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    • 专利摘要:
    A chemically enhanced resist composition comprising: (A) a salt represented by formula (I); in which R21 represents a hydrocarbon group, Q1 and Q2 each independently represent a fluorine atom, and A1 represents at least one organic cation (B) a salt represented by formula (II): in which A '+ represents at least an organic cation, and (c) a resin which contains a structural unit having an acid sensitive group and which is itself insoluble or poorly soluble in an aqueous alkaline solution, but becomes soluble in an aqueous alkaline solution by the action of 'an acid.
    公开号:BE1018475A3
    申请号:E2008/0165
    申请日:2008-03-19
    公开日:2011-01-11
    发明作者:Satoshi Yamaguchi；Yoshiyuki Takata；Kaoru Araki
    申请人:Sumitomo Chemical Co；
    IPC主号:
    专利说明:

    CHEMICALLY AMPLIFIED RESIST COMPOSITION
    Field of the invention
    The present invention relates to a chemically amplified resist composition.
    Background of the invention
    A chemically amplified resist composition used for microfabrication of semiconductors employing a lithographic process, contains a resin which comprises a structural unit having an acid-sensitive group and which is itself insoluble or poorly soluble in an aqueous alkaline solution, but becomes soluble in an aqueous alkaline solution by the action of an acid, and an acid generator comprising a compound generating an acid by irradiation.
    In the manufacture of semiconductors, it is desirable to form patterns having high resolution and good line edge roughness and it is expected that a chemically amplified resist composition will provide such patterns.
    US 2006-0194982 A1 discloses a chemically amplified resist composition containing the salt represented by the following formula:
    wherein E represents a hydrogen atom or a hydroxyl group, and a resin which contains a structural unit having an acid-sensitive group and which is itself insoluble or poorly soluble in an aqueous alkaline solution, but becomes soluble in a solution aqueous alkaline by the action of an acid.
    US 2003/0194639 A1 discloses a chemically amplified resist composition containing the salt represented by the following formula:
    as an acid generator.
    US 2003/0194639 A1 also discloses a chemically amplified resist composition containing the salt represented by the following formula:
    as an acid generator.
    Summary of the invention
    An object of the present invention is to provide a chemically amplified resist composition.
    This and other objects of the present invention will become apparent from the following description.
    The present invention relates to the following points.
    A chemically amplified resist composition comprising: (A) a salt represented by formula (I):
    wherein R21 represents a C1-C30 hydrocarbon group which may be substituted, and at least one -CH2- unit in the hydrocarbon group may be substituted with -CO- or -O-, Q1 and Q2 each independently represent an atom of fluorine or a C1-C6 perfluoroalkyl group, and A + represents at least one organic cation selected from a cation represented by formula (Ia):
    in which P1, P2 and P3 each independently represent a C1-C30 alkyl group, which may be substituted by at least one group chosen from a hydroxyl group, a C3-C12 cyclic hydrocarbon group and a C1-C6 alkoxy group; C12, or a C3-C30 cyclic hydrocarbon group which may be substituted by at least one group chosen from a hydroxyl group and a C1-C12 alkoxy group, a cation represented by the formula (Ib):
    wherein P4 and P5 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, and a cation represented by the formula (Ic):
    in which P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20 and P21 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a group C1-C12 alkoxy, B represents a sulfur or oxygen atom and m represents 0 or 1, (B) a salt represented by the formula (II):
    in which A '+ represents at least one organic cation chosen from the cations represented by the abovementioned formulas (Ia), (Ib) and (Ie), and E "represents at least one organic anion chosen from an anion represented by the formula ( II-1):
    wherein Q3 represents a C1-C10 perfluoroalkyl group, and an anion represented by the formula (II-2):
    wherein Q4 represents a C1-C10 perfluoroalkyl group, and (C) a resin which contains a structural unit having an acid-sensitive moiety and which is itself insoluble or poorly soluble in an aqueous alkaline solution, but becomes soluble in a aqueous alkaline solution by the action of an acid; 2. The chemically amplified resist composition according to item 1, wherein Q1 and Q2 each independently represent a fluorine atom or a trifluoromethyl group; The chemically amplified resist composition according to item 1, wherein Q1 and Q2 are fluorine atoms; 4 · The chemically amplified resist composition according to any one of 1 to 3, wherein Q3 represents a trifluoromethyl group, a pentafluoroethyl group or a nonafluorobutyl group; The chemically amplified resist composition according to any one of 1-3, wherein Q4 is a trifluoromethyl group or a pentafluoroethyl group; 6 · The chemically amplified resist composition according to any one of 1 to 4, wherein E "is an anion represented by the formula (II-1): The chemically amplified resist composition according to any one of points 1 to 6, wherein A + and A '+ are the same or different and each independently represents a cation represented by the formula (Id), (le) or (If):
