2- unit in the divalent acyclic hydrocarbon group may be replaced by -CO-, -O- or -S-; and a cation represented by the formula (VUId):
    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; 8. The chemically amplified resist composition according to any one of 1 to 6, wherein A + and A '+ are the same or different and each independently represents a cation represented by the formulas (City), (VUIf), (VlIIg) or (VUIj):

    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 hydrogen atom in the grouping C1-C20 alkyl may be substituted with a hydroxyl group, a C1-C12 alkoxy group or a C3-C12 cyclic hydrocarbon group, and at least one hydrogen atom of the C3-C30 cyclic hydrocarbon group 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 represent, each independently, 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 each independently represent an integer of 0 to 5, P40 and P41 represent each independently, a C1-C6 alkyl group or a group C3-C6 cycloalkyl, or P40 and P41 are joined to form a C3-C7 divalent acyclic hydrocarbon group which forms the ring together with the adjacent S + element, P42 represents a hydrogen atom, P43 represents an alkyl group C1-C6 or a C6-C12 aromatic group, which may be substituted by at least one group chosen from the C1-C6 alkoxy group, the C2-C12 acyl group and the nitro group, or P42 and P43 are connected for forming a C3-C7 divalent acyclic hydrocarbon group which forms a 2-oxocycloalkyl group together with the -CHCO-adjacent group, and at least one -CH2- unit of the divalent C3-C7 hydrocarbon group can be replaced by -CO- , -O- or -S-; 9. The chemically amplified resist composition according to any one of 1 to 6, wherein A + and A '+ are the same or different and each independently represents a cation represented by the formulas (VUIh) or (VHIk):
    wherein P25, P26 and P27 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, P44 and P45 are joined to form a hydrocarbon group. a C3-C7 divalent acyclic which forms the ring together with the adjacent S + element, P46 represents a phenyl or naphthyl group; 10. The chemically amplified resist composition according to any one of 1 to 6, wherein A + and A '+ are the same or different and each independently represents a cation represented by the formulas (VII) or (VIII):
    wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group, P47 and P48 are joined to form a divalent C4-C5 acyclic hydrocarbon group which forms the ring together with the adjacent S + element, P49 represents a phenyl group; 11. The chemically amplified resist composition according to any one of items 1 to 10, wherein the chemically amplified resist composition comprises the salt represented by the formula (Π) and at least one salt selected from the salt represented by the formula (II) and the salt represented by formula (III); 12. The chemically amplified resist composition according to any one of items 1 to 10, wherein the chemically amplified resist composition comprises at least two salts selected from the salt represented by the formula (Π); 13. The chemically amplified resist composition according to any one of items 1 to 6, wherein at least two salts selected from a salt represented by formula (II) and a salt represented by formula (III) are at least two selected salts. from the salt represented by formula (II), wherein A + represents the cation (Villa) or (City), and the salt represented by formula (III), wherein A '+ represents the cation (Villa) or (City ); 14. The chemically amplified resist composition according to any one of 1 to 13, wherein the chemically amplified resist composition also comprises a basic compound.
    Description of Preferred Embodiments
    The present chemically amplified resist composition comprises a resin which comprises a structural unit having an acid-sensitive moiety and a structural unit represented by the formula (I), and which itself is insoluble or poorly soluble in an aqueous alkaline solution, but becomes soluble in an aqueous alkaline solution under the action of an acid (referred to simply as RESINE hereinafter), and at least two salts selected from a salt represented by the formula (II) (referred to simply as salt (II) ci -after) and a salt represented by the formula (III) (referred to simply as salt (III) below).
    First, the structural unit having an acid-sensitive group will be illustrated.
    In the present specification, the substituent "-COOR" may be described as "a structure having a carboxylic acid ester" and may also be abbreviated to "ester group". Specifically, the substituent "-COOC (CH 3) 3" may be described as "a structure having a carboxylic acid tert-butyl ester" or may be abbreviated to "tert-butyl ester moiety".
    In this specification, an "acid-sensitive group" refers to a group that can be removed by the action of an acid.
    Examples of the acid-sensitive group include 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 ester group alicyclic ring, wherein a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, and a lactone type ester group, wherein a carbon atom adjacent to the oxygen atom is a carbon atom quaternary. The expression "quaternary carbon atom" denotes a "carbon atom linked to four substituents different from a hydrogen atom". As the acid-sensitive group, there may be mentioned by way of example a group having a quaternary carbon atom connected to three carbon atoms and a group -OR ', in which R' represents an alkyl group.
    Examples of the acid-sensitive 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 ester group of the acetal type, such as a methoxymethyl ester group, an ethoxymethyl ester group, a 1-ethoxyethyl ester group, a 1-isobutoxyethyl ester group, a 1-isopropoxyethyl ester group, a 1-ethoxypropoxy ester group or 2-methoxyethoxyethyl, 1- (2-acetoxyethoxy) ethyl ester, 1- [2- (1-adamantyloxy) ethoxy] ethyl ester, 1- [2- (1-adamantane-carbonyloxy) 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 ester group of isobornyl, 1-alkylcycloalkyl ester, 2-alkyl-2-adamantyl ester and 1- (1-adamantyl) -1-alkylalkyl ester, at least one hydrogen atom in the adamantyl group may be substituted 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 norbomene carboxylic acid ester, 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.
    As a structural unit having an acid-sensitive moiety, the structural unit represented by formula (IVa) or (TVb) is preferable:
    In the formula (IVa), R2 represents a hydrogen atom or a methyl group and R3 represents a C1-C8 hydrocarbon group. It is preferred that R3 represents the straight-chain or branched C1-C8 alkyl group.
    Examples of the C1-C8 hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopentyl, cyclohexyl, cyclooctyl, 2-methylcyclopentyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 4,4-dimethylcyclohexyl, 2-norbomyl and 5-methyl-2-norbomyl, and a C1-C4 alkyl group such that a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and sec-butyl group is preferable, more preferably, the methyl, ethyl, n-propyl and isopropyl groups are preferred.
    In the formula (IVa), R4 represents a methyl group, n represents an integer from 0 to 14, ZI represents a single bond or - (CH2) r -COO-, and r represents an integer from 1 to 4. prefers that n is 0 or 1. ZI will preferably represent the single bond or -CH 2 -COO-, more preferably the single bond.
    In formula (IVb), R5 represents a hydrogen atom or a methyl group and R6 represents a C1-C8 hydrocarbon group. Examples of the C1-C8 hydrocarbon group include the same groups as those mentioned above. Preferable examples of such groups include a C1-C4 alkyl group, such as a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and sec-butyl group, more preferably by way of example, the groups methyl, ethyl, n-propyl and isopropyl.
    In formula (IVb), R7 and R8 each independently represent a hydrogen atom or a C1-C8 monovalent hydrocarbon group, which may have at least one heteroatom.
    Examples of the C 1 -C 8 monovalent hydrocarbon group include a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl group.
    R7 and R8 may be joined to form a C1-C8 divalent hydrocarbon group which may have at least one heteroatom that forms a ring together with adjacent carbon atoms to which R7 and R8 are bound. Specific examples of the divalent C1-C8 hydrocarbon group include an ethylene group and a trimethylene group.
    R7 and R8 may also be joined to form a carbon-carbon double bond between the carbon atom to which R7 is bonded and the carbon atom to which R8 is bonded.
    In formula (IVb), q represents an integer from 1 to 3, Z2 represents a single bond or - (CH2) s-COO-, and s represents an integer from 1 to 4. It is preferred that s is 0 or 1. Z2 will preferably represent the single bond or -CH2-COO- and, more preferably, the single bond.
    The structural unit represented by formula (IVa) is derived from the monomer represented by formula (IVa-1):
    (IVa-1) wherein R2, R3, R4, Z1 and n are the same as defined above.
    Specific examples of the monomer represented by the formula (IVa-1) include the following compounds:


    The structural unit represented by formula (IVb) is derived from the monomer represented by formula (IVb-1):
    (IVb-1) wherein R5, R6, R7, R8, Z2 and q are the same as defined above.
    Specific examples of the monomer represented by the formula (IVb * 1) include the following:

    As the structural unit having an acid-sensitive moiety, the structural imitation represented by formulas (IXa) or (IXb) is also preferred:
    in which R 30 represents a hydrogen atom or a methyl group, R 31 represents a C 1 -C 8 alkyl group, R 32 represents a C 1 -C 8 alkyl group or a C 1 -C 8 alkoxy group, d represents an integer from 0 to 3 and, when d is 2 or 3, the groups R32 may be identical or different, R33 represents a hydrogen atom or a methyl group, R34 represents a C1-C8 alkyl group, R35 represents a C1-C8 alkyl group; or a C1-C8 alkoxy group, e represents an integer from 0 to 3 and, when e is 2 or 3, the R35 groups may be the same or different.
    Examples of the C1-C8 alkyl group include the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and n-hexyl groups, and the C1-alkyl group. -C4 is better. Examples of the C1-C8 alkoxy group include methoxy, ethoxy. n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy and n-hexyloxy, and the C1-C4 alkoxy group is preferable.
    The structural unit represented by formula (IXa) is derived from the monomer represented by formula (IXa-1):
    wherein R30, R31, R32 and d have the same meanings as defined above and the structural unit represented by formula (IXb) is derived from the monomer represented by formula (IXb-1): (IXb-1) wherein R33, R34, R35 and e are the same as defined above.
    Examples of the monomers represented by formulas (IXa-1) and (IXb-1) include the following compounds:


