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    • 专利摘要:
    The present invention provides a chemically amplified resin composition, comprising a resin comprising a structural unit represented by the formula (1) wherein R1 represents a hydrogen atom or a methyl group, the ring Y represents a C3 cyclic hydrocarbon group to C30 wherein -CH2- is substituted with -COO-, and at least one hydrogen atom of the C3-C30 cyclic hydrocarbon group can be replaced, and p is an integer of 1 to 4, and which is -Even insoluble or poorly soluble in an aqueous alkaline solution but becomes soluble in an aqueous alkaline solution under the action of an acid, and a salt represented by the formula (II) wherein Y1 and Y2 each independently represent one of the other a fluorine atom or a C1-C6 perfluoroalkyl group, A + represents an organic counterion and R21 represents a C1 to C30 hydrocarbon group which may be substituted and at least one -CH2- of the C1 to C30 hydrocarbon group may be substituted with -CO- or -O-.
    公开号:BE1018262A3
    申请号:E2007/0590
    申请日:2007-12-12
    公开日:2010-08-03
    发明作者:Yoshiyuki Takata；Takayuki Miyagawa；Kunishige Edamatsu
    申请人:Sumitomo Chemical Co；
    IPC主号:
    专利说明:

    CHEMICAL AMPLIFIED RESIN COMPOSITION
    FIELD OF THE INVENTION
    The present invention relates to a chemical amplification reserve composition.
    BACKGROUND OF THE INVENTION
    A chemically amplified resist composition used for semiconductor microfabrication and using a lithographic process contains an acid generator comprising a compound generating an acid by irradiation.
    In semiconductor microfabrication, it is desirable to form patterns having a high resolution, and a chemical amplification resist composition is expected to provide such patterns.
    US 2006 - 0194982 A1 discloses a chemically amplified resist composition containing the salt represented by the formula:
    and the resin containing the following structural units:
    SUMMARY OF THE INVENTION
    Objects of the present invention are to provide a chemically amplified resist composition giving patterns having a better resolution.
    This object of the invention, and others, will become apparent from the following description.
    The present invention relates to the following: <1> a chemically amplified resist composition comprising: a resin comprising a structural unit having an acidolabile group and a structural unit represented by formula (I):
    wherein R1 represents a hydrogen atom or a methyl group, the ring Y represents a C3 to C30 cyclic hydrocarbon group in which a -CH2- is substituted with -COO-, and at least one hydrogen atom of the hydrocarbon group C3 to Cm cyclic can be replaced, 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 an aqueous alkaline solution under the action of a acid, and a salt represented by the formula (II)
    wherein Y1 and Y2 each independently represent a fluorine atom or a C1- to β perfluoroalkyl group, A + represents an organic counterion and R21 represents a C1 to C30 hydrocarbon group which may be substituted and at least one -CH2- of the C1-C30 hydrocarbon group may be substituted with -CO- or -O-, <2> The chemical amplification reserve composition of <1>, wherein the structural unit has an acid-labile group is a structural unit represented by the formula (Ilia):
    wherein R2 is a hydrogen atom or a methyl group, R3 is a C1-C8 straight or branched chain alkyl group or a C3-C8 cyclic alkyl group, R4 is a methyl group, n is an integer of 0 to 14, Z1 represents a single bond or - (CH2) r-COO-, and r represents an integer from 1 to 4, or a structural unit represented by the formula (IIIb):
    wherein R5 represents a hydrogen atom or a methyl group, R6 represents a linear or branched C1-C8 alkyl group or a C3-C8 cyclic alkyl group, R7 and R8 are each independently of one another a hydrogen atom or a C1 to C8 monovalent hydrocarbon group which may comprise at least one heteroatom, and R7 and R8 may be bonded to form a divalent C1 to C78 hydrocarbon group which may comprise at least one heteroatom which forms a ring with the adjacent carbon atoms to which R7 and R8 are bonded, and R7 and R8 can be bonded 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 from 1 to 3, Z2 represents a single bond or - (CH2) s.COO-, and s represents an integer from 1 to 4, <3> The chemical amplification reserve composition of <1> or < 2>, in which the resin further comprises a structural unit represented by the formula (IV):
    in which R 9 represents a hydrogen atom or a methyl group, R 10 and R 11 each independently represent a hydrogen atom, a methyl group or a hydroxyl group, R 12 represents a methyl group, t represents a integer from 0 to 12, Z3 represents a single bond or - (CHbVCOO- and u represents an integer from 1 to 4, <4> The chemically amplified resist composition according to any of the points <1> to < 3>, wherein the structural unit represented by formula (I) is a structural unit represented by formulas (Va), (Vb) or (Vc):
    in which R 1 represents a hydrogen atom or a methyl group, p represents an integer from 1 to 4, R 13 represents a methyl group, z represents an integer from 0 to 5, R 14 represents a C 1 to C 4 hydrocarbon group, a carboxyl group or a cyano group, y represents an integer from 0 to 3, R15 represents a C1-C4 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 R14 may be the same or different, when z is 2 or 3, the R15 may be the same or different, <5> The chemically amplified resist composition according to any one of <1> to <4 in which the salt represented by the formula (II) is a salt represented by the formula (VI):
    wherein Y1 and Y2 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group, A + represents an organic counter-ion, and R22 represents a linear-chain C1-C20 hydrocarbon group; branched which may be substituted, or a C3-C30 cyclic hydrocarbon group which may be substituted, and at least one -CH2- of the linear or branched C1-C20 hydrocarbon group or the C3-C30 hydrocarbon group may be substituted by -CO- or -O-, <6> 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 the following formula (X):
    wherein Y1 and Y2 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group, A + represents an organic counterion, Z4 represents or a C1-C4 alkylene group, Q represents - CH2-, -CO- or -CH (OH) - and the ring X1 represents a C3-C30 mononuclear or polynuclear hydrocarbon group in which two hydrogen atoms are replaced by = 0 in the Q position when Q is -CO- or wherein a hydrogen atom is replaced by a hydroxyl group at the Q position when Q is -CH (OH) -, and at least one hydrogen atom of the C3-C30 mononuclear or polynuclear group may be replaced by an alkyl group C1 to C6, C1-C6 alkoxy, C1-C4 perfluoroalkyl, C1-C6 hydroxyalkyl, hydroxyl or cyano, <7> Chemical amplification resist composition according to claim 1 any of the points <1> to <6>, where A + is at least one cat ion selected from the group consisting of a cation represented by the formula (VI la):
    wherein P1, P2 and P3 each independently represent a C1 to C30 alkyl group which may be substituted by at least one group selected from a hydroxyl group, a C3 to C12 cyclic hydrocarbon group and a group C1-C12 alkoxy 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 (Vllb):
    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 (Vile) :
    wherein Ρβ and P7 each independently represent a C1-C12 alkyl group or a C3-C12 cycloalkyl group, or P6 and P7 are linked to form a divalent C3-C12 acyclic hydrocarbon group which forms a ring with the adjacent S +, and at least one -CH2- of the divalent C3-C12 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 else P8 and P9 are linked to give a divalent acyclic hydrocarbon group which forms a 2-oxocycloalkyl group with the -CHCO- adjacent, and at least one -CH2- of the divalent acyclic hydrocarbon group may be substituted with -CO-, -O- or -S-, and a cation represented by the formula (Vlld): wherein P10, P11, P12, P13 , P14, P15, P16, P17, P18, P19, P20 and P21 each independently represent one of the 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 + is a cation represented by the formulas (Vile), (Vllf) or (Vllg):
    wherein P28, P29 and P30 each independently represent a C1-C20 alkyl group or a C3-C30 cyclic hydrocarbon group except for a phenyl group, and at least one atom. hydrogen of the C 1 -C 20 alkyl group may be replaced by a hydroxyl group, a C 1 -C 12 alkoxy group or a C 3 -C 12 cyclic hydrocarbon group and at least one hydrogen atom of the C 3 -C 30 cyclic hydrocarbon group may be replaced by a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, and P31, P32, P33, P34, P35 and P36 are each independently of one another a hydroxyl group, a group C1-C12 alkyl, C1-C12 alkoxy or C3-C12 cyclic hydrocarbon group, and I, k, j, i, h and g each independently represent an integer of 0 to 5, <9> The resist composition according to any one of <1> to <6>, wherein A + e st a cation represented by the formula (VIII):
    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, <10> chemical amplification according to any one of <1> to <6>, wherein A + is a cation represented by the formula (Vlli):
    wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group; <11> The chemically amplified resist composition according to any one of <1 > to <10>, wherein the resist composition further comprises a basic compound.
    DESCRIPTION OF THE PREFERRED EMBODIMENTS The present chemically amplified resist composition contains a resin which comprises a structural unit having an acidolabile group and a structural unit represented by the formula (I), and which is itself insoluble or sparingly soluble in a aqueous alkaline solution but becomes soluble in an aqueous alkaline solution under the action of an acid (hereinafter simply called RESINE), and a salt represented by the formula (II) (hereinafter simply called salt (II)).
    First, the structural unit having an acidolabile group will be illustrated.
    In the present description, "-COOR" may be described as a structure having a carboxylic acid ester ", and may also be abbreviated to" ester group. "Specifically," -COOR (CH 3) 3H may be described as a " structure having a tert-butyl carboxylic acid ester "or be abbreviated to" tert-butyl ester group ".
    Examples of the acidolabile group include a structure having a carboxylic acid ester such as an alkyl ester group in which a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, an alicyclic ester group in which an atom of carbon adjacent to the oxygen atom is a quaternary carbon atom and a lactone ester group in which a carbon atom adjacent to the oxygen atom is a quaternary carbon atom. A "quaternary carbon atom" refers to a "carbon atom bound to four substituents other than hydrogen atoms". For the acidolabile group, an example is a group having a quaternary carbon atom bonded to three carbon atoms and -OR ', where R' is an alkyl group.
    Examples of the acidolabile group include an alkyl ester group wherein a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, such as a tert-butyl ester group, an acetal ester group such as a methoxymethyl ester group ethoxymethyl ester, 1-ethoxyethyl ester, 1-isobutoxyethyl ester, 1-isopropoxyethyl ester, 1-ethoxypropoxylic ester, 1- (2-methoxyethoxy) ethyl ester, 1- (2-acethoxyethoxy) ethyl ester, 1- [2- (1-adamantyloxy) ethoxy] -ethyl, 1- [2- (1-adamantan-carbonyloxy) ethoxy] ethyl, tetrahydro-2-furyl ester and tetrahydro-2-pyranyl ester, an alicyclic ester group in which a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, such as isobromyl ester group, 1-alkylcycloalkyl ester, 2-alkyl-2-adamantyl ester and 1- (1-adamantyl) -1-alkylalkyl ester. At least one hydrogen atom of the adamantyl group may be replaced by a hydroxyl group.
    Examples of the structural unit include a structural unit derived from an acrylic acid ester, a structural unit derived from a methacrylic acid ester, a structural unit derived from a norbomene carboxylic acid ester, a structural unit derived from a tricyclodecenecarboxylic acid ester and a structural unit derived from a tetracyclodecene carboxylic acid ester. Structural units derived from acrylic acid esters and methacrylic acid esters are preferable.
    The structural unit represented by formula (Ilia) or (IIIb) is preferable as a structural unit having an acidolabile group.
    In the formula (Ilia), R2 represents a hydrogen atom or a methyl group, and R3 represents a C1-C6 straight or branched chain alkyl group or a C3-C6 cyclic alkyl group. It is preferred that R3 represents C1-C8 linear or branched chain alkyl group.
    Examples of the C8 to C8 straight or branched chain alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl and n-butyl groups. octyl, and C 1 -C 4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and sec-butyl are preferable, and the methyl, ethyl, n-propyl and isopropyl groups are more preferable. preferable.
    Examples of the C3-C8 cyclic alkyl group include cyclopentyl, cyclohexyl, cyclooctyl, 2-methylcyclopentyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 4,4-dimethylcyclohexyl, 2-norbomyl and 5-methyl groups. -2-norbornyl.
    In the formula (Ilia), R4 represents a methyl group, n represents an integer from 0 to 14, Z1 represents a single bond or - (CH2) rCOO-, and r represents an integer from 1 to 4. It is preferred n is 0 or 1. Z1 preferably represents the single bond or -CH2-COO-, and more preferably it represents the single bond.
    In formula (IIIb), R5 represents a hydrogen atom or a methyl group, and R6 represents a C1-C8 straight or branched chain alkyl group or a C3-C8 cyclic alkyl group with chemical amplification. Examples of the C1-C8 linear or branched chain alkyl group include the same groups as mentioned above. Preferred examples thereof include C1-C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and sec-butyl, and more preferable examples thereof include methyl, ethyl, n-propyl and isopropyl groups.
    Examples of the C3-C8 cyclic alkyl group include the same groups as mentioned above.
    In formula (IIIb), 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 C1 to C8 monovalent hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl groups. .
    R7 and R8 may be linked to form a divalent C1-C8 hydrocarbon group which may include at least one heteroatom that forms a ring with adjacent carbon atoms to which R7 and R8 are bonded. Specific examples of the divalent C1 to C8 hydrocarbon group include ethylene and trimethylene groups.
    R7 and R8 may also be linked 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 (IIIb), 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 represents 0 or 1. Z2 preferably represents the single bond or -CH2-COO-, and more preferably it represents the single bond.
    The structural unit represented by the formula (Ilia) is derived from the monomer represented by the formula (IIIa-1):
    wherein R2, R3, R4, Z1 and n are as defined above.
    Specific examples of the monomer represented by the formula (IIIa-1) include the following:


    The structural unit represented by formula (IIIb) is derived from the MONOMER REPRESENTED BY FORMULA (IIIB-1):

    Also preferred as the structural unit having an acidolabile group is the structural unit represented by formula (IIIc) or (IIId):
    where R 30 represents a hydrogen atom or a methyl group, R 31 represents a C 1-6 alkyl group, R 32 represents a C 1-6 alkyl group or a C 1-6 alkoxy group, d represents an integer from 0 to 3; and when d is 2 or 3, R 32 may be the same or different, R 33 is hydrogen or methyl, R 34 is C 1-6 alkyl, R 35 is C 1-6 alkyl or a group C1 to C6 alkoxy, e is an integer from 0 to 3, and when e is 2 or 3, the R35 may be the same or different.
    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, and the alkyl group is Ci to C4 is preferable. 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, and the alkoxy group C1 to C4 is preferable.
    The structural unit represented by the formulas (IIIc) is derived from the monomer represented by the formula (III-1):
    wherein R30, R31, R32 and d are as defined above, and the structural unit represented by formula (IIId) is derived from the monomer represented by the formula (IIId-1):
    wherein R33 R34, R35 and e are as defined above.
    Examples of monomers represented by the formulas (III-1) and (III-1) include the following.


    The RESIN may contain a structural unit having an acidolabile group and may contain two or more types of structural units having an acidolabile group.
    It is preferred that the RESIN has the structural unit selected from the structural unit represented by the formula (Ilia) as a structural unit having an acidolabile group, from the point of view of RESINE resistance to etching by channel. dried. When the structural unit represented by the formula (Ilia) is in particular the structural unit derived from 2-methyl-2-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, 2-acrylate ethyl 2-adamantyl, 2-ethyl-2-adamantyl methacrylate, 2-isopropyl-2-adamantyl acrylate or 2-isopropyl-2-adamantyl methacrylate, there is a tendency to obtain a composition endowed with excellent sensitivity and excellent resistance to heat.
    It is also preferred that the RESIN has the structural units represented by the formulas (Ilia) and (Ille) as a structural unit having an acidolabile group, from the point of view of the line edge roughness.
    The monomer represented by the formula (IIIa-1) can usually be produced by reaction of the corresponding adamantanol or its metal salt with an acrylic halide or a methacrylic halide. The monomer represented by the formula (IIIb-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 (III-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 (IIId-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 then be illustrated.
    In the formula (I), R 1 represents a hydrogen atom or a methyl group, the ring X represents a C 3 to C 30 cyclic hydrocarbon group in which a -CH 2 - is substituted with -COO-. At least one hydrogen atom of the C3-C30 cyclic hydrocarbon group may be substituted, and examples of substituents include C1-C6 alkyl, carboxyl and cyano.
    The ring X may be a mononuclear hydrocarbon group and may be a polynuclear hydrocarbon group.
    Preferred structural units represented by formula (I) are those of formulas (Va), (Vb) or (Vc) below:
    in which R1 and p have the same meanings as defined above, R13 represents a methyl group, x represents an integer from 0 to 5, R14 represents a C1-C14 hydrocarbon group, a carboxyl group or a cyano group, y represents an integer from 0 to 3, R15 represents a C1-C4 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 R14 may be the same or different, when z is 2 or 3, the R15 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 it is more preferred that p is 1.
    It is preferred that x is 0 in the formula (Va). It is preferred that y is 0 in formula (Vb). It is preferred that z is 0 in the formula (Vc). The structural unit represented by the formula (Va) is derived from the monomer represented by the formula (Va-1):
    wherein R1, R13, x and p are as defined above.
    Examples of the monomer represented by the formula (Va-1) include the following.
    The structural unit represented by formula (Vb) is derived from the monomer represented by formula (Vb-1):
    wherein R1, R14, y and p are the same as defined above.
    Examples of the monomer represented by the formula (Vb-1) include the following.
    A structural unit represented by the preferred formula (Vc) is derived from the monomer represented by the formula (Vc-1)
    wherein R1 R15, z and p are as defined above.
    Examples of the monomer represented by the formula (Vc-1) include the following:
    The structural unit represented by formula (Vb) is preferred as the structural unit represented by formula (I), and the following structural units:
    are more preferable from the point of view of the resin pattern obtained after the lithographic process.
    The molar proportion of the structural unit having an acidolabile group in the RESINE is usually from 20 to 95% by weight, based on the sum of the structural units having an acidolabile group and the structural unit represented by the formula (I) in the RESIN, and the molar proportion of the structural unit represented by the formula (I) in the RESINE is usually from 5 to 80% by weight, based on the sum of the structural units having an acidolabile group and the structural unit represented by the formula (I) in the RESINE, although the proportion varies according to the type of radiation for pattern formation exposure the type of acidolabile group, and the like.
    The RESIN comprises the structural unit having an acid-labile group and the structural unit represented by the formula (I), and which is itself insoluble or poorly soluble in an aqueous alkaline solution but becomes soluble in an aqueous alkaline solution under the action of an acid.
    The RESIN may contain one or more other structural units in addition to the structural unit having an acidolabile group and the structural unit represented by formula (I).
    Examples of the other structural unit include a structural unit represented by formula (IV):
    in which R 9 represents a hydrogen atom or a methyl group, R 10 and R 11 each independently represent a hydrogen atom, a methyl group or a hydroxyl group, R 12 represents a methyl group, t represents a integer from 0 to 12, and Z3 represents a single bond or - (ChfeVCOO- and u represents an integer from 1 to 4, a structural unit represented by formula (VIII):
    wherein R16 represents a hydrogen atom or a methyl group, and AR represents a C3-C30 fluorinated alkyl group which may contain from 1 to 5 hydroxyl groups and at least one heteroatom selected from oxygen, nitrogen and sulfur, and a structural unit represented by formula (IX):
    wherein R17 represents a hydrogen atom or a methyl group, the ring X 'represents a C3-C8o cyclic hydrocarbon group in which a -CH2- group is substituted with a -COO- group and at least one hydrogen atom of the C3 - C30 cyclic hydrocarbon group can be replaced.
    The RESIN preferably contains the structural unit represented by formula (IV). The RESIN preferably also contains the structural units represented by formulas (IV) and (IX).
    In formula (IV) it is preferred that R10 and R11 are each independently of one another a hydrogen atom or a hydroxyl group. Preferably, t is 0 or 1, and more preferably t is 0. Z 3 is preferably single bonds or -CH 2 -COO-. The structural unit represented by formula (IV) is derived from the monomer represented by the formula ( IV-1):
    wherein R9, R10, R11, R12, Z3 and t are the same as those defined above.
    Specific examples of the monomer represented by the formula (IV-1) include the following.