    in which 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 hydrogen atom in the C1-C20 alkyl group. may be substituted with a hydroxyl group, a C1-C12 alkoxy group or a C3-C12 cyclic hydrocarbon group, and at least one hydrogen atom of the C3-C30 cyclic hydrocarbon group may be substituted by a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, and P31, P32 / P33 / P34, P35 and P36 each independently represent a hydroxyl group, a C1-C12 alkyl group, a C1-C6 alkoxy group, C12 or a C3-C12 cyclic hydrocarbon group, and 1, k, j, i, h and g each independently represent an integer of 0 to 5; The chemically amplified resist composition according to any one of 1 to 6, wherein A + and A '+ are the same or different, and each independently represents a cation represented by the formula (Ig):
    wherein P41, P42 and P43 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group; 9 · The chemically amplified resist composition according to any one of 1 to 6, wherein A + and A '+ are the same or different or each independently represents a cation represented by the formula (Ih):
    wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group; The chemically amplified resist composition according to any one of items 1 to 9, wherein R21 represents a group represented by the formula:
    wherein Z1 represents a single bond or - ((¾) f-, f represents an integer of 1 to 4, Y1 represents -CH2-, -CO- or -CH (OH) -; the ring X1 represents a monocyclic hydrocarbon group or polycyclic C3-C30 wherein a hydrogen atom is substituted by a hydroxyl group in the Y1 position when Y1 is -CH (OH) -, or in which two hydrogen atoms are substituted with = 0 in the Y1 position when Y1 represents -CO-, and at least one hydrogen atom in the C3-C30 monocyclic or polycyclic hydrocarbon group may be substituted by a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 perfluoroalkyl group; C4, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group 11. The chemically amplified resist composition according to item 10, wherein the group represented by the formula:
    is a group represented by formulas (1), (m) or (n):
    12. The chemically amplified resist composition according to any one of 1 to 6, wherein A + is a cation represented by the formula (Ih):
    wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group, and R21 represents a group represented by the formula:
    wherein Z1 represents a single bond or - (CH2) f-, f represents an integer from 1 to 4, Y1 represents -CH2-, -CO- or -CH (OH) -; the ring X1 represents a C3-C30 monocyclic or polycyclic hydrocarbon group, in which a hydrogen atom is substituted with a hydroxyl group at the Y1 position when Y1 represents -CH (OH) -, or in which two hydrogen atoms are substituted by = O at the Y1 position when Y is -CO-, and at least one hydrogen atom of the C3-C30 monocyclic or polycyclic hydrocarbon group may be substituted by a C1-C6 alkyl group, a C1-C6 alkoxy group; C6, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group; 13. The chemically amplified resist composition according to item 12, wherein the group represented by the formula:
    is a group represented by formulas (1), (m) or (n):
    The chemically amplified resist composition according to any one of 1 to 4, wherein A '+ is a cation represented by the formula (Ih):
    wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group, and E "is an anion represented by the formula (11-1):
    wherein Q3 represents a C1-C10 perfluoroalkyl group; The chemically amplified resist composition according to any one of 1 to 4, wherein A + and A '+ are the same or different and each independently represents a cation represented by the formula (Ih):
    wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group, R21 is a group represented by the formula:
    wherein Z1 represents a single bond or - (CH2) f-, f is an integer from 1 to 4, Y1 represents -CH2-CO- or -CH (OH) -; the ring X1 represents a C3-C30 monocyclic or polycyclic hydrocarbon group, in which a hydrogen atom is substituted with a hydroxyl group at the Y1 position when Y1 represents -CH (OH) -, or in which two hydrogen atoms are substituted by = O at the Y1 position when Y is -CO-, and at least one hydrogen atom of the C3-C30 monocyclic or polycyclic hydrocarbon group may be substituted by a C1-C6 alkyl group, a C1-C6 alkoxy group; C6, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group, and E "is an anion represented by the formula (II-1): O3SO3 (XI-1) wherein Q3 represents a C1-C10 perfluoroalkyl group; 16. The chemically amplified resist composition according to any one of items 1 to 15, wherein the quantitative ratio of the salt represented by the formula (I) to the salt represented by the formula ( II) is 9/1 to 1/9; · The chemically amplified resist composition of any one of items 1 to 16, wherein the resin contains a structural unit derived from a monomer having a bulky acid-sensitive moiety; 18- The resist composition according to item 17, wherein the acid-sensitive large group is a 2-alkyl-2-adamantyl ester group or a 1- (1-adamantyl) -1-alkylalkyl ester group; The resist composition according to item 18, wherein the monomer having an acid-sensitive bulky group is a 2-alkyl-2-adamantyl acrylate group, 2-alkyl-2-adamantyl methacrylate, 1- (acrylate) acrylate, 1-adamantyl) -1-alkylalkyl, 1- (1-adamantyl) -1-alkylalkyl, 5-norbornene-2-carboxylic acid 2-alkyl-2-adamantyl, 5-norbornene-2-carboxylate 1- (1-adamantyl) -1-alkylalkyl, 1-adamantyl) -1-alkylalkyl, 2-alkyl-2-adamantyl α-chloroacrylate or 1- (1-adamantyl) -1-alkylalkyl α-chloroacrylate; 20. The resist composition according to any one of 1 to 19, wherein the resist composition also comprises a basic compound.