    The RESIN may contain a structural unit having an acid-sensitive moiety and may contain two or more types of structural units having an acid-sensitive moiety.
    It is preferred that the RESIN has the structural unit selected from the structural unit represented by the formula (IVa), as the structural unit having an acid-sensitive group, from the point of view of the dry etch resistance of the RESIN. If the structural unit represented by formula (IVa) corresponds, in particular, to the structural unit derived from a 2-methyl-2-adamantyl acrylate, a 2-methyl-2-adamantyl methacrylate, a 2-ethyl-2-adamantyl acrylate, a 2-ethyl-2-adamantyl methacrylate, a 2-isopropyl-2-adamantyl acrylate or a 2-isopropyl-2-adamantyl methacrylate it tends to a composition having excellent sensitivity and excellent heat resistance.
    It is also preferred that the RESIN have the structural units represented by the formulas (IVa) and (EXa) as the structural unit having an acid-sensitive group, from the point of view of the roughness of the line edges.
    The monomer represented by the formula (IVa-1) can usually be produced by a reaction of the corresponding adamantanol, or its metal salt, with an acrylic halide or a methacrylic halide. The monomer represented by the formula (IVb-1) can usually be produced by reacting the corresponding alcohol compound, or its metal salt, with an acrylic halide or a methacrylic halide. The monomer represented by the formula (IXa-1) can usually be produced by reacting the corresponding cyclohexanol, or its metal salt, with an acrylic halide or a methacrylic halide. The monomer represented by the formula (EXb-1) can usually be produced by reacting the corresponding cyclopentanol, or its metal salt, with an acrylic halide or a methacrylic halide.
    The structural unit represented by formula (I) will now be illustrated.
    In formula (I), R1 represents a hydrogen atom or a methyl group, ring X represents a C3-C30 cyclic hydrocarbon group in which a -CH2- unit is substituted with -COO-. At least one hydrogen atom of the C3-C30 cyclic hydrocarbon group may be substituted and there may be mentioned as examples of the substituent, a C1-C6 alkyl group, a carboxyl group and a cyano group.
    The ring X may be a monocyclic hydrocarbon group and may be a polycyclic hydrocarbon group.
    As a structural unit represented by the formula (I), the following formulas (Via), (VIb) or (Vie) will be preferred:
    in which R 1 and p have the same meanings as those mentioned above, R 3 represents a methyl group, X represents an integer from 0 to 5, R 14 represents a C 1 -C 4 hydrocarbon group, a carboxyl group or a cyano group. , y represents an integer from 0 to 3, R 5 represents a C 1 -C 4 hydrocarbon group, a carboxyl group or a cyano group, z represents an integer from 0 to 3 and, when y is 2 or 3, the groups RI 4 may be the same or different and when z is 2 or 3, the groups RI 5 may be the same or different.
    Examples of the C1-C4 hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
    It is preferred that p is 1 or 2 and, more clearly, that p is 1.
    It is preferred that x is 0 in the formula (Via). It is preferred that there be 0 in formula (VIb). It is preferred that z is 0 in the formula (Life).
    The structural unit represented by the formula (Via) is derived from the monomer represented by the formula (VIa-1):
    wherein R1, R13, x and p are the same as defined above.
    Examples of the monomer represented by the formula (Vla-1) include the following compounds:
    The structural unit represented by formula (VIb) is derived from the monomer represented by formula (VIb-1):
    wherein R1, R14, y and p are the same as defined above.
    Examples of the monomer represented by the formula (VIb-1) include the following compounds:
    The structural unit represented by the formula (Life) is derived from the monomer represented by the formula (VIc-1):
    in which RI, RI5, z and p are the same as those defined above.
    Examples of the monomer represented by the formula (VIc-1) include the following compounds:
    As the structural unit represented by formula (I), the structural unit represented by formula (VIb) is preferred, and more preferably, the following units are preferred:
    from the point of view of the resist pattern obtained after a lithographic process.
    The molar ratio of structural unit having an acid-sensitive moiety in the RESINE is usually from 20 to 95% based on the molar sum of the structural unit having an acid-sensitive moiety and the structural unit represented by the acidic moiety. formula (I) in the RESINE, and the molar ratio of the structural unit represented by the formula (I) in the RESINE is usually 5 to 80% based on the molar sum of the structural unit having a sensitive group to the acids and the structural unit represented by the formula (I) in the RESINE, although the ratio varies depending on the type of radiation used for the pattern exposure, the type of group sensitive to acids, etc.
    The RESIN comprises the structural unit having an acid-sensitive group and the structural unit represented by formula (I) and is itself insoluble or poorly soluble in an aqueous alkaline solution, but becomes soluble in an aqueous alkaline solution under action of an acid.
    The RESIN may contain the other structural unit (s) in addition to the structural unit having an acid-sensitive moiety and the structural unit represented by formula (I).
    Examples of the other structural unit include a structural unit represented by the formula (V): (V) wherein R 9 represents a hydrogen atom or a methyl group, R 10 and R 11 represent, each independently, a hydrogen atom , a methyl group or a hydroxyl group, RI2 represents a methyl group, t represents an integer from 0 to 12 and Z3 represents a single bond or - (CH2) u-COO- and u represents an integer from 1 to 4, a structural unit represented by the formula (X):
    in which RI6 represents a hydrogen atom or a methyl group and AR represents a C1-C30 alkyl group containing fluorine, which may contain 1 to 5 hydroxyl groups and at least one heteroatom chosen from an oxygen atom, an atom nitrogen and a sulfur atom, and a structural unit represented by the formula (XI):
    (XI) in which R 7 represents a hydrogen atom or a methyl group, a ring X 'represents a C 3 -C 30 cyclic hydrocarbon group, in which one -CH 2 - unit is substituted with a -COO- group, and at least one hydrogen atom of the C3-C30 cyclic hydrocarbon group may be substituted.
    The RESIN preferably comprises the structural unit represented by the formula (V). The RESIN also preferably comprises the structural units represented by formulas (V) and (XI).
    In formula (V), it is preferred that R10 and R11 each independently represent a hydrogen atom or a hydroxyl group. Preferably, t is 0 or 1 and, more preferably, t is 0, Z3 is preferably single bonds or -CH2-COO-.
    The structural unit represented by formula (V) is derived from the monomer represented by formula (V-1):
    (V-1) in which R 9, R 10, R 11, R 12, Z 3 and t have the same meanings as those defined above.
    Specific examples of the monomer represented by the formula (V-1) include the following compounds:

    As the structural unit represented by formula (V), structural units derived from the following monomers are preferred:
    in matters of resolution.
    The monomer represented by the formula (V-1) can usually be produced by reacting the corresponding hydroxyl-containing adamantane compound with an acrylic halide or a methacrylic halide.
    In the formula (X), examples of the C1-C30 alkyl group containing fluorine include a C1-C30 perfluoroalkyl group, such as a trifluoromethyl, pentafluoroethyl, heptafluoropropyl and nonafluorobutyl group; a C1-C30 perfluoroalkoxyalkyl group, such as a 1-trifluoromethoxyethyl group and a 1-pentafluoroethoxyethyl group; a C1-C30 perfluoroalkoxy-perfluoroalkyl group, such as a 1-trifluoro-methoxydifluoroethyl group and a 1-pentafluoroethoxy-difluoroethyl group; as well as the following groups (in the following formulas, a continuous drawn with an open end represents a link extending from the adjacent group).
    As a structural unit represented by the formula (X), there will be mentioned by way of example the structural units derived from the following monomers:
    As the structural unit represented by the formula (X), the structural units derived from the following monomers are preferred:
    Provided an excellent resolution is obtained when the resin containing the structural unit derived from this monomer is used in the present resist composition.
    The monomer to provide the structural unit represented by the formula (X) can be produced in the usual manner by reacting the corresponding fluorine-containing alcohol compound with an acrylic halide or a methacrylic halide.
    In formula (XI), examples of ring X 'include the same groups as those mentioned in ring X.
    As a structural unit represented by the formula (XI), there will be mentioned, by way of example, the structural units derived from the following monomers:

    As the structural unit represented by formula (XI), structural units derived from the following monomers will be preferred:
    in the plane of the adhesion of the resist to a substrate.
    The monomer to give the structural unit represented by the formula (XI) can be produced by reacting the corresponding alicyclic lactone having a hydroxyl group with the acrylic acid or methacrylic acid whose production process is described. for example, in JP-2000-26446-A.
    As a structural unit other than the structural units represented by the formulas (V), (X) and (XI), for example, a structural unit derived from an alicyclic compound having an olefinic double bond, such as a structural unit represented by formula (I):
    (1) wherein R 25 and R 26 are each independently hydrogen, C 1 -C 3 alkyl, C 1 -C 3 hydroxyalkyl, carboxyl, cyano, hydroxyl, or COOU, wherein U represents an alcohol residue, or R25 and R26 can be joined together to form a carboxylic anhydride residue represented by -C (= O) 0C (= O) -; a structural unit derived from an unsaturated aliphatic dicarboxylic anhydride, such as a structural unit represented by the formula (2):
    , and a structural unit represented by formula (3): (2)
    O)
    The resin containing a structural unit derived from 2-norbornene represents a strong structure, since the alicyclic group is directly present on its main chain and has this property of 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, in addition to 2-norbornene. corresponding. The structural unit derived from 2-norbornene is formed by opening its double bond and can be represented by the above formula (1). The structural unit derived from maleic anhydride and itaconic anhydride, which are the structural units derived from unsaturated aliphatic dicarboxylic anhydrides, is formed by opening their double bonds and can be represented by the above formula (2) and by formula (3), respectively.
    As regards R 25 and R 26, examples of a C 1 -C 3 alkyl group, a methyl, ethyl and n-propyl group, and examples of the C 1 -C 3 hydroxyalkyl group are a hydroxymethyl group and a 2-hydroxyethyl group.
    For R 25 and R 26, the group -COO 2 represents an ester formed from the carboxyl group and, as the alcohol residue corresponding to U, there will be mentioned, for example, an optionally substituted group, such as the C 1 -C 8 alkyl group, the 2-oxooxolan-3-yl group, the 2-oxooxolane-4-yl group, etc., and, as a substituent on the C1-C8 alkyl group, there will be mentioned a hydroxyl group, an alicyclic hydrocarbon residue, etc.
    Specific examples of the monomer used to obtain the structural unit represented by formula (1) mentioned above may include 2-norbornene, 2-hydroxy-5-norbornene, 5-norbornene-2-carboxylic acid, methyl norbornene-2-carboxylate, 2-hydroxyethyl 5-norbornene-2-carboxylate, 5-norbornene-2-methanol and 5-norbornene-2,3-dicarboxylic anhydride.
    If U represents the acid-sensitive group in the -COO-group, the structural unit represented by the formula (1) is a structural unit having the acid-sensitive group, even if it has the norbornane structure. Examples of monomers yielding the structural unit having the acid-sensitive moiety include 5-norbornene-2-carboxylic acid tert-butyl, 5-norbomene-2-carboxylic acid 1-cyclohexyl-1-methyl-ethyl groups, 1-methylcyclohexyl 1-methylcyclohexyl norbomene-2-carboxylate, 2-methyl-2-adamantyl 5-norbornene-2-carboxylate, 2-ethyl-2-adamantyl 5-norbornene-2-carboxylate, 5-norbornene-2-carboxylate 1- (4-Methylcyclohexyl) -1-methylethyl, 5-norbomene-2-carboxylate of 1- (4-hydroxycyclohexyl) -1-methyl-ethyl, 5-norbomene-2-carboxylate of 1-methyl-1- ( 4-oxo-cyclohexyl) ethyl, 1- (1-adamantyl) -1-methylethyl 5-norbomene-2-carboxylate and the like.
    The ratio of the other structural unit (s) is usually 0 to 60 mol% relative to all the structural units of the RESINE.
    The RESIN can be produced by carrying out the polymerization reaction of the corresponding monomer (s). The RESINE can also be produced by carrying out the oligomerization reaction of the corresponding monomer or monomers, followed by the polymerization of the oligomer obtained.
    The polymerization reaction is usually carried out in the presence of a radical initiator.
    There is no limitation on the radical initiator and examples include an azo compound, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 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- methyl-propionate) 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-propyl peroxydicarbonate tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate and 3,5,5-trimethylhexanoyl peroxide; and an inorganic peroxide, such as potassium peroxodisulfate, ammonium peroxodisulfate and hydrogen peroxide. Of these, the azo compound is preferable and, more preferably, 2,2'-azobis-isobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1) are preferred. acetonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and dimethyl-2,2'-azobis (2-methylpropionate), and 2,2'-azobis-isobutyronitrile compounds are particularly preferred and 2,2'-azobis (2,4-dimethylvaleronitrile).
    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 mixed ratio is not particularly limited.
    The amount of radical initiator is preferably from 1 to 20 mol% relative to 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 which is sufficient to dissolve the monomer, the radical initiator and the resin obtained. Examples include 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 alcohol-type solvent, such as isopropyl alcohol; a cyclic ester type solvent, such as γ-butyrolactone; a glycol ether ester solvent, such as monomethyl ether and propylene glycol acetate; and an acyclic ester solvent, such as ethyl lactate. These solvents can be used alone or one of their mixtures can be used.
    The amount of solvent is not limited and it is preferred in practice that it be 1 to 5 parts by weight based on 1 part of all the monomers or oligomers.
    If an alicyclic compound having an olefinic double bond and an unsaturated aliphatic dicarboxylic anhydride are used as the monomers, it is preferred to use them in excess amount, because of their tendency not to be readily polymerizable.
    After completion of the polymerization reaction, the produced RESINE can be isolated, for example, by adding to the reaction mixture obtained, a solvent, wherein the present resin is insoluble or poorly soluble, and then filtering the precipitated RESINE. If necessary, the isolated RESINE can be purified, for example, by washing with a suitable solvent.
    The RESINE itself is insoluble or poorly soluble in an aqueous alkaline solution, but becomes soluble in an aqueous alkaline solution under the action of an acid.
    The present chemically amplified resist composition comprises at least two salts selected from salt (II) and salt (III).
    Regarding the salt (Π), Y1 and Y2 represent, each independently, 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 the trifluoromethyl group being preferable.
    It is preferred that Y 1 and Y 2 are each independently fluorine or trifluoromethyl and it is most preferred that Y 1 and Y 2 are fluorine atoms.
    R21 represents a C1-C30 hydrocarbon group, wherein at least one -CH2- unit may be substituted with -CO- or -O-. 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. The C1-C30 hydrocarbon group may be substituted.
    Examples of the substituent include a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group and a cyano group, the hydroxyl group. being preferable 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 moiety include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxy-butyl and 6-hydroxyhexyl flushes.
    As specific examples of the anionic part of salt (II), mention will be made of the following compounds:







    In the salt (Π), A + represents an organic counterion. As examples of the organic counterion, there may be mentioned a cation represented by the formula (Villa):
    (Villa) wherein PI, P2 and P3 each independently represent a C1-C30 alkyl group, which may be substituted by at least one group selected from a hydroxyalkyl group, a C3-C12 cyclic hydrocarbon group and an alkoxy group C1-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 (referred to simply as cation (Villa) hereinafter), a cation represented by the formula (VUIb):
    (VTIIb) wherein P4 and P5 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group (referred to simply as cation (VIIIb) hereinafter ), a cation represented by the formula (City):
    (City) 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 form one cycle 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-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 group - CHCO-adjacent, and at least one -CH2- unit of the divalent acyclic hydrocarbon group may be replaced by -CO-, -O- or -S- (referred to simply as cation (City) hereinafter), and a cation represented by the formula (VUId):
    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 (referred to simply as cation (VUId) below).
    Examples of the C1-C12 alkoxy group in (Villa), (VUIb) and (VUId) cations 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 (Villa) cation 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 hydroxyl group, the cyclic C3-C12 hydrocarbon group and the C1-C12 alkoxy group in the (Villa) cation include methyl groups. 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 group chosen from hydroxyl group and the C1-C12 alkoxy group in the cation (Villa) include cyclopentyl, cyclohexyl and 1-adamantyl groups, 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-octylphenyl, 1-naphthyl, 2-naphthyl, fluorenyl, 4-phenylphenyl, 4-hydroxyphenyl, 4-methoxyphenyl, 4-tert-butoxyphenyl, 4-n-hexyloxyphenyl.
    Examples of the C1-C12 alkyl group in the (VUIb), (Ville) and (VlIId) cations include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl.
    Examples of the C 3 -C 12 cycloalkyl group of the (City) cation include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl groups. Examples of the divalent C3-C12 acyclic hydrocarbon group formed by linking P6 and P7 are trimethylene, tetramethylene or pentamethylene groups. Examples of the cyclic group formed together with the adjacent S + element and the divalent acyclic hydrocarbon group include tetramethylenesulfonio, pentamethylenesulphonio and oxybisethylenesulphonio groups.
    Examples of the aromatic group in the cation (City) include phenyl, tolyl, xylyl, 4-n-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-cyclohexylphenyl, 4-phenylphenyl and naphthyl groups. The aromatic group may be substituted and the examples of substituents include a C1-C6 alkoxy group, for example a methoxy, ethoxy, n-propoxy, n-butoxy, tert-butoxy and n-hexyloxy group; a C 1 -C 2 acyloxy group, such as an acetyloxy and 1-adamantylcarbonyloxy group; and a nitro group.
    Examples of the divalent acyclic hydrocarbon group formed by bonding P8 and P9 include methylene, ethylene,


    As specific examples of the cation (VIIId), mention may be made of the following compounds:

    As organic counter-ion represented by A +, the cations (Villa) and 'City' are preferable.
    As the organic counterion represented by A +, the cations represented by the following formulas (City), (VIII) (VIII) and (VIII) are also preferred:
    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 hydrogen atom of the alkyl group C1-C20 may be substituted by a hydroxyl group, a C1-C12 alkoxy group or a C3-C12 cyclic hydrocarbon group and at least one hydrogen atom of the C3-C30 cyclic hydrocarbon group may be substituted with a group hydroxyl, a C1-C12 alkyl group or a C1-C12 alkoxy group, and P31, P32, P33, P34, P35 and P36 are each independently 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 each independently represent an integer of 0 to 5, P40 and P41 represent, each independently , a C1-C6 alkyl group or a group C C3-C6alkyl, or P40 and P41 are joined to form a divalent C3-C7 hydrocarbonaceous group which forms the ring together with the adjacent S + element, P42 represents a hydrogen atom, P43 represents a C1alkyl group -C6 or a C6-C12 aromatic group which may be substituted with at least one group selected from C1-C6 alkoxy group, C6-C12 acyl group and nitro group, or P42 and P43 are joined to form a a C3-C7 divalent acyclic hydrocarbon group which forms a 2-oxocycloalkyl group together with the -CHCO-adjacent group, and at least one -CH2- unit of the divalent C3-C7 hydrocarbon group may be replaced by -CO-, - O- or -S-.
    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.
    Examples of the C1-C12 alkoxy group and the C3-C30 cyclic hydrocarbon group include the same groups as mentioned above.
    Examples of the C1-C12 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, n-octyl and n-decyl, and examples of the cyclic hydrocarbon group. C3-C12 include cyclopentyl, cyclohexyl and cyclooctyl groups.
    Examples of the C1-C6 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and n-hexyl groups, and examples of the C3-C6 cycloalkyl group include cyclobutyl, cyclopentyl groups. or cyclohexyl.
    Examples of the divalent C3-C7 acyclic hydrocarbon group formed by linking P40 and P41 include trimethylene, tetramethylene or pentamethylene groups. Examples of the divalent C3-C7 acyclic hydrocarbon group formed by binding P42 and P43 include the same groups as mentioned above.
    Examples of the C 6 -C 12 aromatic group include phenyl, naphthyl, 4-methylphenyl, 4-ethylphenyl, 4-n-butylphenyl, 4-sec-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-cyclohexylphenyl and 4-phenylphenyl.
    More preferably, it is preferred as organic counter-ion represented by A +, the cations represented by the formulas (VUIh) and (VHIk):
    wherein P25, P26 and P27 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, P44 and P45 are joined to form a hydrocarbon group. a C3-C7 divalent acyclic which forms the ring together with the adjacent S + element, P46 represents a phenyl or naphthyl group, and the cations represented by the formulas (VIIIi) and (VIII1) are particularly preferred:
    wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group, P47 and P48 are joined to form a divalent C4-C5 acyclic hydrocarbon group which forms the ring together with the adjacent S + element, P49 represents a phenyl group.
    As examples of the alkyl group and the alkoxy group, mention will be made of the same groups as those mentioned above.
    As salt (II), the salt represented by formula (VII) is preferred:
    (VII) in which A +, Y1 and Y2 have the same meanings as those defined above and R22 represents a C1-C20 linear or branched chain hydrocarbon group, which may be substituted, or a cyclic C3-C30 hydrocarbon group; which may be substituted, and at least one -CH2- unit of the C1-C20 linear or branched chain hydrocarbon group or the C3-C30 cyclic hydrocarbon group may be substituted with -CO- or -O-.
    As salt (II), the salt represented by the following formula (XII) is more preferably:
    (XII) in which A +, Y1 and Y2 are the same as those defined above, Z4 represents a single bond or a C1-C4 alkylene group, Q represents -CH2-, -CO- or -CH (OH) - and ring XI represents a C3-C30 monocyclic or polycyclic hydrocarbon moiety, wherein two hydrogen atoms are substituted with = O at the Q position, when Q represents -CO-, or wherein a hydrogen atom is substituted with a hydroxyl group at the Q position, when Q represents -CO (OH) -, and at least one hydrogen atom of 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.
    Examples of the C1-C6 alkyl group, the C1-C6 alkoxy group, the C1-C4 perfluoroalkyl group and the C1-C6 hydroxyalkyl group include the same groups as described above, respectively.
    Examples of the C1-C4 alkylene group include methylene, ethylene, trimethylene and tetramethylene groups. It is preferred that Z4 is the single bond, the methylene moiety or the ethylene moiety, and more preferably Z4 is the single bond or the methylene moiety.
    Examples of ring XI include a C 4 -C 8 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 by a hydroxyl group and 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.
    Specific examples of ring XI include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, an adamanthyl group, a norbornyl group, a 2-oxo-cyclopentyl 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-hydroxy-cyclopentyl group, a 3-hydroxycyclohexyl group, a 4-hydroxycyclohexyl group, a 4-oxo group, 2-adamantyl, a 3-hydroxy-1-adamantyl group, a 4-hydroxy-1-adamantyl group, a 5-oxonorboman-2-yl group, a 1,7,7-trimethyl-2-oxonorboman-2 group; a 3,6,6-trimethyl-2-oxo-bicyclo [3,1,1] heptan-3-yl group, a 2-hydroxy-norboman-3-yl group, a 1,7,7-group; trimethyl-2-hydroxybicyclo [3.1.1] heptan-3-yl, trimethyl-2-hydroxynorboman-3-yl, and the groups s following (in the following formulas, the linear drawn with an open end represent a bond that extends from an adjacent group).
    As salt (II), the salts represented by formula (XIII) are preferred:
    (XIII) wherein P22, P23, P24, Y1, Y2, XI, Q and Z4 are the same as those defined above, and those represented by the formula (XIV):
    (XIV) wherein P47, P48, P49, Y1, Y2, XI, Q and Z4 are the same as those defined above.
    In salt (III), R23 represents a C1-C8 linear or branched chain perfluoroalkyl group and A + represents an organic counterion.
    Examples of the C1-C8 linear or branched chain perfluoroalkyl moiety include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl and heptadecafluorooctyl moieties.
    As examples of the organic counter-ion represented by A '+, mention will be made of the same cations as those mentioned for A +. It is preferred that A '+ is a cation (Villa) or (City) and, more preferably, it is preferred that A' + is a cation (VUIh) or (VHIk) and most preferably it is preferred that A '+ is a cation (VlIIi) or (VIII1).
    The salt (II) can be produced by a process comprising reacting a salt represented by the formula (XV):
    (XV) in which M represents the element Li, Na, K or Ag, and Y1, Y2 and R21 have the same meanings as those defined above (simply designated by salt (XV) below), with a compound represented by the formula (XVI): (XVI) wherein A + has the same meaning as defined above and G represents F, Cl, Br, I, BF4, AsF6, SbF6, PF6 or 004 (referred to simply as the compound ( XVI) below).
    The reaction of the salt (XV) and the compound (XVI), 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 (XVI) is usually 0.5 to 2 moles per 1 mole of the salt (XV). The salt (II) obtained by the above process can be isolated by recrystallization and can be purified by washing with water.
    Salt (III) can be produced by a process comprising reacting a salt of formula (XVII):
    (XVII) in which M 'represents H, Li, Na, K or Ag and R 23 has the same meaning as defined above (referred to simply as salt (XVII) below), with a compound of formula (XVIII) :
    (XVIII) wherein A '+ has the same meaning as defined above and G' represents F, Cl, Br, I, BF4, AsF6, SbF6, PF6 or C104 (referred to simply as compound (XVIII) below) ).
    The reaction of the salt (XVII) and the compound (XVIII) 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 (XVIII) is usually 0.5 to 2 moles per 1 mole of the salt (XVII). The salt (III) obtained by the above process can be isolated by recrystallization and can be purified by washing with water.
    The salt (II) and the salt (III) are usually used as an acid generator and the acid generated by the application of radiation on the salt (II) and the salt (III) acts catalytically against the acid-sensitive groups of the RESINE, cleaves the acid-sensitive group, so that the RESINE becomes soluble in an aqueous alkaline solution. This composition is suitable for a chemically amplified positive resist composition.
    As the resist composition of the present invention, a resist composition comprising salt (II) and at least one salt selected from salt (II) and salt (III) is preferred and, more preferably, a resist composition is preferred. comprising at least two salts selected from salt (II).
    When the present resist composition comprises salt (II) and salt (III), the A + ion of salt (II) and the A + ion of salt (III) may be the same and may be different from each other. the other.
    When the resist composition of the invention comprises at least two types of salt (II), they may have the same A + ion and different anionic moieties or they may have different A + ions and anionic moieties.
    When the resist composition of the invention comprises at least two types of salt (III), they may have the same A '+ ion and different anionic moieties or they may have different A' + ions and the same anionic moieties.
    The present resist composition preferably comprises at least two salts selected from salt (II), wherein A + is the cation (Villa) or (City), and salt (III), wherein A '+ is the cation (Villa) or (City).
    It is more preferred that the resist composition of the invention comprises salt (II), wherein A + is the cation (Villa), and at least one salt selected from salt (II) and salt (III).
    As resist composition of the invention, there is particularly preferred a resist composition comprising salt (Π), wherein A + is the cation (Villa), and at least one salt selected from salt (II), wherein A + represents the cation (Villa) or (City), and the salt (III), wherein A '+ is the cation (Villa) or (City) and, most preferably, a resist composition comprising the salt (II) is preferred wherein A + is the cation (Villa), and at least one salt selected from salt (II), wherein A + is the cation (City), and salt (III), wherein A '+ represents the cation ( Villa).
    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 the salt (II) and salt (III) in relation to the amount of total of the resin component, salt (II) and salt (III).
    In the present resist composition, performance degradation due to acid inactivation 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 T1 and T12 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 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 6 alkoxy group, T 3 and T 4 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a. 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-C4 alkyl group, and a group C1-C6 alkoxy, or T3 and T4 are joined together with the carbon atoms to which they are bound to form an aromatic ring,
    :. . * r: S
    T5 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 may be substituted with. 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, T6 represents an alkyl or cycloalkyl group and the alkyl and cycloalkyl groups may be substituted with 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, and W represents -CO-, -NH-, -S- , -SS-, an alkylene group of which at least one methylene unit may be replaced by -O-, or an alkenylene group of which at least one methylene unit may be replaced by -O-, and a quaternary ammonium hydroxide represented by following formula:
    wherein T7, T8, T9 and T10 independently represent an alkyl group, a cycloalkyl group or an aryl group, and the alkyl, cycloalkyl and aryl groups may be substituted with 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.
    The alkyl group in the substituents T1, T2, T3, T4, T5, T6, T7, T8, T9 and T10 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. As examples of the C1-C6 alkoxy group which may be substituted by the C1-C6 alkoxy group, there will be mentioned methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy, n- hexyloxy 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 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 in the substituents T1, T2, T3, T4, T5, T6, T7, T8, T9 and T10 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 with a C1-C4 alkyl group, and a C1-C6 alkoxy group include cyclopentyl groups. cyclohexyl, cycloheptyl or cyclooctyl.