    For the structural unit represented by formula (IV), the structural units derived from the following monomers:
    are preferable from the point of view of resolution.
    The monomer represented by the formula (IV-1) can usually be produced by reaction of the corresponding hydroxylated adamantane compound with an acrylic halide or a methacrylic halide;
    In formula (VIII), examples of the C1 to C30 fluoroalkyl group include a C1 to C30 perfluoroalkyl group such as trifluoromethyl, pentafluoroethyl, heptafluoropropyl and nonafluorobutyl, a 1-pentafluoroethoxyethyl group, a C1 to C4 perfluoroalkoxyperfluoroalkyl group, C30 such as 1-trifluoromethoxydifluoroethyl and 1-pentafluoroethoxydifluoroethyl, and the following groups (in the following formulas, a straight line with an open end refers to a bond extending from the adjacent oxygen group).
    As the structural unit represented by formula (VIII), the structural units derived from the following monomers are given as examples.
    As the structural unit represented by formula (VIII), the structural units derived from the following monomers:
    are preferable because excellent resolution is obtained when using a resin containing the structural unit derived from these monomers in the present resin composition.
    The monomer giving the structural unit represented by the formula (VIII) can usually be produced by reaction of the corresponding fluorinated alcohol compound with an acrylic halide or a methacrylic halide.
    In formula (IX), examples of the ring X 'include the same groups as mentioned for the ring.
    Examples of structural unit represented by formula (IX) are the structural units derived from the following monomers:

    As the structural unit represented by formula (IX), the structural units derived from the following monomers:
    are preferable from the point of view of the adhesiveness of the resin to a substrate.
    The monomer giving the structural unit represented by the formula (IX) can be produced by reacting the corresponding alicyclic lactone having a hydroxyl group with acrylic acid or methacrylic acid, and the process for producing this monomer is by example described in JP2000 - 26446-A.
    As another structural unit the structural units represented by the formulas (IV), (VIII and (IX), a structural unit derived from an alicyclic compound having an olefinic double bond, as a structural unit represented by the formula ( 1):
    wherein R25 and R26 each independently represent a hydrogen atom, a C1-C3 alkyl group, a C1-C3 hydroxyalkyl group, or a carboxyl group, a cyano group, a hydroxyl group or a -COOU group in which U represents an alcohol residue, or R25 and R26 may be bonded together to form a carboxylic acid residue represented by -C (= O) 0C (= O), a structural unit derived from a dicarboxylic anhydride unsaturated, as a structural unit represented by the formula (2): and
    a structural unit represented by formula (3):
    The resin containing a structural unit derived from 2-norbornene has a solid structure, since the alicyclic group is directly present on its main chain, and has excellent resistance to dry etching. The structural unit derived from 2-homomene can be introduced into the main chain by radical polymerization using, for example, an unsaturated aliphatic dicarboxylic anhydride such as maleic anhydride and itaconic anhydride, together with the corresponding 2-norbornene. The structural unit derived from 2-norbornene is formed by opening its double bond, and may be represented by the aforementioned formula (1). The structural unit derived from maleic anhydride and itaconic anhydride, which are the structural units derived from unsaturated aliphatic dicarboxylic anhydrides, are formed by opening their double bond and can be represented by formula (2) and formula (3) above.
    In R25 and R26, examples of the C1-C3 alkyl group include methyl, ethyl and n-propyl groups, and examples of the C1-C3 hydroxyalkyl group include hydroxymethyl and 2-hydroxyethyl groups.
    In R 25 and R 26, the group -COO 2 is an ester formed from the carboxyl group, and the alcohol residue corresponding to U is, for example, an optionally substituted C 1 to C 6 alkyl group, a 2-oxooxolan-3-yl group. , 2-oxooxolan-4-yl and the like, and as a substituent on the C1-C6 alkyl group, a hydroxyl group, an alicyclic hydrocarbon residue and the like.
    Specific examples of the monomer used to give the structural unit represented by the above-mentioned formula (1) may include 2-norbornene, 2-hydroxy-5-norbornene, 5-norbornene-2-carboxylic acid, 2-norbornene, 2-hydroxy-5-norbornene, methyl-5-norbornene carboxylate, 2-hydroxyethyl-5-norbornene 2-carboxylate, 5-norbornene-2-methanol and 5-norbornene-2,3-dicarboxylic anhydride.
    In the group -COOU, when U is the acidolabile group, the structural unit represented by the formula (1) is a structural unit possessing the acidolabile group, even having the norbornane structure. Examples of structural unit-donating monomers having the acidolabile group include tert.-butyl-5-norbornene 2-carboxylate, 1-cyclohexyl-1-methylethyl-5-norbornene 2-carboxylate, 2-carboxylate of 1 5-methylcyclohexyl-5-norbornene, 2-methyl-2-adamantyl-5-norbornene 2-carboxylate, 2-ethyl-2-adamantyl-5-norbornene 2-carboxylate, 1- (4-methoxy) -2-carboxylate 1-Methylcyclohexyl) -1-methylethyl-5-norbornene, 1- (4-hydroxycyclohexyl) -1-methylhexyl-5-norbornene-2-carboxylate, 1-methyl-1- (4-oxocyclohexyl-ethyl) -2-carboxylate 5-norbornene, 1- (1-adamantyl) -1-methylethyl-5-norbornene-2-carboxylate, and the like.
    The proportion of the structural unit (s) (i) is usually from 0 to 60 mol%, based on all the structural units of the resin.
    The RESIN can be produced when the polymerization reaction of the corresponding monomer (s). The RESINE may also be produced by oligomerization of the corresponding monomer (s) followed by polymerization of the oligomer obtained.
    The polymerization reaction is usually carried out in the presence of a radical initiator.
    The radical initiator is not limited, and examples of this initiator include an azo compound such as 2,2'-azobis-isobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1 ' azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4-dimethyl-valeronitrile), 2,2-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2 ' dimethyl azobis (2-methylpropionate) and 2,2'-azobis (2-hydroxymethylpropionitrile), an organic hydroperoxide such as lauroyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-peroxybenzoate n-butyl, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, tert-butyl peroxneodecanoate, tert-butyl peroxypivalate and 3,5,5-trimethylhexanoyl peroxide; , and an inorganic peroxide such as potassium peroxodisulfate, ammonium peroxodisulfate and hydrogen peroxide. Among them, the azo compound is preferable and 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2 ' -azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate) are more preferable, and 2,2'-azobis-isobutyronitrile and 2,2'-azobis (2 , 4-dimethyl-valeronitrile) are particularly preferable.
    These radical initiators can be used alone or in the form of a mixture of two or more types of them. When a mixture of two or more types of them is used, the mixing ratio is not particularly limited.
    The amount of the radical initiator is preferably 1 to 20 mol%, based on the molar amount of all monomers or oligomers.
    The polymerization temperature is usually 0 to 150 ° C, preferably 40 to 100 ° C.
    The polymerization reaction is usually conducted in the presence of a solvent, and the use of a solvent sufficient to dissolve the monomer, the radical initiator and the resulting resin is preferred. Examples include a hydrocarbon solvent such as toluene, an ether solvent such as 1,4-dioxane and tetrahydrofuran, a ketone solvent such as methyl isobutyl ketone, an alcohol solvent such as isopropyl alcohol, a cyclic ester solvent such as γ-butyrolactone, a glycolic ester-ether solvent such as propylene glycol monomethyl ether acetate, and an acyclic ester solvent such as ethyl lactate. These solvents can be used alone, or a mixture of them can be used.
    The amount of solvent is not limited and in practice is preferably 1 to 5 parts by weight based on 1 part of all monomers or oligomers.
    When an alicyclic compound having an olefinic double bond and an unsaturated aliphatic dicarboxylic anhydride are used as the monomers, it is preferable to use them in excess, since they tend not to be readily polymerized.
    At the end of the polymerization reaction, the resin produced can be isolated, for example, by adding to the reaction mixture obtained a solvent in which the present resin is insoluble or poorly soluble and filtration of the precipitated resin. If necessary, the isolated resin can be purified, for example by washing with a suitable solvent.
    Then, the salt represented by formula (II)
    (hereinafter simply called salt (II)) is illustrated.
    In the salt (II) Y1 and Y2 are each independently of one another a fluorine atom or a C1-C6 perfluoroalkyl group. Examples of the C1-C6 perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, undecafluoropentyl and tridecafluorohexyl, and the trifluoromethyl group is preferable.
    It is preferred that Y and Y2 each independently represent fluorine atom or trifluoromethyl group, and it is more preferable that Y1 and Y2 are fluorine atoms.
    R21 represents a C1 to C30 hydrocarbon group in which at least one -CH2- may be substituted with -CO- or -O-. The C1 to C30 hydrocarbon group may be a straight or branched chain hydrocarbon group. The C1 to C30 hydrocarbon group may have a mononuclear or polynuclear structure, and may include one or more aromatic groups. The C1 to C30 hydrocarbon group may have one or more double bonds. The C1 to C30 hydrocarbon group may be substituted.
    Examples of substituents include C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 4 perfluoroalkyl, C 1 -C 6 hydroxyalkyl, hydroxyl and cyano, and the hydroxyl group is preferable as a substitute.
    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, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy and n-hexyloxy. Examples of the C1-C4 perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl and nonafluorobutyl groups. Examples of the C 1 -C 6 hydroxyalkyl group include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl and 6-hydroxyhexyl groups.
    Specific examples of the anion portion of salt (II) include the following.