    Description of Preferred Embodiments
    In the salt represented by formula (I) (hereinafter simply referred to as salt (I)), R21 represents a C1-C30 hydrocarbon group, which may be substituted, and at least one -0¾- the hydrocarbon group may be substituted with -CO- or -O-.
    The C1-C30 hydrocarbon group may be a linear or branched chain hydrocarbon group. The C1-C30 hydrocarbon group may have a monocyclic or polycyclic structure and may have one or more aromatic groups. The C1-C30 hydrocarbon group may have one or more carbon-carbon double bonds.
    It is preferred that the C1-C30 hydrocarbon moiety has at least one ring structure and, more preferably, it is preferred that the C1-C30 hydrocarbon moiety has a ring structure. Examples of cyclic structure include cyclopropane, cyclohexane, cyclooctane, norbornane, adamantane, cyclohexene, benzene, naphthalene, anthracene, phenanthrene and fluorene structures.
    Examples of the substituent include a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group, and the grouping is preferred. hydroxyl as a substituent.
    Examples of the C1-C6 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and n-hexyl. Examples of the C1-C6 alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy and n-hexyloxy. Examples of the C1-C4 perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl and nonafluorobutyl groups. Examples of the C1-C6 hydroxyalkyl group include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl and 6-hydroxyhexyl.
    It is preferred that Q 1 and Q 2 each independently represent fluorine atom or trifluoromethyl group, and it is most preferred that Q 1 and Q 2 are fluorine atoms.
    Specific examples of the anion portion of the salt (I) include the following anions:



    F-, "F F, p FF
    - o c '; / OxX', rH ~ - c> V- '° - ^ - ^ XN - A Xo ^ a
    O3S; CN 03S y ^ ^ 03S ^ CM
    O O O
    F--, .-- F F,, F
    o3s "Y" - o3s> Y0 "- ^^" '- ^ cn O b
    F. Jt F. P
    - ,, --ΚΥΟν / χ XH, - Λ _X., 0 .. Λ, 0.
    S Y - - 03 03 03 03 03 03 03 03 03 03 03 03 03 03 03 03 03 03 03 03 03 03 03 03 03 03 03 O O O O O O O O O O O 0 ° 3SX'-Or · 0 ··,
    F "F I I
    x "fv / fr l - 9 r ^ 1 - u3b | [vX- · ^ 3> <yvc * 'v -' ' yx Χ <.γΌ> io FT ^ * ί 1 i YC F.JF f ^ Yl F -F f " Ί _ 0
    - o3s> Y ^ ^ ch3 - o, s> Y0 ^ it ^ c2H> 'V ^ VrvTS
    0 0 ch3 f f
    ## EQU1 ## where: ## STR5 ##





    ^ N 91
    It is preferred that R is a group represented by the formula:
    wherein Z1 is a single bond or - (0¾) f-, f is an integer of 1 to 4, Y1 is -CH2-, -CO- or -CH (OH) -; the ring X1 represents a C3-C30 monocyclic or polycyclic hydrocarbon group, in which a hydrogen atom is substituted with a hydroxyl group at the Y1 position when Y1 represents -CH (OH) -, or in which two hydrogen atoms are substituted by = O at the Y1 position when Y1 represents -CO-, and at least one hydrogen atom of the C3-C30 monocyclic or polycyclic hydrocarbon group may be substituted by a C1-C6 alkyl group, a C1-C6 alkoxy group; C6, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group.
    Examples of the C1-C6 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and n-hexyl. Examples of the C1-C6 alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy and n-hexyloxy. Examples of the C1-C4 perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl and nonafluorobutyl groups. Examples of the C1-C6 hydroxyalkyl group include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl and 6-hydroxyhexyl.
    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, wherein a hydrogen atom may be substituted with a hydroxyl group or wherein two hydrogen atoms may be substituted with = 0, and wherein at least one hydrogen atom may be substituted with the C1-C6 alkyl group, the C1-C6 alkoxy group, the C1-C6 perfluoroalkyl group; C4, the C1-C6 hydroxyalkyl group, the hydroxyl group or the cyano group.
    Specific examples of the X1 ring include 2-oxocyclopentyl, 2-oxocyclohexyl, 3-oxo-cyclopentyl, 3-oxocyclohexyl, 4-oxocyclohexyl, 2-hydroxycyclopentyl, 2-hydroxycyclohexyl, 3-hydroxy-cyclopentyl, 3-hydroxycyclohexyl, 4 hydroxycyclohexyl, 4-oxo-2-adamantyl, 3-hydroxy-1-adamantyl, 4-hydroxy-1-adamantyl, 5-oxonorbornan-2-yl, 1,7,7-trimethyl-2-oxonorbornan-2-yl 3,6,6-trimethyl-2-oxo-bicyclo [3.1.1] -heptan-3-yl, 2-hydroxy-norbornan-3-yl, 1,7,7-trimethyl-2-hydroxynorbornan-3- yl, 3,6,6-trimethyl-2-hydroxy-bicyclo [3.1.1] heptan-3-yl,

    and the like, (in the above formulas, a continuous drawn, with one open end represents a bond extending from an adjacent group).