    The aryl group in the substituents T1, T2, T3, T4, T5, T6, T7, T8, T9 and T10 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. or a naphthyl group.
    The alkoxy group in the substituents T3, T4 and T5 preferably contains about 1 to 6 carbon atoms and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert. butoxy, n-pentyloxy and n-hexyloxy.
    The alkylene and alkenylene groups in the substituent W contain, preferably, 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, 1,3-propene -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-methyl-aniline, 4-methylaniline, 4-nitroaniline , 1-naphthylamine, 2-naphthylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3-dimethyldiphenylmethane, 4,4'-diamino-3,3 1,4-diethyl diphenylmethane, 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, ethyldiheptylamine, 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'-dipyridylsulfur, 4,4 dipyridyl disulfide, 1,2-bis (4-pyridyl) ethylene, 2,2'-dipicolylamine and 3,3'-dipolyol-1-amine.
    Examples of quaternary ammonium hydroxide include tetramethylammonium hydroxide compounds, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, (3-trifluoromethylphenyl) trimethylammonium hydroxide, and hydroxyethyl) trimethyl ammonium (so-called "choline").
    A hindered amine compound having a piperidine backbone as described in JP 11-52575 A1 can also be used as a neutralizing agent.
    On the subject of pattern formation having a higher resolution, quaternary ammonium hydroxide is preferably used as the neutralizing agent.
    When the basic compound is used as the neutralizing agent, the present resist composition preferably comprises 0.01 to 1% by weight of the basic compound relative to the total amount of the resin component and the salt (Π).
    The present resist composition may contain, if necessary, a small amount of various additives, such as a sensitizing agent, a dissolution inhibitor, other polymers, a surfactant, a stabilizer and a dye, as long as the effect of the present invention is not hindered.
    The present resist composition is usually in the form of a liquid resist composition, in which the aforementioned ingredients are dissolved in a solvent, and then the liquid resist composition is applied to a substrate, such as a silicon wafer, by a conventional method, such as spin coating. The solvent used is 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 can be employed.
    Examples of the solvent include a glycol ether ester, such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol 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 a mixture of two or more of them can be used.
    A resist film applied to the substrate and then dried is subjected to exposure for patterning, heat treatment is then carried out to facilitate a deblocking reaction, and development is carried out with an alkaline developer. The alkaline developer used may be any of a variety of aqueous alkaline solutions used in the art. In general, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly referred to as "choline") is often used.
    It should be noted that the embodiments disclosed herein are examples in all respects and are not limiting. It is understood that the scope of the present invention is not determined by the foregoing descriptions, but by the appended claims, and includes all variants of the meanings and equivalents of the claims.
    The invention will now be described more specifically by way of examples which are not intended to limit the scope of the present invention. The term "%" and the term "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 expressed on a weight basis. , unless otherwise stated. The weight average molecular weight of any material used in the following examples is a value obtained by gel permeation chromatography [type HLC-8120GPC, column (three columns): TSK Multipore HXL-M gel, solvent: tetrahydrofuran manufactured by TOSOH CORPORATION] using styrene as a standard reference material. The structures of the compounds were determined by NMR (type GX-270 or EX-270 type, manufactured by JEOL LTD) and by mass spectrometry (liquid chromatography type 1100, manufactured by AGILENT TECHNOLOGIES LTD., Mass spectrometry: LC / MSD type or LC / MSD TOF type, manufactured by AGILENT TECHNOLOGIES LTD.).
    EXAMPLE OF SYNTHETIC SALT 1
    (1) 230 parts of a 30% aqueous solution of sodium hydroxide are added to a mixture of 100 parts of methyldifluoroethyl acetate (fluorosulfonyl) and 250 parts of deionized water in an ice bath. The resulting mixture is heated and refluxed at 100 ° C for 3 hours. At the end of a cooling step, the cooled mixture is neutralized with 88 parts of concentrated hydrochloric acid and the solution obtained is concentrated so that 164.8 parts of sodium salt of difluorosulphoacetic acid are obtained ( containing an inorganic salt, purity: 62.6).
    (2) 5.0 parts of sodium difluorosulfoacetate (purity: 62.6%), 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 a cooling step, the mixture is filtered to recover solids, and these solids are washed with tert-butyl methyl ether to give 5.5 parts of the salt represented by formula (a) mentioned above. The purity of the latter is 35.6%, which value was calculated from the 1 H-NMR analysis result: 1 H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (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) To a quantity of 5.4 parts of the salt represented by formula (a) obtained in step (2) (35.6% purity), a mixed solvent consisting of 16 parts of acetonitrile and 16 parts of deionized water. A solution prepared by mixing 1.7 parts of triphenylsulfonium chloride, 5 parts of acetonitrile and 5 parts of deionized water is added to the resulting mixture. After stirring for 15 hours, the resulting mixture is concentrated and extraction is carried out with 142 parts of chloroform. The resulting organic layer is washed with deionized water and concentrated. The resulting concentrate was washed with 24 parts of tert-butyl methyl ether and the solvent was decanted for removal to give 1.7 parts of the salt represented by the above-mentioned formula (b) under form of a white solid which has been designated B1.
    1H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (ppm) 1.83 (d, 2H, J = 12.7Hz), 2.00 (d, 2H, J = 12.0 Hz), 2.29 to 2.32 (m, 7H), 2.53 (s, 2H), 7.75 to 7.91 (m, 15H).
    MS (ESI (+) spectrum): M + 263.2 (C18H15S + = 263.09) MS (ESI spectrum (-)): M-323.0 (C12H13F2O6S- = 323.04) EXAMPLE OF SYNTHETIC SALT 2
    (1) 460 parts of a 30% aqueous sodium hydroxide solution are added to a mixture of 200 parts of methyldifluoro (fluorosulfonyl) acetate and 300 parts of deionized water in an ice bath. The resulting mixture is heated and refluxed at 100 ° C for 2.5 hours. After a cooling step, the cooled mixture is neutralized with 175 parts of concentrated hydrochloric acid and the solution obtained is concentrated so that 328.19 parts of sodium salt of difluorosulfoacetic acid (containing an inorganic salt) are obtained. purity: 62.8%).
    (2) 75.1 parts of p-toluenesulfonic acid are added to a mixture consisting of 123.3 parts of the sodium salt of difluorosulfoacetic acid (purity: 62.8%), 65.7 parts of adamantanemethanol and 600 parts of dichloroethane, and the resulting mixture is heated and refluxed for 12 hours. The mixture is concentrated to remove dichloroethane and 400 parts of tert-butyl methyl ether are added to the resulting residue. The resulting mixture is stirred and filtered to obtain a solid. 400 parts of acetonitrile are added to the solid and the mixture obtained is stirred and filtered. 400 parts of acetonitrile are added to the solid and the mixture obtained is stirred and filtered. The filtrates obtained are mixed and concentrated so that 99.5 parts of the salt represented by the formula (c) mentioned above is obtained.
    1H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (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 is stirred at room temperature for 24 hours and the white precipitates are filtered, washed and dried to give 207.9 parts of 1- (2-oxo-2-phenylethyl) tetrahydro-thiophenium bromide as crystals. white.
    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 (c), 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 in step (3) and 159 parts of deionized water are added to the resulting solution. 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-butyl methyl ether are added to the concentrate and the resulting mixture is 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 (d) as a white solid, which was designated B2.
    1H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (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 (ESI (+) spectrum): M + 207.0 (C12H14O5S + = 207.08) MS (ESI spectrum (-)): M-323.0 (C13H17F2O5S- = 323.08) EXAMPLE OF SYNTHETIC SALT 3
    (1) 10.0 parts of the salt represented by the formula (a) (purity: 55.2%), which was obtained by a method similar to that described in the salt synthesis examples (1) and (2), to a mixed solvent consisting 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, 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 give 5.2 parts of the salt represented by formula (e) mentioned above as a white solid, which we have designated by B3.
    1H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (ppm) 1.83 (d, 2H, J = 12.5Hz), 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; (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 (C12H14O5 + = 207.08) MS (ESI (-) spectrum): M-323.0 (C12H13F2O6S- = 323.04) SALT SYNTHESIS EXAMPLE 4
    (1) 230 parts of a 30% aqueous solution of sodium hydroxide are added to a mixture of 100 parts of methyldifluoro (fluorosulfonyl) acetate and 150 parts of deionized water in an ice bath. The resulting mixture is heated and refluxed at 100 ° C for 3 hours. After a cooling step, the cooled mixture is neutralized with 88 parts of concentrated hydrochloric acid and the solution obtained is concentrated so that 164.4 parts of the sodium salt of difluorosulphoacetic acid (containing an inorganic salt) are obtained. purity: 62.7%).
    (2) 1.9 parts of the sodium salt of difluorosulfoacetic acid (purity: 62.7%) and 9.5 parts of Ν, Ν-dimethylformamide are mixed, followed by the addition of 1.0 part of Ι, Γ carbonyl diimidazole. The resulting mixture is stirred for 2 hours. The solution obtained is added to a solution prepared by mixing 1.1 parts of (3-hydroxy-1-adamantyl) methanol, 5.5 parts of Ν, Ν-dimethylformamide and 0.2 part of sodium hydride, and then Stir it for 2 hours. The resulting solution is stirred for 15 hours to give the salt-containing solution represented by formula (f) above.
    (3) 17.2 parts of chloroform and 2.9 parts of an aqueous solution of 14 are added to the solution containing the salt represented by formula (f), 8% triphenylsulfonium chloride. The resulting mixture is stirred for 15 hours, then separated into an organic layer and an aqueous layer. The aqueous layer is extracted with 6.5 parts of chloroform to give a chloroform layer. The organic layer and the chloroform layer are mixed to wash with deionized water and then concentrated. The resulting concentrate is mixed with 5.0 parts of tert-butyl methyl ether and the resulting mixture is stirred and filtered to give 0.2 part of the salt represented by the above-mentioned formula (g) as a solid. white, which has been designated B4.
    1 H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (ppm) 1.38 to 1.51 (m, 12H), 2.07 (s, 2H), 3.85 (s, 2H) ), 4.41 (s, 1H), 7.75 to 7.89 (m, 15H).
    MS (ESI (+) spectrum): M + 263.07 (C18H15S + = 263.09) MS (ESI spectrum (-)): M-339.10 (C13H17F206S- = 339.07) EXAMPLE OF SALT SYNTHESIS
    (1) 230 parts of 30% aqueous sodium hydroxide solution are added to a mixture of 100 parts of methyl difluoro (fluorosulfonyl) acetate and 250 parts of deionized water in an ice bath. The resulting mixture is heated and refluxed at 100 ° C for 2.5 hours. After a cooling step, the cooled mixture is neutralized with 88 parts of concentrated hydrochloric acid and the solution obtained is concentrated so that 158.4 parts of sodium salt of difluorosulphoacetic acid (containing an inorganic salt, purity: 65.1%).
    (2) 50.0 parts of the sodium salt of difluorosulfoacetic acid (purity: 65.1%), 18.76 parts of cyclohexylmethanol and 377 parts of dichloroethane are mixed and 31.26 parts of p-acid are added. toluenesulfonic. The mixture obtained is heated and refluxed for 6 hours. The mixture obtained is concentrated to remove the dichloroethane, then 200 parts of heptane are added to the residue obtained. The resulting mixture is stirred and filtered. The solid obtained is mixed with 200 parts of acetonitrile. The resulting mixture is stirred and filtered. The filtrate obtained is concentrated to give 39.03 parts of the salt represented by the formula (h) mentioned above.