    In salt (II), A + represents an organic counterion. Examples of organic counterion include a cation represented by the formula (VIIa):
    wherein P1, P2 and P3 each independently represent a C1 to C30 alkyl group which may be substituted by at least one group selected from a hydroxyl group, a C3 to C12 cyclic hydrocarbon group and a group C1 to C12 alkoxy, or a C3 to C12 cyclic hydrocarbon group and a C1 to C12 alkoxy group, or a C3 to C30 cyclic hydrocarbon group which may be substituted by at least one group selected from a hydroxyl group and a group C1-C12 alkoxy (hereinafter simply called cation (VIIa)), a cation represented by the formula (Vllb):
    wherein P4 and P5 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group (hereinafter simply called a cation (Vllb) a cation represented by the formula (Vile):
    wherein P6 and P7 each independently represent a C1-C12 alkyl group or a C3-C12 cycloalkyl group, or P6 and P7 are linked to form a divalent acyclic hydrocarbon group which forms a ring with the adjacent S +, and at least one -CH2- 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 linked to form a divalent acyclic hydrocarbon group which forms a 2-oxocycloalkyl group with the adjacent -CHCO-, and at least one -CH2- of the divalent acyclic hydrocarbon group can be replaced by -CO-, -O- or -S- (hereinafter simply called cation (Vile), and a cation represented by the formula (Vlld):
    wherein P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20 and P21 each independently of one another is a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, B represents a sulfur or oxygen atom and m is 0 or 1 (and hereinafter simply called cation (VIId).
    Examples of the C1-C12 alkoxy group in the (Vlla), (Vllb) and (VIId) cations include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tertiary, and the like. butoxy, n-pentyloxy, n-hexyloxy, n-octyloxy and 2-ethylhexyloxy.
    Examples of the C3-C12 cyclic hydrocarbon group in the cation (VIIa) include cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, phenyl, 2-methylphenyl, 4-methylphenyl, 1-naphthyl and 2-naphthyl.
    Examples for the C1-C30 alkyl group which may be substituted by at least one group selected from hydroxyl group, a C1-C12 cyclic hydrocarbon group and a C1-C12 alkoxy group in the cation (Vlla) include groups methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl and benzyl.
    Examples of the C3-C30 cyclic hydrocarbon group which may be substituted by at least one of a hydroxyl group and a C1-C12 alkoxy group in the cation (VIIa) include cyclopentyl, cyclohexyl, 1-adamantyl, 2- adamantyl, bicyclohexyl, phenyl, 2-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert.-butylphenyl, 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 4-n-hexylphenyl, 4 n-octyl-phenyl, 1-naphthyl, 2-naphthyl, fluorenyl, 4-phenylphenyl, 4-hydroxyphenyl, 4-methoxyphenyl, 4-tert.-butoxyphenyl, 4-n-hexyloxyphenyl.
    Examples of the C 1 -C 12 alkyl group in (Vllb), (Vile) and (VIId) cations include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tertiary, and the like. butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl.
    Examples of the C3-C12 cycloalkyl group in the (Vile) cation include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cycooctyl and cyclodecyl. Examples of the divalent C 3 -C 12 acyclic hydrocarbon group formed by the bonding of P 6 and P 7 include trimethylene, tetramethylene, pentamethylene groups. Examples of the cyclic group formed with the adjacent S + and the divalent acyclic hydrocarbon group include tetramethylenesulfonio, pentamethylenesulphonio and oxybisethylenesulphonio groups.
    Examples of the aromatic group in the (City) cation include phenyl, tolyl, xylyl, 4-n-butylphenyl, 4-isobutylphenyl, 4-tert.-butylphenyl, 4-cyclohexylphenyl, 4-phenylphenyl, and naphthyl. The aromatic group may be substituted, and the exemplary substituents include a C 1-6 alkoxy group such as methoxy, ethoxy, n-propoxy, n-butoxy, tert-butoxy and n-hexyloxy, a C2 acyloxy group. C12 as an acetyloxy group and a 1-adamantylcarbonyloxy group, and a nitro group.
    Examples of the divalent acyclic hydrocarbon group formed by the bonding of P8 and P9 include methylene, ethylene, trimethylene, tetramethylene and pentamethylene, and examples of the 2-oxocycloalkyl group formed together with the adjacent -CHCO- and the divalent acyclic hydrocarbon group include a 2-oxocyclopentyl group and a 2-oxocyclohexyl group.
    Examples of the cation (VII) include the following:

    Specific examples of the cation (VIIb) include the following:
    Specific examples of the cation (Vile) include the following:

    Specific examples of the cation (VI Id) include the following:

    As the organic counterion represented by A +, the cation (VI la) is preferred. As the organic counterion represented by A +, cations represented by the following formulas (Vile), (Vllf) and (Vllg) are also preferred:
    in which P28, P29 and P30 each independently represent a C 1 -C 20 alkyl group or a C 3 -C 30 cyclic hydrocarbon group with the exception of a phenyl group, and at least one atom of hydrogen in the C 1 -C 20 alkyl group may be replaced by a hydroxyl group, a C 1 -C 12 alkoxy group or a C 3 -C 12 cyclic hydrocarbon group, and at least one hydrogen atom in the C 3 to C 12 cyclic hydrocarbon group; C12 may be replaced by a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, and P31, P32, P33, P34, P35 and P36 each independently represent a hydroxyl group , C 1 -C 12 alkyl, C 1 -C 12 alkoxy or C 3 -C 12 cyclic hydrocarbon group, and I, k, j, i, h and g each independently represent a number of integer from 0 to 5.
    Examples of the C1-C20 alkyl group and the C3-C30 cyclic hydrocarbon group include the same groups as mentioned above.
    As the organic cation represented by A +, a cation represented by the formula (VI Ih) is preferred:
    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 and particularly preferred is a cation represented by the formula (Vlli):
    wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group.
    Examples of the alkyl group and the alkoxy group include the same groups as mentioned above.
    The salt represented by the formula (VI) is preferred as salt (II):
    wherein A +, Y1 and Y2 have the same meanings as defined above, and R22 represents a C 1 -C 20 straight or branched chain hydrocarbon group which may be substituted or a C 3 -C 30 cyclic hydrocarbon group which may be substituted, and at least one -CH2- of the C3-C30 cyclic hydrocarbon group may be substituted with -CO- or -O-.
    The salt represented by formula (X) below is more preferred as salt (II):
    in which A +, Y1 and Y2 are as defined above, Z4 represents a single bond or a C1-C4 alkylene group, Q represents -CH2-, -CO or -CH (OH) and the ring X1 represents a hydrocarbon group mononuclear or polynuclear C3 to C30 wherein two hydrogen atoms are replaced by = 0 in the Q position when Q is -CO- or in which a hydrogen atom is replaced by a hydroxyl group in the Q position when Q is -CH (OH) -, and at least one hydrogen atom of the C3 to C30 mononuclear or polynuclear hydrocarbon group may be replaced by a C1 to C6 alkyl group, a C1 to C6 alkoxy group, a C1 to C6 perfluoroalkyl group, a C1-C4 hydroxyalkyl group, a hydroxyl group or a cyano group.
    Examples of the C1-C6 alkyl group of the C1-C6 alkoxy group, the C1-C4 perfluoroalkyl group and the C1-C6 hydroxyalkyl group respectively include the same groups as those described above.
    Examples of the C 1 -C 4 alkylene group include methylene ethylene, trimethylene and tetramethylene groups. It is preferred that Z4 is the single bond, the methylene group or the and more preferably Z4 is the single bond or the methylene group.
    Examples of the X1 ring include a C4-C8 cycloalkyl group such as a cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl group, an adamantyl group and a norbornyl group, where a hydrogen atom may be replaced by a hydroxyl group, or in which two hydrogen atoms may be replaced by = 0, and where at least one hydrogen atom may be replaced by the C1-C6 alkyl group, the C1-C6 alkoxy group, the C1-C4 perfluoroalkyl group, the C1-C6 hydroxyalkyl, the hydroxyl group or the cyano group.
    Specific examples of the X1 ring include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, an adamantyl group, a norbornyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, a 3-oxocyclopentyl group, a 3-oxocyclohexyl group, 4-oxocyclohexyl group, 2-hydroxycyclopentyl group, 3-hydroxycyclohexyl group, 3-hydroxycyclohexyl group, 4-oxo-2-adamantyl group, 3-hydroxy-1-adamantyl group, 4-hydroxy-1-adamantyl group, 5-oxonorboman-2-yl group, 1,7,7-trimethyl-2-oxobornornan-2-yl group, 3,6,6-trimethyl-2-oxo group Bicyclo [3.1.1] heptan-3-yl, a 2-hydroxy-norborboman-3-yl group, a 1,7,7-trimethyl-2-hydroxynorboman-3-yl group, a 3,6-group , 6-trimethyl-2-hydroxybicyclo- [3.1.1] heptan-3-yl, and the following groups (in the following formulas, a straight line with an open end refers to a bond that extends from a group adjacent):
    It is preferred that the salt (II) is a salt represented by the following formula (XI):
    wherein P22, P23, P24, Y1, Y2, X1, Q and Z4 are as defined above.
    The salt (II) can be produced by a process comprising reacting a salt represented by the formula (XII):
    in which M represents Li, Na, K or Ag, and Y1, Y2 and R21 have the same meanings as defined above (hereinafter simply called salt (XII)), with a compound represented by the formula (XIII):
    wherein A * has the same meaning as defined above, and G represents F, Cl, Br, I, BF4t AsFe, SbF6, PFe or ClO4 (and hereinafter simply referred to as compound (XIII)).
    The reaction of salt (XII) and compound (XIII) 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 10 ° C, with stirring.
    The amount of component (XIII) is usually 0.5 to 2 moles per 1 mole of salt (XII). The salt (II) obtained by the above process can be isolated by recrystallization and can be purified by washing with water.
    The salt (XII) can be produced by a process comprising the esterification of an alcohol compound represented by the formula (XIV):
    wherein R21 has the same meaning as defined above (hereinafter simply referred to as alcohol compound (XIV)), with a carboxylic acid represented by formula (XV):
    in which M, Y1 and Y2 have the same meanings as those defined above (hereinafter simply called carboxylic acid (VX).
    The esterification reaction of the alcohol compound (XIV) and the carboxylic acid (XV) can generally be carried out by mixing the materials in an aprotic solvent such as dichloroethane, toluene, ethylbenzene, monochlorobenzene, acetonitrile and Ν, Ν-dimethylformamide at a temperature of 20 to 200 ° C, preferably 50 to 150 ° C. In the esterification reaction, an acid catalyst or a dehydrating agent is usually added, and examples of the acid catalyst include organic acids such as p-toluenesulfonic acid, and inorganic acids such as sulfuric acid. Examples of the dehydrating agent include 1,1-carbonyldiimidazole and N, N'-dicyclohexylcarbodiimide.
    The esterification reaction may preferably be carried out with dehydration as this tends to reduce the reaction time. Examples of a dehydration process include the Dean and Stark process.
    The amount of carboxylic acid (XV) is usually 0.2 to 3 moles, preferably 0.5 to 2 moles per 1 mole of the alcohol compound (XIV).
    The amount of the acid catalyst may be a catalytic amount or the amount equivalent to the solvent, and is usually from 0.001 to 5 moles per 1 mole of the alcohol compound (XIV). The amount of the dehydrating agent is usually 0.2 to 5 moles, preferably 0.5 to 3 moles per 1 mole of the alcohol compound (XIV).
    The salt (II) is usually used as an acid generator, and the acid generated by irradiation of the salt (II) acts catalytically with respect to the acidolabilic groups of the RESINE, cleaves the acidolabile groups, and the RESINE becomes soluble in an alkaline aqueous solution. Such a composition is suitable for a positive reserve composition with chemical amplification.
    The present composition preferably contains from 80 to 99.9% by weight of the resin component and from 0.1 to 20% by weight of the salt (II), based on the total amount of the resin component and salt (II).
    In the present resist composition, deterioration in performance caused by acid inactivation that occurs as a result of post-exposure delay can be reduced by addition of an organic base compound, particularly an organic base compound containing nitrogen, as a deactivator.
    Specific examples of the nitrogenous organic base compound include an amino compound represented by the following formulas:
    wherein T1 and T12 independently of one another are hydrogen, alkyl, cycloalkyl or aryl, and alkyl, cycloalkyl and aryl may be substituted by at least one a hydroxyl group, an amino group which may be substituted by a C 1 -C 4 alkyl group and a C 1 -C 6 alkoxy group which may be substituted by a C 1 -C 6 alkoxy group, T 3 and T 4 independently represent one of other a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, and the alkyl, cycloalkyl, aryl and alkoxy group may be substituted by at least one group selected from a hydroxyl group, a group amino which may be substituted by C 1 -C 4 alkyl and C 1 -C 6 alkoxy, or T 3 and T 4 bond together with the carbon atoms to which they are attached to form an aromatic ring, T 5 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 group may be substituted by at least one group selected from a hydroxyl group, an amino group which may be substituted by a C1-C4 alkyl group and a C1-C6 alkoxy group, T6 represents an alkyl or cycloalkyl group, and the alkyl and cycloalkyl group may be substituted by at least one group selected from a hydroxyl group, an amino group which may be substituted by C1-C4alkyl and C1-C6alkoxy) and W represents -CO-, -NH-, -S-, -SS-, an alkylene group of which at least one methylene group may be replaced by -O-, or an alkenylene group of which at least one methylene group may be replaced by -O-, and a quaternary ammonium hydroxide represented by the following formula:
    wherein T7, T8, T9 and T10 independently of one another are an alkyl group, a cycloalkyl group or an aryl group, and the alkyl, cycloalkyl and aryl group may be substituted by at least one group selected from a group hydroxyl, an amino group which may be substituted by a C1-C4 alkyl group and a C1-C6 alkoxy group.
    The alkyl group in T1, T2, T3, T4, T5, T6, T7, T8, T9 and T10 preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
    Examples of amino groups which may be substituted by the C1-C4 alkyl group include amino, methylamino, ethylamino, n-butylamino, dimethylamino and diethylamino groups. Examples of the C1-C6 alkoxy group which may be substituted by the C1-C6 alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy groups. and 2-methoxyethoxy.
    Specific examples of the alkyl group which may be substituted by at least one group selected from a hydroxyl group, an amino group which may be substituted by a C 1 -C 4 alkyl group and a C 1 -C 6 alkoxy group which may be substituted by a C1-C6 alkoxy group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, 2- (2-methoxyethoxy) ethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-aminoethyl, 4-aminobutyl and 6-aminohexyl.
    The cycloalkyl group in T1, T2, T3, T4, T5, T6, T7, T8, T9 and T10 preferably has from 5 to 10 carbon atoms. Specific examples of the cycloalkyl group which may be substituted by at least one group selected from 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 cyclopentyl groups, cyclohexyl, cycloheptyl and cyclooctyl.
    The aryl group in T1, T2, T3, T4, T5, T6, T7, T8, T9 and T10 preferably has from 6 to 10 carbon atoms. Specific examples of the aryl group which may be substituted by at least one group selected from a hydroxyl group, an amino group which may be substituted by a C 1 -C 4 alkyl group and a C 1 -C 6 alkoxy group include phenyl and naphthyl groups. .
    The alkoxy group in T3, T4 and T5 preferably has from 1 to 6 carbon atoms, and specific examples of this group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy and n-hexyloxy.
    The alkylene and alkenylene groups of W preferably have from 2 to 6 carbon atoms. Specific examples of the alkylene group include ethylene, trimethylene, tetramethylene, methylenedioxy and ethylene-1,2-dioxy groups, and specific examples of the alkenylene group include ethane-1,2-diyl groups, 1-propene-1,3 -diyl and 2-butene-1,4-diyl.
    Specific examples of the amine compound include n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline , 4-nitroaniline, 1-naphthylamine, 2-naphthylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3 5-dimethyl-diphenylmethane, 4,4'-diamino-3,3-diethyl-diphenylmethane, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, N-methylaniline, piperidine, diphenylamine, triethylamine, trimethylamine, tripyopylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine,Methyldinonylamine, Methyldidecylamine, Ethyldibutylamine, Ethyldipentylamine, Ethyldihexylamine, Ethyldiheptylamine, Ethyldioctylamine, Ethyldinonylamine, Ethyldidecylamine, Dicyclohexylmethylamine, Tris [2- (2-methoxyethoxy) ethyl] amine , triisopropanolamine, Ν, Ν-dimethylaniline, 2,6-diisopropylaniline, imidazole, benzimidazole, pyridine, 4-methylpyridine, 4-methylimidazole, bipyridine, 2,2'-dipyridylamine, diisopropylamine, 2-pyridylketone, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) -ethane, 1,3-di (4-pyridyl) propane, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, bis (2-pyridyl) ethylene, 1,2-bis (4-pyridyl) ethylene, 1,2-bis (4-pyridyloxy) ethane, 4,4-dipyridyl sulfide, 4,4'-disulfide dipyridyl, 1,2-bis (4-pyridyl) ethylene, 2,2'-dipicolylamine and 3,3'-dipicolylamine.
    Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyftrimethylammonium hydroxide, hydroxide, and the like. (3-trifluoromethylphenyl) trimethylammonium and (2-hydroxyethyl) trimethylammonium hydroxide (called "choline").
    A hindered amine having a piperidine backbone as disclosed in JP 11-52575 A1 can also be used as a quencher.
    From the point of view of pattern formation with higher resolution, quaternary ammonium hydroxide is preferably used as a quencher.
    When the basic compound is used as a quencher, the present resist composition preferably comprises from 0.01 to 1% by weight of the basic compound, based on the total amount of the resin component and salt (II).
    The present resist composition may contain, if necessary, a small amount of various additives such as a sensitizer, a solution-suppressing agent, other polymers, a surfactant, a stabilizer and a dye, as long as the effect of the present invention is not inhibited.
    The present resist composition is generally in the form of a liquid reserve composition wherein the aforementioned ingredients are dissolved in a solvent, and the liquid resist composition is applied to a substrate such as a silicon wafer, by a conventional method as a spin coating. The solvent used is sufficient to dissolve the aforementioned ingredients, have a suitable drying rate and give a uniform and smooth coating after evaporation of the solvent. Solvents generally used in the art can be used.