    As cycle X1, the adamantane ring is preferred. More preferably, the group represented by the following formulas (1), (m) or (n):
    as grouping R21. In the aforementioned formulas (1), (m) and (n), a continuous drawn with an open end represents a bond extending from an adjoining group.
    A + represents at least one organic cation chosen from a cation represented by formula (Ia):
    in which P1, P2 and P3 each independently represent a C1-C30 alkyl group, which may be substituted by at least one group chosen from a hydroxyl group, a C3-C12 cyclic hydrocarbon group and a C1-C6 alkoxy group; C12, or a C3-C30 cyclic hydrocarbon group which may be substituted with at least one group chosen from a hydroxyl group and a C1-C12 alkoxy group (which will be simply denoted hereinafter by cation (la)), a cation represented by the formula (Ib):
    in which P4 and P5 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group (which will be simply designated hereinafter by cation (Ib) ), and a cation represented by the formula (le):
    in which P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P and P each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a group C1-C12 alkoxy, B represents a sulfur or oxygen atom and m represents 0 or 1 (which will simply be designated hereinafter by cation (Ic)).
    Examples of the C1-C12 alkoxy group present in cations (Ia), (Ib) and (Ic) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy n-pentyloxy, n-hexyloxy, n-octyloxy and 2-ethylhexyloxy.
    Examples of the C3-C12 cyclic hydrocarbon group present in the cation (Ia) include cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, phenyl, 2-methylphenyl, 4-methylphenyl, 1-naphthyl and 2-naphthyl.
    Examples of the C 1 -C 30 alkyl group which may be substituted by at least one of the groups selected from the hydroxyl group, the C 3 -C 12 cyclic hydrocarbon group and the C 1 -C 12 alkoxy group present in the cation (the ) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl and benzyl groups.
    Examples of the C3-C30 cyclic hydrocarbon group which may be substituted by at least one group selected from the group consisting of hydroxyl group and the C1-C12 alkoxy group present in the cation (la) include cyclopentyl, cyclohexyl, 1-adamantyl groups. , 2-adamantyl, bicyclohexyl, phenyl, 2-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 4-n-hexylphenyl, , 4-n-octylphenyl, 1-naphthyl, 2-naphthyl, fluorenyl, 4-phenylphenyl, 4-hydroxyphenyl, 4-methoxyphenyl, 4-tert-butoxyphenyl, 4-n-hexyloxyphenyl.
    Examples of the C 1 -C 12 alkyl group present in cations (Ib) and (Ic) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n- pentyl, n-hexyl, n-octyl and 2-ethylhexyl.
    Examples of cation (Ia) include the following cations:

    Examples of cation (Ib) are the following cations:
    Examples of cation (Ic) are the following cations:


    As the organic cation represented by A +, cation (Ia) is preferred.
    As the organic cation represented by A +, the cations represented by the following formulas (Id), (Ic) and (If) are also preferred:
    in which P28, P29 and P30 each independently represent a C1-C20 alkyl group or a C3-C30 cyclic hydrocarbon group, with the exception of a phenyl group, and at least one hydrogen atom of the alkyl group C1-C20 may be substituted with a hydroxyl group, a C1-C12 alkoxy group or a C3-C12 cyclic hydrocarbon group, and at least one hydrogen atom of the C3-C30 cyclic hydrocarbon group may be substituted by a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, and P31, P32, P33, P34, P35 and P36 represent, each independently, a hydroxyl group, a C1-C12 alkyl group, a group C1-C12 alkoxy or a C3-C12 cyclic hydrocarbon group, and 1, k, j, i, h and g each independently represent an integer of 0 to 5.
    Examples of the C 1 -C 20 alkyl group include a methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, n-octyl, n-decyl and n-icosyl group.
    As examples of the C1-C12 alkoxy group and the C3-C30 cyclic hydrocarbon group, mention may be made of the same groups as those mentioned above.
    A cation represented by the formula (Ig) will be clearly preferred as the organic cation represented by A +:
    in which P41, P42 and P43 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, and it will be particularly preferred in terms of production, a cation represented by the formula (Ih):
    wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group.
    As examples of the alkyl group and the alkoxy group, mention may be made of the same groups as those mentioned above.
    As salt (I), the salt represented by the following formula is preferred:
    wherein A +, Q 1, Q 2, X 1, Y 1 and Z 1 have the same meanings as above, and the salt represented by the following formula is most preferred:
    in which P22, P23, P24, Q1, Q2, χ1, γ1 and Z1 have the same meanings as those mentioned above, and the salts represented by the following formulas are particularly preferred:
    in which P22, P23, P24, Q1 and Q2 have the same meanings as those indicated above.