    1 H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (ppm) 0.90 to 1.27 (m, 5H), 1.58 to 1.71 (m, 6H), 4.02 (d, 2H).
    (3) 39.03 parts of the salt represented by formula (h), which was obtained in step (2), are dissolved in 195.2 parts of deionized water. A solution prepared by mixing 39.64 parts of triphenylsulphonium chloride and 196.4 parts of deionized water is added to the resulting solution and 500 parts of acetonitrile are then added thereto. The resulting mixture is stirred for 15 hours and then concentrated. The residue obtained is extracted twice with 250 parts of chloroform and the organic layers obtained are mixed and washed with deionized water and then concentrated. The resulting concentrate is mixed with 200 parts of tert-butyl methyl ether and the resulting mixture is stirred and filtered to give 40.16 parts of the salt represented by the above-mentioned formula (i) as a white solid, which has been designated B5.
    1H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (ppm) 0.88 to 1.28 (m, 5H), 1.56 to 1.71 (m, 6H), 4.01 (d, 2H), 7.75 to 7.90 (m, 15H).
    MS (ESI (+) spectrum): M + 263.1 (C18H15S + = 263.09) MS (ESI spectrum (-)): M-271.1 (C9H13F2O5S- - 271.05).
    EXAMPLE OF SALT SYNTHESIS 6
    (1) 460 parts of a 30% aqueous solution of sodium hydroxide 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 heated and refluxed at 100 ° C for 2.5 hours. At the end of a cooling phase, the cooled mixture is neutralized with 175 parts of concentrated hydrochloric acid and the solution obtained is concentrated so that 328.19 parts of the sodium salt of difluorosulfoacetic acid are obtained. (containing an inorganic salt, purity: 63.5%).
    (2) 24.0 parts of p-toluenesulfonic acid are added to a mixture of 39.4 parts of sodium salt of difluorosulfoacetic acid (purity: 63.5%), 21.0 parts of adamantanemethanol and 200 parts of dichloroethane, and the resulting mixture is heated and refluxed for 7 hours. The mixture is concentrated to remove the dichloroethane and 250 parts of tert-butyl methyl ether are added to the resulting residue. The resulting mixture is stirred and filtered to give the solid. 250 parts of acetonitrile are added to the solid and the mixture obtained is stirred and filtered. The filtrate obtained is concentrated so that 32.8 parts of the salt represented by formula (c) mentioned above is obtained.
    (3) 32.8 parts of the salt represented by formula (c) above, which was obtained above in step (2), are dissolved in 100 parts of deionized water. A solution prepared by mixing 28.3 parts of triphenylsulfonium chloride and 140 parts of methanol was added to the resulting solution and stirred for 15 hours. The resulting mixture is concentrated. The residue obtained is extracted twice with 200 parts of chloroform. The organic layers obtained are mixed and washed several times with deionized water, until the aqueous layer obtained is neutralized. The solution obtained is concentrated. 300 parts of tert-butyl methyl ether are added to the concentrate and the mixture is 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 (j) as a white solid, which was designated B6.
    1H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (ppm) 1.52 (d, 6H), 1.63 (dd, 6H), 1.93 (s, 3H), 3, 81 (s, 2H), 7.76 to 7.90 (m, 15H).
    MS (ESI (+) spectrum): M + 263.2 (C18H15S + = 263.09) MS (ESI (-) spectrum): M-323.0 (C13H17F2O5S- = 323.08) SALT SYNTHESIS EXAMPLE 7
    (1) 26.5 parts of diphenylsulfide are dissolved in 79.4 parts of acetonitrile. 29.5 parts of silver perchlorate (I) are added, then a solution prepared by mixing 52.3 parts of acetonitrile and 26.2 parts of n-butyl iodide is added. The resulting mixture is stirred for 24 hours. The precipitate is filtered to remove the solvent and the filtrate is concentrated. The concentrate is mixed with 135.9 parts of tert-butyl methyl ether and the resulting mixture is stirred and filtered. 101.7 parts of tert-butyl methyl ether are added to the solid and the resulting mixture is stirred and filtered to give 14.8 parts of n-butyl-diphenylsulfonium perchlorate as a white solid.
    1 H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): 6 (ppm) 0.88 (t, 3H), 1.41 to 1.49 (m, 2H), 1.52 to 1.64 (m, 2H), 4.31 (t, 2H), 7.69-7.82 (m, 6H), 8.08 (d, 4H).
    (2) 5.00 parts of the salt represented by the above-mentioned formula (c), which was obtained by a process similar to that described in steps (1) and (2) of the synthesis example, are mixed together. of the aforementioned salt 6 to 50.0 parts of chloroform. To the resulting mixture, a mixture prepared by mixing 13.94 parts of n-butyldiphenylsulfonium perchlorate obtained above in step (1) is added to 41.82 parts of deionized water. The resulting mixture is stirred for 15 hours and separated into an organic layer and an aqueous layer. The aqueous layer is extracted with 10.0 parts of chloroform to give a chloroform layer. The organic layer and the chloroform layer are mixed and washed several times with deionized water until the resulting aqueous layer is neutralized and concentrated. The concentrate obtained is mixed with 37.6 parts of tert-butyl methyl ether and the mixture obtained is stirred and then filtered. The solid obtained is mixed with 16.8 parts of ethyl acetate and the mixture obtained is stirred and filtered to give 2.89 parts of the salt represented by the formula (a) mentioned above in the form of a solid. white, which is designated B7.
    1 H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (ppm) 0.88 (t, 3H), 1.42 to 1.67 (m, 16H), 1.91 (s, 3H) ), 3.80 (s, 2H), 4.33 (t, 2H), 7.71-7.83 (m, 6H), 8.09 (d, 4H).
    MS (ESI (+) spectrum): M + 243.11 (C16H19S + = 243.12) MS (ESI (-) spectrum): M-323.10 (C13H17F2O5S- = 323.08) SALT SYNTHESIS EXAMPLE 8
    (1) 6.56 parts of diphenylsulfide are dissolved in 19.7 parts of acetonitrile. 7.30 parts of silver perchlorate (I) are added, and a solution prepared by mixing 10.0 parts of acetonitrile and 5.00 parts of methyl iodide is added. The resulting mixture is stirred for 24 hours. The precipitate is filtered to remove the solvent and the filtrate is concentrated. The concentrate is mixed with 39.2 parts of tert-butyl methyl ether and the resulting mixture is stirred and filtered to give 9.38 parts of methyldiphenylsulfonium perchlorate as a white solid.
    1 H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (ppm) 3.81 (s, 3H), 7.67 to 7.79 (m, 6H), 8.01 to 8.04 (m, 4H).
    (2) 8.29 parts of the salt represented by the above-mentioned formula (c), which was obtained by a process similar to that described in steps (1) and (2) of the synthesis example of above salt 6, 49.7 parts of chloroform. To the resulting mixture is added a mixture prepared by mixing 9.38 parts of methyldiphenylsulfonium perchlorate obtained in step (1) above with 28.14 parts of deionized water. The resulting mixture is stirred for 15 hours, then separated into an organic layer and an aqueous layer. The aqueous layer is extracted with 33.1 parts of chloroform to obtain a chloroform layer. The organic layer and the chloroform layer are mixed and washed repeatedly with deionized water until the resulting aqueous layer is neutralized and then concentrated. The resulting concentrate is mixed with 33.8 parts of tert-butyl methyl ether and the resulting mixture is stirred. The supernatant liquid is removed by decantation to obtain 7.81 parts of the salt represented by the above-mentioned formula (1) in the form of a colorless liquid, which has been designated B8.
    1H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (ppm) 1.50 (d, 6H), 1.61 (dd, 6H), 1.91 (s, 3H), 3, 80 (s, 2H), 3.82 (s, 3H), 7.67 to 7.79 (m, 6H), 8.02 to 8.05 (m, 4H).
    MS (ESI (+) spectrum): M + 201.0 (C13H13S + = 201.07) MS (ESI (-) spectrum): M-323.0 (C13H17F2O5S- = 323.08) SALT SYNTHESIS EXAMPLE 9
    (1) 5.0 parts of the salt represented by formula (a) (purity: 49.1%), which was obtained by a process similar to that described in steps (1) and (2) of example of synthesis of the aforementioned salt 1, 50.0 parts of chloroform. To the resulting mixture was added 42.0 parts of an aqueous solution of triphenylsulfonium chloride (concentration: 5.0%). After stirring for 15 hours, the resulting mixture is separated into an organic layer and an aqueous layer. The resulting aqueous layer is extracted with 25.0 parts of chloroform to give a chloroform layer. The organic layer and the chloroform layer are mixed and the resulting solution is washed several times with deionized water until the resulting aqueous layer has been neutralized. The solution is concentrated and the resulting concentrate is mixed with 29.6 parts of tert-butyl methyl ether and the supernatant liquid is decanted off. The resulting residue is mixed with 16.6 parts of ethyl acetate and the supernatant liquid is removed by decantation to give 1.6 part of the salt represented by the above-mentioned formula (m) as a solid. pale yellow, which has been designated B9.
    1 H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (ppm) 1.82 (d, 2H), 1.99 (d, 2H), 2.21 to 2.35 (m, 7H) ), 2.52 (s, 2H), 3.81 (s, 3H), 7.67 to 7.79 (m, 6H), 8.01 to 8.06 (m, 4H).
    EXAMPLE OF SALT SYNTHESIS 10
    (1) 5.0 parts of thioanisole are dissolved in 15.0 parts of acetonitrile. 8.35 parts of silver perchlorate (I) are added, then 11.4 parts of a solution of acetonitrile containing 5.71 parts of methyl iodide are added. The resulting mixture is stirred for 24 hours. The precipitate is filtered off and the filtrate is concentrated. The concentrate is mixed with 36.8 parts of tert-butyl methyl ether and the resulting mixture is stirred and filtered to give 8.22 parts of dimethylphenylsulfonium perchlorate as a white solid.
    1H-NMR (dimethylsulfoxide-d6, internal standard tetramethylsilane): δ (ppm) 3.25 (s, 6H), 7.67-7.80 (m, 3H), 8.03-8.08 (m, 2H).
    (2) 5.98 parts of the salt represented by the above-mentioned formula (c), which was obtained by a process similar to that described in steps (1) and (2) of the synthesis example of above salt 6, 35.9 parts of chloroform. To the resulting mixture is added a solution obtained by mixing 4.23 parts of dimethylphenylsulfonium perchlorate obtained above in step (1) with 12.7 parts of deionized water. The resulting mixture is stirred for 4 hours and separated into an organic layer and an aqueous layer. The aqueous layer is extracted with 23.9 parts of chloroform to give a chloroform layer. The organic layer and the chloroform layer are mixed and washed repeatedly with deionized water until the resulting aqueous layer is neutralized and then concentrated. The resulting concentrate is mixed with 31.8 parts of tert-butyl methyl ether and the resulting mixture is filtered to give 5.38 parts of the salt represented by the above-mentioned formula (n) as a white solid. which has been designated B10.
    1H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (ppm) 1.51 (d, 6H), 1.62 (dd, 6H), 1.92 (s, 3H), 3, 26 (s, 6H), 3.80 (s, 2H), 7.68 to 7.80 (m, 3H), 8.03 to 8.06 (m, 2H).
    MS (ESI (+) spectrum): M + -139.0 (C8H11S + = 139.06) MS (ESI spectrum (- »: M-323.0 (C13H17F2O5 S = 323.08) EXAMPLE OF SALT SYNTHESIS 11
    (1) 460 parts of a 30% aqueous solution of sodium hydroxide are added to a mixture of 200 parts of methyl difluorosulfonylacetate and 300 parts of deionized water in an ice bath. The resulting mixture is heated and refluxed at 100 ° C for 2.5 hours. After a cooling period, the cooled mixture is neutralized with 175 parts of concentrated hydrochloric acid and the resulting solution is concentrated so that 328.19 parts of the sodium salt of difluorosulfoacetic acid (containing an inorganic salt) are obtained. purity: 62.8%).
    (2) 5.0 parts of sodium difluorosulfoacetate (purity: 62.8%) obtained in step (1), 2.6 parts of 4-oxo-1-adamantanol and parts of ethylbenzene, and then 0.8 parts of concentrated sulfuric acid The resulting mixture is refluxed for 30 hours. After a cooling step, the mixture is filtered to solids and these solids are washed with tert-butyl methyl ether to give 5.5 parts of the salt represented by formula (a) mentioned above. Its purity is 57.6%, which value was calculated from the 1 H-NMR analysis result.
    1H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (ppm) 1.84 (d, 2H), 2.00 (d, 2H), 2.29 to 2.32 (m, 7H) ), 2.54.