    Examples of the solvent include a glycol ether ester such as ethyl glycol acetate, methyl glycol acetate and propylene glycol monopropyl ether acetate, and acyclic esters such as ethyl lactate, butyl acetate amyl acetate and ethyl pyruvate, a ketone such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone, and a cyclic ether such as γ-butyrolactone. These solvents can be used alone, and two or more can be mixed for use.
    A resist film applied to the substrate and then dried is subjected to patterning exposure, then heat treated to facilitate a deblocking reaction, and then developed using an alkaline developer. The alkaline developer used may be any of various alkaline solutions used in the art. In general, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly called "choline") is often used.
    It should be understood that the embodiments disclosed herein are examples in all respects and are not limiting. The idea is that the scope of the present invention is determined, not by the foregoing descriptions, but by the appended claims, and covers all variants of the meanings and scope of the claims.
    The present invention will be more specifically described by way of examples, which are not to be construed as limiting the scope of the present invention. The "%" and "parts" used to represent the content of any compound and the amount of any material used in the Examples and Comparative Examples which follow are on a weight basis, unless otherwise expressly stated. The weight average molecular weight of any material used in the examples which follow is a value found by gel permeation chromatography (type HLC-8120GPC, column (three columns): TSK Multipore HXL-M gel, solvent, tetrahydrofuran, TOSOH CORPORATION] using styrene as the standard reference material. The structures of compounds were determined by NMR (type GX-270 or type EX-270, manufacture of JEOL LTD) and mass spectrometry (liquid chromatography: type 1100, manufacture of AGILENT TECHNOLOGIES LTD., Mass spectrometry: type LC / MSD or LC / MSD TOF, manufacture of AGILENT TECHNOLOGIES LTD.), EXAMPLE 1- Synthetic salt
    (1) 230 parts of 30% aqueous sodium hydroxide solution was added to a mixture of 100 parts of methyldifluoro (fluorosulfonyl) acetate and 250 parts of ion-treated water in a bath of ice cream. The resulting mixture was heated and refluxed at 100 ° C for 3 hours. After cooling, the cooled mixture was neutralized with 88 parts of concentrated hydrochloric acid and the resulting solution was concentrated to obtain 164.8 parts of sodium salt of difluorosulfoacetic acid (containing an inorganic salt, purity). : 62.6%).
    (2) 5.0 parts of sodium difluorosulfoacetate (purity: 62.8%), 2.6 parts of 4-oxo-1-adamantanol and 100 parts of ethylbenzene were mixed and 0.8 part was added concentrated sulfuric acid. The resulting mixture was refluxed for 30 hours. After cooling, the mixture was filtered to give solids, and the solids were washed with tert.-butyl methyl ether to give 5.5 parts of the salt represented by the above formula (a). Its purity was 35.6%, calculated by the result of a 1 H NMR analysis.
    1 H NMR (dimethyl sulfoxide - d6I internal standard: tetramethylsilane): d (ppm) 1.84 (d, 2H, J = 13.0 Hz), 2.00 (d, 2H, J = 11.9 Hz) 2.29 - 2.32 (m, 7H), 2.54 (s, 2H).
    (3) To 5.4 parts of the salt represented by the formula (a), and obtained in (2) (purity: 35.6%), a mixed solvent of 16 parts of acetonitrile and 16 parts of water treated with ion exchange. A solution prepared by mixing 1.7 parts of triphenylsulfonium chloride, 5 parts of acetonitrile and 5 parts of ion-treated water was added to the resulting mixture. After 15 hours of stirring, the mixture obtained was concentrated and extracted with 142 parts of chloroform. The organic layer obtained was washed with water treated with ion exchange and concentrated. The resulting concentrate was washed with 24 parts of tert.-butyl methyl ether and the solvent was decanted to give 1.7 part of the salt represented by the above-mentioned formula (b) as a white solid which the we called B1.
    1 H NMR (dimethyl sulfoxide - d6, internal standard: tetramethylsilane): d (ppm) 1.83 (d, 2H, J = 12.7 Hz), 2.00 (d, 2H, J = 12.0 Hz) ), 2.29 - 2.32 (m, 7H), 2.53 (s, 2H), 7.75 - 7.91 (m, 15H).
    MS (ESI (+) spectrum): M + 263.2 (C18H15S + = 263.09) MS (ESI (-) spectrum): M-323.0 (C12H13F206S · = 323.04).
    EXAMPLE 2.- Synthetic salt
    (1) 230 parts of 30% aqueous sodium hydroxide solution were added to a mixture of 100 parts of methyldifluoro (fluorosulfonyl) acetate and 150 parts of ion-treated water in a bath of ice cream. The resulting mixture was heated and refluxed at 100 ° C for 3 hours. After cooling, the cooled mixture was neutralized with 88 parts of concentrated hydrochloric acid and the resulting solution was concentrated to obtain 164.4 parts of sodium salt of difluorosulfoacetic acid (containing an inorganic salt, purity : 62.7%).
    (2) 1.9 part of the sodium salt of difluorosulfoacetate acid (purity: 62.7%), and 9.5 parts of Ν, Ν-dimethylformamide were mixed and 1.0 part of 1 , 1'-carbonydiimidazole. The resulting mixture was stirred for 2 hours. The solution obtained was 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 stirred for 2 hours. The resulting solution was stirred for 15 hours to give the salt-containing solution represented by the above-mentioned formula (C).
    (3) To the solution containing the salt represented by the formula (c) obtained in (2), 17.2 parts of chloroform and 2.9 parts of a 14.8% strength aqueous solution of chloroform were added. triphenylsulfonium. The resulting mixture was stirred for 15 hours and then separated into an organic layer and an aqueous layer. The aqueous layer was extracted with 6.5 parts of chloroform to give a layer in chloroform. The organic layer and the chloroform layer were mixed, washed with ion-exchanged water and concentrated. The resulting concentrate was mixed with 5.0 parts of tert-butyl methyl ether and the resulting mixture was stirred and filtered to give 0.2 part of the salt represented by the above formula (d) as a white solid. which we called B2.
    NMR (dimethyl sulfoxide - d6, internal standard: tetramethylsilane): d (ppm) 1.38 - 1.51 (m, 12H), 2.07 (s, 2H), 4.41 (s, 1H), 7.75-7.89 (m, 15H).
    MS (ESI (+) spectrum): M + 263.07 (C18H15S + = 263.09) MS (ESI (-) spectrum): M-329.10 (C13H17F2O6S · = 330.07).
    EXAMPLE 3 Synthetic salt
    (1) 230 parts of 30% aqueous sodium hydroxide solution were added to a mixture of 100 parts of methanol (2-fluoroaluminum acetate) and 250 parts of treated water. by ion exchange, in an ice bath. The resulting mixture was heated and refluxed at 100 ° C for 2.5 hours. After cooling, the cooled mixture was neutralized with 88 parts of concentrated hydrochloric acid and the resulting solution was concentrated to give 158.4 parts of sodium salt of difluorosulfoacetic 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 were mixed and 31.26 parts of p-toluenesulfonic acid. The resulting mixture was refluxed for 6 hours. The resulting mixture was concentrated for removal of dichloroethane, then 200 parts of heptane was added to the resulting residue. The resulting mixture was stirred and filtered. The solid obtained was mixed with 200 parts of acetonitrile. The resulting mixture was stirred and filtered. The resulting filtrate was concentrated to give 39.03 parts of the salt represented by formula (e) above.
    1H NMR (dimethyl sulfoxide, internal standard: tetramethylsilane): d (ppm) 0.90 - 1.27 (m, 5H), 1.58 - 1.71 (m, 6H), 4.02 ( d, 2H).
    (3) 39.03 parts of the salt represented by the formula (e), obtained in (2), were dissolved in 195.2 parts of ion-exchanged water. To the resulting solution was added a solution prepared by mixing 39.64 parts of triphenylsulfonium chloride and 196.4 parts of ion-treated water, and then 500 parts of acetonitrile were added. The resulting mixture was stirred for 15 hours and then concentrated. The residue obtained was extracted twice with 250 parts of chloroform, and the organic layers obtained were mixed and washed with water treated with ion exchange, and then concentrated. The resulting concentrate was mixed with 200 parts of tert.-butyl methyl ether and the resulting mixture was stirred and filtered to give 40.16 parts of the salt represented by the above-mentioned formula (f) as a white solid. called it B4.
    1 H NMR (dimethyl sulfoxide, internal standard: tetramethylsilane): d (ppm) 0.88 - 1.28 (m, 5H), 1.56 - 1.71 (m, 6H), 4.01 ( d, 2H), 7.75-7.90 (m, 15H).
    MS (ESI (+) spectrum): M + 263.1 (C18H15S + = 263.09) MS (ESI (-) spectrum): M-271.1 (C9H13F2O5S · = 271.05.
    EXAMPLE 4.- Synthetic salt
    (1) 460 parts of 30% aqueous sodium hydroxide solution was added to a mixture of 200 parts of methyldifluoro (fluorosulfonyl) acetate and 300 parts of ion-treated water in a bath of ice cream. The resulting mixture was heated and refluxed at 100 ° C for 2.5 hours. After cooling, the cooled mixture was neutralized with 175 parts of concentrated hydrochloric acid and the resulting solution was concentrated so that 328.19 parts of sodium salt of difluorosulfoacetic acid (containing an inorganic salt, purity 63.5%).
    (2) 24.0 parts of p-toluenesulfonic acid was added to a mixture of 39.4 parts of the sodium salt of difluorosulfoacetic acid (purity: 63.5%), 21.0 parts of 1 adamantane-methanol and 200 parts of dichloroethane, and the resulting mixture was refluxed for 7 hours. The mixture was concentrated to remove the dichloroethane and 250 parts of tert-butyl methyl ether were added to the obtained residue. The resulting mixture was stirred and filtered to give the solid. 250 parts of acetonitrile were added to the solid, and the resulting mixture was stirred and filtered. The resulting filtrate was concentrated to give 32.8 parts of the salt represented by formula (g) above.
    (3) 32.8 parts of the salt represented by the above-mentioned formula (g), obtained in (2), were dissolved in 100 parts of ion-treated 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 was concentrated. The resulting residue was washed 2X with 200 parts of chloroform. The organic layers obtained were mixed and washed several times with water treated with ion exchange, until the resulting aqueous layer was neutralized. The resulting solution was concentrated. 300 parts of tert.-butyl methyl ether were added to the concentrate and stirred. The resulting mixture was filtered and the resulting solid was dried to give 39.7 parts of the salt represented by the above formula (h) as a white solid which was named B5.
    1H NMR (dimethyl sulfoxide - d6, internal standard: tetramethylsilane): δ (ppm) 1.52 (d, 6H), 1.63 (dd, 6H), 1.93 (s, 3H), 3.81 (s, 2H), 7.76 - 7.90 (m, 15H).
    MS (ESI (+) spectrum): M + 263.2 (C18H15S + = 263.09) MS (E (1) (-)) spectrum: M-323.0 (C13H17F2O5S- = 323.08).
    EXAMPLE 5. Synthetic salt
    (1) 26.5 parts of diphenylsulfide were dissolved in 79.4 parts of acetonitrile. 29.5 parts of silver perchlorate (1) were added thereto, followed by a solution prepared by mixing 52.3 parts of acetonitrile and 26.2 parts of n-butyl iodide. The resulting mixture was stirred for 24 hours. The precipitate was filtered for removal and the filtrate was concentrated. The concentrate was mixed with 135.9 parts of tert.-butyl methyl ether and the resulting mixture was stirred and filtered. 101.7 parts of tert.-butyl methyl ether were added to the solid and the resulting mixture was stirred and filtered to give 14.8 parts of n-butyldiphenylsulfonium perchlorate as a white solid.
    1H NMR (Dimethyl sulfoxide, internal standard tetramethylsilane): δ (ppm) 0.88 (t, 3H), 1.41 -1.49 (m, 2H), 1.52 - 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 aforementioned formula (g), obtained by a process similar to that described in the example of synthetic salt 4 (1) and (2) described above, were mixed with 50 0 parts of chloroform. A mixture prepared by mixing 13.94 parts of n-butyldiphenylsulfonium perchlorate obtained in (1) above and 41.82 parts of ion-treated water was added to the resulting mixture. The resulting mixture was stirred for 15 hours, and separated into an organic layer and an aqueous layer. The aqueous layer was extracted with 10.0 parts of chloroform to give a chloroform layer. The organic layer and the chloroform layer were mixed and washed several times with ion-exchange treated water until the resulting aqueous layer was neutralized and then concentrated. The resulting concentrate was mixed with 37.6 parts of tert.-butyl methyl ether and the resulting mixture was stirred and filtered. The resulting solid was mixed with 16.8 parts of ethyl acetate and the resulting mixture was stirred and filtered to give 2.89 parts of the salt represented by the above-mentioned formula (i) as a white solid. which we called B6.
    1 H NMR (dimethyl sulfoxide - d6, internal standard: tetramethylsilane): δ (ppm) 0.88 (t, 3H), 1.42 -1.67 (m, 16H), 1.91 (s, 3H) , 3.80 (s, 2H), 4.44 (t, 2H), 7.71-7.83 (m, 6H), 8.98 (d, 4H).
    MS (ESI (+) spectrum): M + 243.1 1 (C 16 H 19 S + = 243.12) MS (ESI (-) spectrum): M-323.10 (C 13 H 17 F 2 O 5 S '= 323.08).
    EXAMPLE 6 Synthetic Salt
    (1) 6.56 parts of diphenylsulfide were dissolved in 19.7 parts of acetonitrile. To this was added 7.30 parts of silver perchlorate (1) and a solution prepared by mixing 10.0 parts of acetonitrile and 5.00 parts of methyl iodide. The resulting mixture was stirred for 24 hours. The precipitate was filtered for removal and the filtrate was concentrated. The concentrate was mixed with 39.2 parts tert.-butyl methyl ether and the resulting mixture was stirred and filtered to give 9.38 parts of methydiphenylsulfonium perchlorate as a white solid.
    1 H NMR (dimethyl sulfoxide - d6, internal standard: tetramethylsilane): d (ppm) 3.81 (s, 3H), 7.67 - 7.79 (m, 6H), 8.01 - 8.04 ( m, 4H).