    In the salt represented by formula (II) (hereinafter simply referred to as salt (II)), A '+ represents at least one organic cation chosen from the cations represented by the abovementioned formulas (la), ( Ib) and (the).
    As the organic cation represented by A '+, cation (I) is preferred. As the organic cation represented by A '+, the cations represented by the abovementioned formulas (Id), (Ic) or (If) are also preferred.
    As the organic cation represented by A '+, a cation represented by the above-mentioned formula (Ig) is particularly preferred, and a cation represented by the aforementioned formula (Ih) from a production point of view is particularly preferred.
    E represents at least one organic anion selected from an anion represented by the formula (II-1):
    and an anion represented by the formula (I1-2):
    The anion represented by the formula (11-1) being preferred.
    Q3 represents a C1-C10 perfluoroalkyl group and a C1-C8 perfluoroalkyl group is preferred. Examples of the C1-C10 perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, tetradecafluorohexyl, heptadecafluorooctyl, perfluoro-cyclohexyl and perfluoro-4-ethylcyclohexyl groups.
    Specific examples of the anion represented by formula (II-2) include the following:
    From the point of view of the roughness of the line edges, it is preferred that Q 3 represents the trifluoromethyl, pentafluoroethyl or nonafluorobutyl group.
    Q4 represents a C1-C10 perfluoroalkyl group and a C1-C8 perfluoroalkylalkyl group is preferred. As examples, the same may be mentioned as those described for Q3.
    Specific examples of the anion represented by formula (II-2) include the following:
    From the point of view of the roughness of the line edges, it is preferred that Q4 represents the trifluoromethyl or pentafluoroethyl group.
    Particularly preferred salt (II) is a salt represented by the following formula:
    The salt (I) can be produced by a process comprising reacting a salt of formula (LI):
    in which M represents Li, Na, K or Ag, and Q1, Q2 and R21 have the same meanings as those defined above (hereinafter simply referred to as salt (LI)), with a compound of formula (XI):
    wherein A + has the same meaning as defined above and G represents F, Cl, Br, I, BF4, AsF6, SbF6, PF6 or C104 (which will be simply referred to hereinafter as compound (XI)).
    The reaction of the salt (LI) and the compound (XI) is usually carried out in an inert solvent, such as acetonitrile, water, methanol and dichloromethane, at a temperature of about 0.degree. To 150.degree. preferably from 0 to 100 ° C, with stirring.
    The amount of the compound (XI) is usually from 0.5 to 2 moles per mole of the salt (LI). The salt (I) obtained by the process mentioned above can be isolated by recrystallization and can be purified by washing with water.
    The salt (LI) used for the production of the salt (I) can be produced by a process of esterifying an alcohol compound represented by the formula (LU):
    in which R21 has the same meaning as that defined above (which will be hereinafter simply denoted by alcohol compound (LU)), with a carboxylic acid represented by the formula (IX):
    in which M, Q1 and Q2 have the same meanings as those defined above (which will be referred to simply hereinafter as carboxylic acid (IX)).
    The esterification reaction of the alcohol compound (LU) and the carboxylic acid (IX) can generally be carried out by mixing the materials in an aprotic solvent, such as dichloroethane, toluene, ethylbenzene, monochlorobenzene, Acetonitrile and N, N-dimethylformamide at a temperature of 20 to 200 ° C, preferably 50 to 150 ° C. An acid catalyst or a dehydrating agent is usually added to the esterification reaction, 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 are 1,1'-carbonyldiimidazole and N, N'-dicyclohexylcarbodiimide.
    The esterification reaction may preferably be carried out with dehydration, which tends to reduce the reaction time. As an example of the dehydration process, mention may be made of the Dean and Stark process.
    The amount of carboxylic acid (IX) is usually 0.2 to 3 moles, preferably 0.5 to 2 moles per mole of the alcohol compound (LU).
    The amount of the acid catalyst may be a catalytic amount or an amount equivalent to the solvent and is usually in the range of 0.001 to 5 moles per mole of the alcohol compound (LU). The amount of desiccant is usually 0.2 to 5 moles, preferably 0.5 to 3 moles per mole of the alcohol compound (LU).
    The carboxylic acid (IX) can be produced, for example, by a process comprising reacting an ester compound represented by the following formula:
    wherein Q1 and Q2 have the same meanings as defined above and R30 represents a C1-C6 alkyl group, with a compound represented by the following formula:
    in which M has the same meaning as that defined above, in water.
    The salt (II) can be produced by a process consisting in reacting a salt of formula (II):
    in which M 'represents Li, Na, K or Ag, and E "has the same meaning as that defined above (hereinafter simply referred to as salt (III)), with a compound of formula (XII ):
    wherein A '+ has the same meaning as defined above and G' represents F, Cl, Br, I, BF4, AsF6, SbF6, PF6 or C104 (which will be referred to simply hereinafter as compound (XII )).