    (3) To 4.3 parts of the salt represented by formula (a) obtained in step (2) (purity: 57.6%), 43.0 parts of chloroform are added. To the resulting mixture, 2.2 parts of the sulfonium salt represented by the above-mentioned formula (o) and 11.7 parts of deionized water are added. After a stirring period of 15 hours, the mixture obtained is separated into an organic layer and an aqueous layer. The organic layer is washed several times with deionized water until the resulting aqueous layer is neutralized and then concentrated. The resulting concentrate is mixed with 15.0 parts of tert-butyl methyl ether and the supernatant liquid is removed by decantation. The resulting residue is dried to give 2.3 parts of the salt represented by the above-mentioned formula (p) in the form of a white solid which has been designated Bll.
    1 H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): δ (ppm) 1.82 (d, 2H), 1.98 (d, 2H), 2.27 to 2.35 (m, 7H) ), 2.51 (s, 2H), 7.52 (d, 4H), 7.74 to 7.89 (m, 20H), 7.91 (d, 4H).
    The monomers used in the following resin synthesis examples are the following monomers M1, M2, M3, M4, M5 and M6:
    EXAMPLE OF SYNTHESIS OF RESIN 1
    13.50 parts of the monomer M1, 3.53 parts of the monomer M2 and 18.66 parts of the monomer M3 are dissolved in a quantity of 1,4-dioxane corresponding to 1.5 times the amount, the amount of all the monomers. which is used (molar ratio of the monomers: monomer M1 monomer M2: monomer M3 = 40: 11:49). To the solution is added 2,2-azobisisobutyronitrile and 2,2'-azobis (2,4-
    dimethylvaleronitrile) as an initiator in the ratio of 1 mol% and 3 mol%, respectively, based on the molar amount of all the monomers, and then the resulting mixture is heated at 74 ° C. for about 5 hours. The reaction solution is 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 a mixed solvent based on methanol and water, in order to purify it. As a result, a copolymer having a weight average molecular weight of about 9200 is obtained with a yield of 80%. This copolymer contains the following structural units. It has been designated AL resin
    EXAMPLE OF SYNTHESIS OF RESIN 2
    30.00 parts of the monomer M1, 14.27 parts of the monomer M2 and 10.28 parts of the monomer M4 are dissolved in an amount of methyl isobutyl ketone corresponding to 2.6 times the amount of all the monomers used ( molar ratio of the monomers: M1 monomer: M2 monomer: M4 monomer = 50:25:25). To the solution is added 2,2'-azobisisobutyronitrile as initiator, in a ratio of 2 mol% to the molar amount of all the monomers. The resulting mixture is heated at 87 ° C for about 6 hours. The reaction solution is poured into a large amount of a mixed solvent based on methanol and water to cause precipitation. The precipitate is isolated and washed twice with a large amount of mixed methanol solvent and water to purify it. As a result, the copolymer with a weight average molecular weight of about 9400 is obtained in 47% yield. This copolymer contains the following structural units. It has been designated A2 resin.
    EXAMPLE OF SYNTHESIS OF RESIN 3
    15.00 parts of the monomer M1, 4.89 parts of the monomer M2, 11.12 parts of the monomer M3 and 8.81 parts of the monomer M4 are dissolved in a quantity of 1,4-dioxane corresponding to 1.5 times the amount. of all the monomers that are used (molar ratio of monomers: monomer ML monomer M2: monomer M3: monomer M4 = 35: 12: 23: 30). To the solution is added 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) as initiator, in a ratio of 1 mol% and 3 mol%, respectively, relative to to the molar amount of all the monomers. The resulting mixture is heated at 77 ° C for about 5 hours. The reaction mixture is cooled and then poured into a large amount of a mixed solvent of methanol and water to precipitate. The precipitate is isolated and washed twice with a large amount of a mixed solvent based on methanol and water for the purpose of purifying it. As a result, the copolymer having a weight average molecular weight of about 8,100 is obtained in a yield of 78%. This copolymer contains the following structural units. It has been designated A3 resin.
    EXAMPLE OF SYNTHESIS OF RESIN 4
    In a four-neck flask equipped with a thermometer and a condenser, 77.24 parts of 1,4-dioxane were charged and sparged with nitrogen gas for 30 minutes. Under a nitrogen atmosphere and after the solvent has been heated to a temperature of 74 ° C, a solution prepared by mixing 45.00 parts of the monomer M1, 10.07 parts of the monomer M2, 50 is added dropwise. , 78 parts of M3 monomer, 14.51 parts of M4 monomer, 8.37 parts of M5 monomer, 0.88 part of 2,2'-azobisisobutyronitrile, 3.97 parts of 2,2'-azobis (2,4 dimethylvaleronitrile) and 115.86 parts of 1,4-dioxane, with the solvent heated in the course of 2 hours, while maintaining the temperature at 74 ° C. (molar ratio of the monomers, M1 monomer: M2 monomer: M3 monomer: M4 monomer: M5 monomer = 34: 8: 34: 16: 8). After the addition, the resulting mixture is maintained at 74 ° C for 5 hours. The reaction mixture is cooled and diluted with 141.61 parts of 1,4-dioxane. The mixture obtained is poured into a mixed solution consisting of 1339 parts of methanol and 335 parts of deionized water with stirring, the mixture is stirred and the resin deposited in the mixture is corrected by filtration. 837 parts of methanol are added to the deposit, the mixture is stirred and then the solid is corrected by filtration. The series of operations including addition, stirring and filter correction are repeated two more times, then the whole is dried under reduced pressure to give 96.4 parts of copolymer having a weight average molecular weight of 8924 and a ratio Mw (weight average molecular weight) / Mn (number average molecular weight) of 1.87 in a yield of 75%. This copolymer contains the following structural units. It has been designated by A4 resin.
    EXAMPLE OF SYNTHESIS OF RESIN 5
    In a four-necked flask equipped with a thermometer and a condenser, 83.33 parts of 1,4-dioxane were charged and bubbled with nitrogen gas for 30 minutes. Under a nitrogen atmosphere and after the solvent has been heated to 74 ° C, a solution prepared by mixing 8.68 parts of monomer M2, 36.05 parts of monomer M3, 32, is added dropwise to the heated solvent. 31 parts of the M4 monomer, 16.83 parts of the M5 monomer, 45.00 parts of the M6 monomer, 1.01 part of 2,2'-azobisisobutyronitrile, 4.56 parts of 2,2'-azobis (2,4- dimethylvaleronitrile) and 124.99 parts of 1,4-dioxane within 2 hours while maintaining the temperature at 74 ° C (monomer ratio: monomer M2: monomer M3 monomer M4: monomer M5: monomer M6 = 6: 21: 31: 14: 28). After the addition step, the resulting mixture is maintained at 74 ° C for 5 hours. The reaction mixture is cooled and diluted with 152.76 parts of 1,4-dioxane. The mixture obtained is poured into a mixed solution consisting of 1444 parts of methanol and 361 parts of deionized water with stirring, the mixture is stirred and the resin deposited in the mixture is corrected by filtration. 903 parts of methanol are added to the deposit, the mixture is stirred, and the solid is corrected by filtration. The series of operations including addition, stirring and filter correction are repeated two more times, then dried under reduced pressure to obtain 97.9 parts of copolymer having a weight average molecular weight of 7830 and obtaining a ratio Mw (weight average molecular weight) / Mn (number average molecular weight) of 1.80 in a yield of 71%. This copolymer contains the following structural units. It has been designated A5 resin.
    EXAMPLE OF SYNTHESIS OF RESIN 6
    In a four-necked flask equipped with a thermometer and a condenser, 82.87 parts of 1,4-dioxane were charged and bubbled with nitrogen gas for 30 minutes. Under the nitrogen atmosphere and after the solvent has been heated to 74 ° C, a solution prepared by mixing 45.00 parts of the monomer M1, 10.07 parts of the monomer M2, 74, is added dropwise to the heated solvent. 68 parts of M3 monomer, 8.37 parts of M5 monomer, 0.88 part of 2,2'-azobis-isoburyronitrile, 3.97 parts of 2,2-azobis (2,4-dimethyl-valeronitrile) and 124, 31 parts of 1,4-dioxane over 2 hours while maintaining the temperature at 74 ° C (monomer ratio: monomer ML monomer M2: monomer M3 monomer M5 = 34: 8: 50: 8). After the addition step, the resulting mixture is maintained at 74 ° C for 5 hours. The reaction mixture is cooled and diluted with 151.93 parts of 1,4-dioxane. The mixture obtained is poured into a mixed solution composed of 1436 parts of methanol and 359 parts of deionized water with stirring, the mixture is stirred and the resin deposited in the mixture is corrected by filtration. 898 parts of methanol are added to the deposit, the mixture is stirred and the solid is then corrected by filtration. The series of operations including addition, stirring and filter correction are repeated two more times, and then the whole is dried under reduced pressure to give 101.1 parts of copolymer having a weight average molecular weight of 90%. obtaining a ratio Mw (weight average molecular weight) / Mn (number average molecular weight) of 1.87 with a yield of 73%. This copolymer contains the following structural units. It has been designated A6 resin.
    EXAMPLES 1 TO 17 AND COMPARATIVE EXAMPLES 1 TO 6 Acid Generator Acid Generator B1
    B2 acid generator:
    B3 acid generator:
    B4 acid generator:
    Acid generator B5: Acid generator B6: Acid generator B7: Acid generator B8: Acid generator B9:
    Acid generator B10:
    Bll acid generator:
    Cl acid generator:
    C2 Acid Generator: Resin
    Resins Al to A6 Neutralizing Agent Q1: 2,6-Diisopropylaniline
    Solvent yl: Propylene glycol monomethyl ether acetate 145 parts 2-Heptanone 20.0 parts
    Monomethyl ether of propylene glycol 20.0 parts y-Butyrolactone 3.5 parts
    The following components are mixed and dissolved, then filtered through a fluororesin filter having a pore diameter of 0.2 μm, to prepare a liquid resist.
    Resin (type and quantity are described in Tables 1-1 and 1-2).
    Acid generator (type and quantity are described in Tables 1-1 and 1-2).
    Neutralizing agent (type and amount are described in Tables 1-1 and 1-2). Solvent (the type is described in Tables 1-1 and 1-2).
    Each of the silicon wafers was coated with "ARC-29", which is an organic, anti-reflective coating composition available from Nissan Chemical Industries, Ltd., and then fired under the following conditions: 205 ° C, 60 ° C .; seconds, giving an organic antireflective coating with a thickness of 780 Å. Each of the resist liquids, prepared in the manner indicated above, was applied by the centrifugal coating technique to the anti-reflective coating, so that the thickness of the resulting film increases to 0.15 μm after drying. . The silicon wafers thus coated with the respective resist liquids are each preliminarily baked directly on a hot plate at a temperature shown in column "PB" of Table I over a period of 60 seconds. Using an excimer laser with ArF, of the "stepper" type ("FPA5000-AS3" manufactured by CANON INC., NA = 0.75, 2/3 annular), each slice thus obtained is subjected to the respective resist film, exposure in a pattern of lines and spaces, the amount of exposure being gradually changed.
    After exposure, each slice is post-bake cooked on a hot plate at a temperature shown in the "PEB" column of Table I for 60 seconds, followed by 60 seconds etching with an aqueous solution. of tetramethylammonium hydroxide at 2.38% by weight.
    Each of the dark field patterns developed on the antireflective organic 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 effecting exposure and development 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 darkfield pattern allows, after the exposure and development steps, the resist layer surrounding the pattern of lines and spaces to remain on the substrate.
    Effective Sensitivity (ES): It is expressed as the amount of exposure that results in a pattern ratio of lines to the 1: 1 space pattern, after the exposure has been carried out through a mask of pattern of 100 nm lines and spaces and development process.
    Resolution: It is expressed as the minimum size of the space pattern that gives the space pattern separated by the line pattern for the effective sensitivity exposure amount.
    Line Edge Roughness (LER1): Each wall surface of a developed pattern is studied on the organic anti-reflective coating substrate after the development step with a scanning electron microscope. the same as that of Comparative Example 4, its evaluation is marked by the symbol "Δ", when the surface of the wall is smoother than that of Comparative Example 4, its evaluation is marked by the symbol "O" and when the surface of the wall is rougher than that of Comparative Example 4, its evaluation is marked by the symbol "X".