    (2) 8.29 parts of the salt represented by the aforementioned formula (g), obtained by a process similar to that of the synthetic salt example 4 (1) and (2) described above, were mixed with 49 7 parts of chloroform. To the resulting mixture was added a mixture prepared by mixing 9.8 parts of methyldiphenylsulfonium perchlorate obtained in (1) above and 28.14 parts of ion-treated water. The resulting mixture was stirred for 15 hours, and separated into an organic layer and an aqueous layer. The aqueous layer was extracted with 33.1 parts of chloroform to give a chloroform layer. The organic layer and the chloroform layer were mixed and washed several times with ion-exchange treated water until the aqueous layer was neutralized and then concentrated. The resulting concentrate was mixed with 33.8 parts of tert.-butyl methyl ether and the resulting mixture was stirred. The supernatant was decanted to give 7.81 parts of the salt represented by the above-mentioned Formula 0 in the form of a colorless liquid, which was named B7. 1H NMR (dimethylsulfoxide - d6, internal standard: tetramethylsilane): d (ppm) 1.50 (d, 6H), 1.61 (dd, 6H), 1.91 (s, 2H), 3.82 (s, 3H), 7.67 - 7.79 (m, 6H), 8.02 - 8.05 (m, 4H).
    MS (ESI (+) spectrum): M + 201.0 (C13H13S + = 201.07) MS (ESI (-) spectrum): M-323.0 (C13H17F205S · = 323.08).
    EXAMPLE 7 - Synthetic Salt
    (1) 5.0 parts of the salt represented by the formula (a) (purity: 49.1%), obtained by a process similar to that described in the synthetic salt example 4 (1) and (2), describes more top, and 50.0 parts of chloroform were mixed. To the resulting mixture was added 42.0 parts of aqueous triphenylsulfonium chloride solution (concentration: 5.0%). After stirring for 15 hours, the mixture obtained was separated into an organic layer and an aqueous layer. The resulting aqueous layer was extracted with 25.0 parts by weight of chloroform to give a chloroform layer. The organic layer and the chloroform layer were mixed and the resulting solution was washed several times with ion-treated water until the resulting aqueous layer was neutralized. The solution was concentrated and the resulting concentrate was mixed with 29.6 parts of tert.-butyl methyl ether and the supernatant was removed by settling. The resulting residue was mixed with 16.6 parts of ethyl acetate and the supernatant was removed by decantation to give 1.6 part of the salt represented by the above formula (k) under form of a pale yellow oil, which has been called B8.
    1H NMR (dimethyl sulfoxide - d6, internal standard: tetramethylsilane): d (ppm) 1.82 (d, 2H), 1.99 (d, 2H), 2.21 - 2.35 (m, 7H) , 2.52 (s, 2H), 3.81 (s, 3H), 7.67 - 7.79 (m, 6H), 8.01 - 8.06 (m, 4H).
    EXAMPLE 8 Synthetic Salt
    (1) 5.0 parts of thioanisole were dissolved in 15.0 parts of acetonitrile. To this was added 8.35 parts of silver perchlorate (I) and then 11.4 parts of acetonitrile solution containing 5.71 parts of methyl iodide were added. The resulting mixture was stirred for 24 hours. The precipitate was filtered for removal and the filtrate was concentrated. The concentrate was mixed with 36.8 parts of tert.-butyl methyl ether and the resulting mixture was stirred and filtered to give 8.22 parts of dimethylphenylsulfonium perchlorate as a white solid.
    (2) 5.98 parts of the salt represented by the aforementioned formula (g), obtained by a process similar to that described in the example of synthetic salt 4 (1) and (2) described above, were mixed with 35 9 parts of chloroform. A solution obtained by mixing 4.23 parts of dimethylphenylsulfonium perchlorate obtained in (1) above and 12.7 parts of ion-treated water was added to the resulting mixture. The resulting mixture was stirred for 4 hours. hours, and separated into an organic layer and an aqueous layer. The aqueous layer was extracted with 23.9 parts by weight of chloroform to give a chloroform layer. The organic layer and the chloroform layer were mixed and the resulting solution was washed several times with ion-exchanged water until the resulting aqueous layer was neutralized and then concentrated. The resulting concentrate was mixed with 31.8 parts of tert.-butyl methyl ether and the resulting mixture was filtered so that 5.38 parts of the salt represented by the above-mentioned formula (I) in the form of a white solid, which we called B9. H-NMR (dimethyl sulfoxide, 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 - 7.80 (m, 3H), 8.03 - 8.06 (m, 2H).
    MS (ESI (+) spectrum): M + 193.0 (CgHnS + = 139.06) MS (ESI (-) spectrum): M-323.0 (C13H17F2O5S- = 323.08).
    EXAMPLE 9- Synthetic salt
    (1) 460 parts of 30% aqueous sodium hydroxide solution was added to a mixture of 200 parts of methyldifluoro (fluorosulfonyl) acetate and 300 parts of ion-treated water in a bath of ice cream. The resulting mixture was heated and refluxed at 100 ° C for 2.5 hours. After cooling, the cooled mixture was neutralized with 175 parts of concentrated hydrochloric acid, and the solution was concentrated to obtain 328.19 parts of sodium salt of difluorosulfoacetic acid (containing an inorganic salt, purity 62.8%).
    (2) 5.0 parts of sodium difluorosulfoacetate (purity: 62.8%), obtained in (1) above, 2.6 parts of 4-oxo-1-adamantanol and 100 parts of ethylbenzene were mixed and 0.8 part of concentrated sulfuric acid was added thereto. The resulting mixture was refluxed for 30 hours. After cooling, the mixture was filtered to give solids, and the solids were washed with tert.-butyl methyl ether to give 5.5 parts of the salt represented by the above formula (a). Its purity was 57.6%, calculated by the result of a 1 H NMR analysis.
    1H NMR (dimethylsulfoxide - d6, internal standard tetramethylsilane): d (ppm) 1.84 (d, 2H), 2.00 (d, 2H), 2.29 - 2.32 (m, 7H), 2.54 (s, 2H).
    (3) To 4.3 parts of the salt represented by formula (a), obtained in (2) (purity: 57.6%), 43.0 parts of chloroform were added. 2.2 parts of the sulfonium salt represented by the above-mentioned formula (m) and 11.7 parts of ion-treated water were added to the resulting mixture. After stirring for 15 hours, the mixture obtained was separated into an organic layer and an aqueous layer. The organic layer was washed several times with ion-exchange treated water until the resulting aqueous layer was neutralized and then concentrated. The resulting concentrate was mixed with 15.0 parts of tert.-butyl methyl ether and the supernatant removed by decantation. The resulting residue was dried to give 2.3 parts of the salt represented by the above-mentioned formula (n) as a white solid, which was named B10.
    1H NMR (dimethylsulfoxide - d6, internal standard: tetramethylsilane): d (ppm) 1.82 (d, 2H), 1.98 (d, 2H), 2.27 - 2.35 (m, 7H) , 2.51 (s, 2H), 7.52 (d, 4H), 7.74 - 7.89 (m, 20H), 7.91 (d, 4H).
    The monomers used in the following examples of synthetic resins are the following M1, M2, M3, M4, M5 and M6 monomers.
    EXAMPLE 1 Synthetic resin
    13.50 parts of monomer M1, 3.53 parts of monomer M2 and 18.66 parts of monomer M3 were dissolved in a quantity of 1,4-dioxane of 1.5 times the amount of all the monomers to be used (proportion molar monomers: monomer M1: monomer M2: monomer M3 = 40: 11: 49). To the solution was added 2,2-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) as initiators, in a proportion of 1 mol% and 3 mol%, respectively, based on total molar amount of monomers, and the resulting mixture was heated at 74 ° C for about 5 hours.
    The reaction solution was poured into a large amount of a mixed solvent of methanol and water to cause precipitation. The precipitate was isolated and washed twice with a large amount of mixed solvent of methanol and water for purification. As a result, a copolymer having a weight average molecular weight of about 9200 was obtained with a yield of 80%. This copolymer had the following structural units. It is designated as A1 resin.
    EXAMPLE 2 Synthetic resin
    15.00 parts of monomer M1, 4.89 parts of monomer M2.11,12 parts of monomer M3 and 8.81 parts of monomer M4 were dissolved in a quantity of 1,4-dioxane of 1.5 times the amount. of all the monomers to be used (molar proportion of the monomers: monomer M1: monomer M2: monomer M3: monomer M4 = 35: 12: 23: 30). To the solution was added 2,2-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) as initiators, in a proportion of 1 mol% and 3 mol%, based on the amount molar total of monomers. The resulting mixture was heated at 77 ° C for about 5 hours. The reaction solution was cooled, then poured into a large amount of a mixed solvent of methanol and water to cause precipitation. The precipitate was isolated and washed twice with a large amount of mixed solvent of methanol and water for purification. As a result, a copolymer having a weight average molecular weight of about 8100 was obtained with a yield of 78%. This copolymer had the following structural units. It is designated as A2 resin.
    EXAMPLE 3 Synthetic resin
    30.00 parts of monomer M1, 14.27 parts of monomer M2 and 10.28 parts of monomer M4 were dissolved in a quantity of methyl isobutyl ketone of 2.6 times the amount of all the monomers to be used (molar proportion of monomers: monomer M1: monomer M2: monomer M4 = 50: 25:25). To the solution was added 2,2-azobisisobutyronitrile as initiator, in a proportion of 2 mol%, based on the total molar amount of monomers, and the resulting mixture was stirred at 87 ° C for about 6 hours. hours. The reaction solution was cooled and poured into a large amount of a mixed solvent of methanol and water to cause precipitation. The precipitate was isolated and washed twice with a large amount of mixed solvent of methanol and water for purification. As a result, a copolymer having a weight average molecular weight of about 9400 was obtained with a yield of 47%. This copolymer had the following structural units. It is designated as resin A3.
    EXAMPLE 4 Synthetic resin
    In a four neck flask equipped with a thermometer and a condenser, 77.24 parts of 1,4-dioxane were charged and nitrogen gas was bubbled for 30 minutes. In the nitrogen atmosphere, once the solvent was heated to 74 ° C, a solution prepared by mixing 45.00 parts of the M1 monomer, 10.07 parts of the monomer M2, was added dropwise to the hot solvent. , 78 parts of the monomer M3, 14.51 parts of the monomer 4, 8.37 parts of the monomer M5, 0.88 parts of 2,2'-azobis-isobutyronitrile, 3.97 parts of 2,2'-azobis (2 , 4-dimethylvaleronitrile) and 115.86 parts of 1,4-dioxane, within 2 hours, maintaining the temperature at 74 ° C (molar proportion of monomers: monomer M1, monomer M2: monomer M3: monomer M4 : M5 monomer = 34: 8: 34: 16: 8). After the addition, the resulting mixture was held at 74 ° C for 5 hours. The reaction mixture was cooled and diluted with 141.61 parts of 1,4-dioxane. The resulting mixture was poured into a mixed solution of 1339 parts of methanol and 335 parts of ion-exchanged water, stirring, stirring, and the deposited resin.
    in the mixture was collected by filtration. The deposit was added to 837 parts of methanol, the mixture was stirred and the solid was collected by filtration. The series of operations including addition, brewing and filtration harvesting was repeated two more times, then dried under reduced pressure to obtain 96.4 parts of a 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, with a yield of 75%. This copolymer has the following structural units. It is designated as A4 resin.
    EXAMPLE 5 Synthetic resin
    In a four neck flask equipped with a thermometer and a condenser, 83.33 parts of 1,4-dioxane were charged and nitrogen gas was bubbled through for 30 minutes. In the nitrogen atmosphere, once the solvent was heated to 74 ° C, a solution prepared by mixing 8.68 parts of monomer M2, 36.05 parts of monomer M3, was added dropwise to the hot solvent. , 31 parts of M4 monomer, 16.83 parts of M5 monomer, 45.00 parts of monomer M6.1.01 part of 2,2'-azobis-isobutyronitrile, 4.56 parts of 2,2'-azobis (2 parts) , 4-dimethylvaleronitrile) and 124.99 parts of 1,4-dioxane, within 2 hours, maintaining the temperature at 74 ° C (molar proportion of monomers: monomer M2: monomer M3: monomer M4: monomer M5 : monomer M6 = 6: 21: 31: 14: 28). After the addition, the resulting mixture was maintained at 74 ° C.
    for 5 hours. The reaction mixture was cooled and diluted with 152.76 parts of 1,4-dioxane. The resulting mixture was poured into a mixed solution of 1444 parts of methanol and 361 parts of ion-exchanged water, with stirring, the mixture was stirred, and the resin deposited.
    in the mixture was collected by filtration. The deposit was added to 930 parts of methanol, the mixture was stirred and the solid was collected by filtration. The series of operations including addition, brewing and filtration harvesting was repeated two more times, then dried under reduced pressure to obtain 97.9 parts of a copolymer having a weight average molecular weight of 7830. and a ratio Mw (weight average molecular weight) / Mn (number average molecular weight) of 1.80, with a yield of 71%. This copolymer has the following structural units. It is designated as A5 resin. EXAMPLE 6 Synthetic resin
    In a four neck flask equipped with a thermometer and a condenser, 82.87 parts of 1,4-dioxane were charged and nitrogen gas was bubbled for 30 minutes. In the nitrogen atmosphere, once the solvent was heated to 74 ° C, a solution prepared by mixing 45.00 parts of the monomer M1.10.07 parts of the monomer M2, 74 was added dropwise to the hot solvent. , 68 parts of the M3 monomer, 8.37 parts of the M5 monomer, 0.88 parts of 2,2'-azobis-isobutyronitrile, 3.97 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 124, 31 parts of 1,4-dioxane, within 2 hours, maintaining the temperature at 74 ° C (molar proportion of the monomers: monomer M1: monomer M2: monomer M3: monomer M5 = 34: 8: 50: 8 ). After the addition, the resulting mixture was held at 74 ° C for 5 hours. The reaction mixture was cooled and diluted with 151.93 parts of 1,4-dioxane. The resulting mixture was poured into a mixed solution of 1436 parts of methanol and 359 parts of ion-exchanged water, stirred, the mixture was stirred, and the resin deposited in the mixture was collected by filtration. The deposit was added to 898 parts of methanol, the mixture was stirred and the solid was collected by filtration. The series of operations including addition, stirring and filtration harvesting was repeated two more times, then dried under reduced pressure to obtain 101.1 parts of a copolymer having a weight average molecular weight of 90%. and a ratio Mw (weight average molecular weight) / Mn (number average molecular weight) of 1.87, with a yield of 73%. This copolymer has the following structural units. It is designated as resin A6.
    EXAMPLES 1 TO 13 AND COMPARATIVE EXAMPLES 1 TO 2 .- <Acid generator> Acid generator B1:
    B2 acid generator:
    B3 acid generator:
    B4 acid generator:
    B5 acid generator:
    B6 acid generator:
    B7 acid generator:
    B8 acid generator:

    Acid generator B9 Acid generator B10:
    <Resins> Resins A1 to A6 <deactivator> Q1: 2,6-diisopropylamine.
    <Solvent> Y1: propylene glycol monomethyl ether acetate 145 parts 2-heptanone 20.0 parts propylene glycol monomethyl ether 20.0 parts γ-butyrolactone 3.5 parts
    The following components were mixed and dissolved, and then filtered on a fluororesin filter having a pore diameter of 0.2 μm, to prepare the liquid reserve.
    Resin (type and quantity as described in Table 1) Acid generator (type and quantity as described in Table 1) Deactivator (type and quantity as described in Table 1)
    Solvent (type as described in Table 1)
    Silicon wafers were coated with "ARC-29", which is an organic antireflective coating composition available from Nissan Chemical Industries, Ltd., and then fired under the following conditions: 205 ° C, 60 ° C .; seconds, to form an organic anti-reflective coating with a thickness of 780 A. Each of the liquid reserves prepared as above was deposited by centrifugation on the anti-reflective coating, so that the thickness of the resulting film becomes 0.15 μm after drying. The silicon wafers thus coated with the respective liquid reserves were each precooked on a direct hot plate at a temperature indicated in column "PB" of Table 1 for 60 seconds. Using an ArF progressive excimer ("FPA-5000AS3" manufactured by Canon Inc., NA = 0.75, annular 2/3), each slab thus formed with the respective resist film was subjected to pattern with lines and spaces, the amount of exposure being varied gradually.
    After exposure, each slab was baked on a hotplate at a temperature indicated in the "PEB" column of Table 1 for 60 seconds, and then padded for 60 seconds with an aqueous solution. 2.38% by weight of tetramethylammonium hydroxide.
    Each dark zone pattern grown on the organic anti-reflective coating substrate was observed, after development, with a scanning electron microscope, and the results are shown in Table 2. The term "dark area pattern" as used in FIG. 'used herein' means a pattern obtained by exposure and development with a reticle comprising a chromium base surface (light-arresting portion) and linear layers of glass (light-transmitting portion) formed on the chromium surface and aligned with each other . Therefore, the dark area pattern is such that after exposure and development, the resist layer surrounding the line and space pattern remains on the substrate.
    Effective Sensitivity (ES): It is expressed as the amount of exposure such that the line pattern and space pattern are 1: 1 after exposure by a 100 nm mask to lines and spaces and development.
    Resolution: It is expressed as the minimum size of the space pattern that gives the space pattern divided by the line pattern to the exposure amount of the effective sensitivity.
    Table 1
    Table 2
    It can be seen from Table 2 that the resist compositions of the examples, which are in accordance with the invention, give a good reserve pattern in terms of resolution.
    The present composition provides a good resist pattern in terms of resolution and good line edge roughness, and is particularly suitable for ArF excimer laser lithography, KrF excimer laser lithography and ArF immersion lithography.
    权利要求:
    Claims (11)
    [1]
    A chemically amplified resist composition comprising: a resin comprising a structural unit having an acidolabile group and a structural unit represented by the formula (I):

    [2]
    The chemical amplification resist composition according to claim 1, wherein the structural unit having an acid-labile group is a structural unit represented by the formula (Ilia):

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

    [4]
    The chemically amplified resist composition according to claim 1, wherein the structural unit represented by the formula (I) is a structural unit represented by the formulas (Va), (Vb) or (Vc):

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

    [6]
    The chemically amplified resist composition of claim 1, wherein the salt represented by the formula (II) is a salt represented by the formula (X):

    [7]
    The chemically amplified resist composition of claim 1, wherein A + is at least one cation selected from the group consisting of a cation represented by the formula (VIla):

    [8]
    The chemically amplified resist composition of claim 1, wherein A + is a cation represented by the formulas (Vile), (Vllf) or (Vllg):

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

    [10]
    The chemically amplified resist composition of claim 1, wherein A + is a cation represented by the formula (Vlli):

    [11]
    The resist composition of claim 1, wherein the resist composition further comprises a basic compound.
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    法律状态:
    2014-06-30| RE| Patent lapsed|Effective date: 20131231 |
    优先权:
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    JP2006336655|2006-12-14|
    JP2006336655|2006-12-14|
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