    The reaction of the salt (III) and the compound (XII) is usually carried out in an inert solvent, such as acetonitrile, water, methanol and dichloromethane, at a temperature of about 0.degree. To 150.degree. preferably from 0 to 100 ° C, with stirring.
    The amount of the compound (XII) is usually from 0.5 to 2 moles per mole of the salt (LUI). The salt (II) obtained by the above process can be isolated by recrystallization and can be purified by washing with water.
    The present resist composition comprises (A) salt (I), (B) salt (II) and (C) a resin which contains a structural unit having an acid-sensitive moiety and which is itself insoluble or poorly soluble in an aqueous alkaline solution, but which becomes soluble in an aqueous alkaline solution by the action of an acid.
    The salt (I) and the salt (II) are usually used as an acid generator and the acid generated by irradiation of the salt (I) and the salt (II) exerts a catalytic activity with respect to the groups sensitive to In the case of the resin acids, cleavages the acid-sensitive groups, so that the resin becomes soluble in an aqueous alkaline solution.
    In the present resist composition, the A + component of the salt (I) and the A '+ component of the salt (II) may be the same or different from each other. It is preferred that the component A + of the salt (I) and the component A '+ of the salt (II) are identical.
    The resin used for the present composition contains a structural unit having an acid-sensitive group and is itself insoluble or poorly soluble in an aqueous alkaline solution, but the acid-sensitive group is cleaved with an acid.
    In the present specification, the term "acid-sensitive group" refers to a group capable of being removed by the action of an acid.
    In the present specification, the "-COOR" group may be described as "a structure having a carboxylic acid ester" and may also be referred to in the abbreviated form of "ester group". More particularly, the "-COOC (CH 3) 3" group may be described as "a structure having a carboxylic acid tert-butyl ester" or may be referred to in the abbreviated form of "tert-butyl ester group".
    Examples of the acid-sensitive group include a structure having a carboxylic acid ester, such as an alkyl ester group, wherein a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, a alicyclic ester group, wherein a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, and a lactone ester group, wherein a carbon atom adjacent to the oxygen atom is a quaternary carbon. The term "quaternary carbon atom" refers to a "carbon atom joined to four substituents different from the hydrogen atom". As an example of an acid-sensitive group, there will be mentioned a group having a quaternary carbon atom connected to three carbon atoms and a group -OR ', in which R' represents an alkyl group.
    Examples of the acid-sensitive group include an alkyl ester group, wherein a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, such as the tert-butyl ester moiety; an ester group of the acetal type, such as the methoxymethyl ester, ethoxymethyl ester, 1-ethoxyethyl ester, 1-isobutoxyethyl ester, 1-isopropoxyethyl ester, 1-ethoxypropoxyester, 1- (2-methoxyethoxy ester) groups ethyl, 1- (2- (1-adamantyloxy) ethoxy] ethyl ester, 1- [2- (1-adamantane-carbonyloxy) ethoxy] ethyl ester, 1- (2-acetoxyethoxy) ethyl ester, tetrahydro-2-furyl and tetrahydro-2-pyranyl ester; an alicyclic ester group in which a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, such as an isobornyl ester group, a 1-alkyl-cycloalkyl ester, a 2-alkyl-2 ester adamantyl and 1- (1-adamantyl) -1-alkylalkyl ester. At least one hydrogen atom in the adamantyl group may be substituted with 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 norbornenecarboxylic acid ester, a structural unit derived from a tricyclodecenecarboxylic acid ester and a structural unit derived from a tetracyclodecenecarboxylic acid ester. Structural units derived from the acrylic acid ester and the methacrylic acid ester are preferred.
    The resin used for the present composition can be obtained by carrying out the polymerization reaction of one or more monomers having the acid-sensitive group and an olefinic double bond.
    Of the monomers, those having a bulky acid-sensitive group, such as an alicyclic ester group (for example, a 2-alkyl-2-adamantyl ester group and a 1- (1-adamantyl) ester group), are preferred. 1-alkylalkyl), because excellent resolution is obtained using the resin obtained in the present composition.
    Examples of monomers containing the acid-sensitive bulky group include 2-alkyl-2-adamantyl acrylate compounds, 2-alkyl-2-adamantyl methacrylate, 1- (1-adamantyl) -1-alkyl alkyl acrylate, methacrylate 1- (1-adamantyl) -1-alkylalkyl, 5-norbornene-2-carboxylic acid 2-alkyl-2-adamantyl, 5-norbornene-2-carboxylic acid 1- (1-adamantyl) -1-alkylalkyl, a- 2-alkyl-2-adamantyl chloroacrylate and 1- (1-adamantyl) -1-alkylalkyl α-chloroacrylate.