    Table II
    As shown in Table II, the resist compositions of the examples, which are in accordance with the present invention, provide a good resist pattern 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 (14)
    [1]
    A chemically amplified resist composition comprising: a resin which comprises a structural unit having an acid-sensitive moiety and a structural unit represented by the formula (I):

    [2]
    The chemically amplified resist composition of claim 1, wherein the structural unit having an acid-sensitive moiety is a structural unit represented by the formula (IVa):

    [3]
    The chemically amplified resist composition of claim 1, wherein the resin further comprises a structural unit represented by the formula (V):

    [4]
    A chemically amplified resist composition according to claim 1, wherein the structural unit represented by formula (I) is a structural unit represented by formulas (IVa), (IVb) or (IVc):

    [5]
    The chemically amplified resist composition according to claim 1, wherein the salt represented by the formula (II) is a salt represented by the formula (VII):

    [6]
    The chemically amplified resist composition according to claim 1, wherein the salt represented by the formula (II) is a salt represented by the following formula (XII):

    [7]
    A chemically amplified resist composition according to claim 1, wherein A + and A '+ are the same or different and each independently represents at least one cation selected from the group consisting of compounds of formula (Villa):

    [8]
    A chemically amplified resist composition according to claim 1, wherein A + and A '+ are the same or different and each independently represents at least one cation selected from the group consisting of compounds of formula (City), (VIII), (Vlllg) or (Vlllj):

    [9]
    A chemically amplified resist composition according to claim 1, wherein A + and A '+ are the same or different and each independently represents at least one cation selected from the group consisting of compounds of formula (VIII) or (VIII):

    [10]
    A chemically amplified resist composition according to claim 1, wherein A + and A '+ are the same or different and each independently represents at least one cation selected from the group consisting of compounds of formula (VIII) or (VIII):

    [11]
    The chemically amplified resist composition according to claim 1, wherein the chemically amplified resist composition comprises the salt represented by the formula (II) and at least one salt selected from the salt represented by the formula (II) and the salt represented by the formula (III).
    [12]
    The chemically amplified resist composition of claim 1, wherein the chemically amplified resist composition comprises at least two salts selected from the salt represented by the formula (II).
    [13]
    The chemically amplified resist composition according to claim 1, wherein at least two salts selected from a salt represented by the formula (II) and a salt represented by the formula (III) are at least two salts selected from the salt represented by formula (II), wherein A + represents the cation (Villa) or (City), and the salt represented by formula (III), wherein A '+ represents the cation (Villa) or (City).
    [14]
    The chemically amplified resist composition of claim 1, wherein the chemically amplified resist composition also comprises a basic compound.
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    同族专利:
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    法律状态:
    2014-07-31| RE| Patent lapsed|Effective date: 20140131 |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2007018998|2007-01-30|
    JP2007018998|2007-01-30|
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