    This is particularly the case when using 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate or 2-alkyl-2-adamantyl α-chloroacrylate as monomer for the component in the present composition, which tends to provide a resist composition having excellent resolution. Typical examples thereof include 2-methyl-2-adamantyl acrylate compounds, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate , 2-n-butyl-2-adamantyl acrylate, 2-methyl-2-adamantyl α-chloroacrylate, and 2-ethyl-2-adamantyl α-chloroacrylate. When 2-ethyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-isopropyl-2-adamantyl acrylate or 2-methacrylate are used in particular, isopropyl-2-adamantyl for the present composition, which tends to provide a resist composition having excellent sensitivity and excellent heat resistance.
    In the present invention, two or more types of monomers having one or more groups dissociated by the action of the acid may be used together, if necessary.
    The 2-alkyl-2-adamantyl acrylate can be usually produced by reacting 2-alkyl-2-adamantanol or a metal salt thereof with an acrylic halide, and 2-alkyl-2-adamantyl methacrylate can be usually produced by reacting a 2-alkyl-2-adamantanol or a metal salt thereof with a methacrylic halide.
    The resin used for the present composition may also contain one or more other structural units derived from an acid-stable monomer, in addition to the structural units mentioned above, having the acid-sensitive moiety. Here, the term "structural unit derived from acid-stable monomer" refers to "a non-dissociated structural unit of an acid generated by salt (I) and salt (II)".
    Examples of this other structural unit derived from the acid-stable monomer include a structural unit derived from a monomer having a free carboxyl group, such as acrylic acid and methacrylic acid; a structural unit derived from an unsaturated aliphatic dicarboxylic anhydride, such as maleic anhydride and itaconic anhydride; a structural unit derived from 2-norbornene; a structural unit derived from acrylonitrile or methacrylonitrile; a structural unit derived from an alkyl acrylate or alkyl methacrylate, wherein a carbon atom adjacent to the oxygen atom is a secondary or tertiary carbon atom; a structural unit derived from 1-adamantyl acrylate or 1-adamantyl methacrylate; a structural unit derived from a styrene monomer, such as p-hydroxystyrene and n-hydroxystyrene; a structural unit derived from acryloyloxy-γ-butyrolactone or methacryloyloxy-γ-butyrolactone having a lactone ring which may be substituted with an alkyl group; and the like. Here, the 1-adamantyloxycarbonyl group is the acid stable group although the carbon atom adjacent to the oxygen atom is the quaternary carbon atom and the 1-adamantyloxy carbonyl group may be substituted by at least one hydroxyl group.
    Specific examples of the structural unit derived from the acid-stable monomer include a structural unit derived from 3-hydroxy-1-adamantyl acrylate; a structural unit derived from 3-hydroxy-1-adamantyl methacrylate; a structural unit derived from 3,5-dihydroxy-1-adamantyl acrylate; a structural unit derived from 3,5-dihydroxy-1-adamantyl methacrylate; a structural unit derived from α-acryloyloxy-γ-butyrolactone; a structural unit derived from α-methacryloyloxy-γ-butyrolactone; a structural unit derived from β-acryloyloxy-γ-butyrolactone; a structural unit derived from β-methacryloyloxy-γ-butyrolactone; a structural unit represented by formula (1):
    in which R 1 represents a hydrogen atom or a methyl group, R 3 represents a methyl group, a trifluoromethyl group or a halogen atom, e represents an integer from 0 to 3 and, when e represents 2 or 3, the radicals R3 may be the same or different from each other; a structural unit represented by formula (II):
    in which R2 represents a hydrogen atom or a methyl group, R4 represents a methyl group, a trifluoromethyl group or a halogen atom, d represents an integer from 0 to 3 and, when d represents 2 or 3, the radicals R4 may be the same or different from each other; a structural unit derived from p-hydroxystyrene; a structural unit derived from m-hydroxystyrene; a structural unit derived from an alicyclic compound having an olefinic double bond, such as a structural unit represented by the formula (3):
    in which R5 and R6 each independently represent a hydrogen atom, a C1-C3 alkyl group, a C1-C3 hydroxyalkyl group, a carboxyl group, a cyano group, a hydroxyl group or a -COOU group, in which wherein U represents an alcohol residue, or R5 and R6 may be bonded to each other so as to form a carboxylic anhydride residue represented by -C (= O) OC (= O) -; a structural unit derived from an unsaturated aliphatic dicarboxylic anhydride, such as a structural unit represented by formula (4):
    a structural unit represented by formula (5):
    and the like.
    In particular, the resin also containing at least one structural unit selected from the structural unit derived from p-hydroxybenzene, the structural unit derived from n-hydroxystyrene, the structural unit derived from the 3-hydroxy-1-acrylate adamantyl, the structural unit derived from 3-hydroxy-1-adamantyl methacrylate, the structural unit derived from 3,5-dihydroxy-1-adamantyl acrylate, the structural unit derived from 3,5-methacrylate. dihydroxy-1-adamantyl, the structural unit represented by formula (1) and the structural unit represented by formula (2), in addition to the structural unit having the acid-sensitive moiety, is preferable from the point of view the adhesion of the resist to a substrate and the resolution of the resist.
    3-Hydroxy-1-adamantyl acrylate, 3-hydroxy-1-adamantyl methacrylate, 3,5-dihydroxy-1-adamantyl acrylate and 3,5-dihydroxy-1 methacrylate can be produced. adamantyl, for example, by reacting the corresponding hydroxyadamantane with acrylic acid, methacrylic acid or its acidic halide, and they are also commercially available.
    In addition, acroyloxy-γ-butyrolactone and methacryloyloxy-γ-butyrolactone, having a lactone ring which may be substituted by the alkyl group, can be produced by reacting corresponding α- or β-bromo-γ-butyrolactones. with acrylic acid or methacrylic acid, or by reacting corresponding α- or β-hydroxy-γ-butyrolactones with the acrylic halide or methacrylic halide.
    As monomers intended to give the structural units represented by the formulas (1) and (2), particular mention will be made in particular of an alicyclic lactone acrylate and a methacrylate of alicyclic lactones, having the hydroxyl group described below and their mixtures . These esters can be produced, for example, by reacting the corresponding alicyclic lactone having the hydroxyl group with acrylic acid or methacrylic acid, and its production method is described, for example, in JP 2000- 26446 A.
    Examples of the acryloyloxy-y-butyrolactone and methacryloyloxy-y-butyrolactone having the lactone ring which may be substituted by the alkyl group include α-acryloyloxy-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, α-acryloyloxy-β, β-dimethyl-γ-butyrolactone, α-methacryloyloxy-β, β-dimethyl-γ-butyrolactone, α-acryloyloxy-α-methyl-γ-butyrolactone, α-methacryloyloxy-α-methyl γ-butyro-lactone, β-acryloyloxy-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone and β-methacryloyloxy-α-methyl-γ-butyrolactone.
    The resin containing a structural unit derived from 2-norbornene has a strong structure, since the alicyclic group is directly present on its main chain and gives a property of excellent resistance to dry etching. The structural unit derived from 2-norbornene can be introduced into the main chain by radical polymerization using, for example, an unsaturated aliphatic dicarboxylic anhydride, such as maleic anhydride and itaconic anhydride, together with the corresponding 2-norbornene. . The structural unit derived from 2-norbornene is formed by opening its double bond and can be represented by the above formula (3). The structural units derived from maleic anhydride and itaconic anhydride, which are the structural units derived from unsaturated aliphatic dicarboxylic anhydrides, are formed by opening their double bonds and can be represented by the above formula (4) and the formula (5), respectively.
    In R 5 and R 6, examples of the C 1 -C 3 alkyl group include the methyl group, the ethyl group and the n-propyl group, and examples of the C 1 -C 3 hydroxyalkyl group include the hydroxymethyl group and the 2-hydroxy group. ethyl.
    In R 5 and R 6, the -COO 2 group is an ester formed from the carboxyl group and the alcohol residue corresponding to U, for example, is a C 1 -C 8 alkyl group, a 2-oxooxolan-3-yl group. a 2-oxooxolane-4-yl group, etc., optionally substituted and, as a substituent on the C1-C8 alkyl group, there will be mentioned a hydroxyl group, an alicyclic hydrocarbon residue, etc.
    Specific examples of the monomer used to give the structural unit represented by the above formula (3) may include the compounds 2-norbornene, 2-hydroxy-5-norbornene, 5-norbornene-2-carboxylic acid, 5-norbornene-2 methyl carboxylate, 2-hydroxyethyl 5-norbornene-2-carboxylate, 5-norbornene-2-methanol and 5-norbornene-2,3-dicarboxylic anhydride.
    When the substituent U of the -COO 2 group is the acid-sensitive group, the structural unit represented by the formula (3) is a structural unit having the acid-sensitive group, even if it has the norbornane structure. Examples of monomers generating a structural unit having the acid-sensitive moiety include tert-butyl 5-norbornene-2-carboxylate compounds, 1-cyclohexyl-1-methylethyl 5-norbornene-2-carboxylate, 5-norbornene-2 1-methylcyclohexylcarboxylate, 2-methyl-2-adamantyl 5-norbornene-2-carboxylate, 2-ethyl-2-adamantyl 5-norbornene-2-carboxylate, 5-norbornene-2-carboxylate 1- (4-Hydroxycyclohexyl) -1-methylethyl 4-methylcyclohexyl) -1-methylethyl, 5-norbornene-2-carboxylate, 1-methyl-1- (4-oxocyclohexyl) ethyl 5-norbornene-2-carboxylate, 1- (1-adamantyl) -1-methylethyl 5-norbornene-2-carboxylate and the like.
    The resin used in the present composition preferably contains the structural unit (s) having the acid-sensitive group generally in the ratio of 10 to 80 mol% in all structural units of the resin, although the ratio varies depending the radiation type of the pattern-forming exposure, the type of acid-sensitive group, etc.
    When structural units derived, in particular, from 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate, 1- (1-adamantyl) -1-alkylalkyl acrylate or of 1 - (1-adamantyl) -1-alkylalkyl methacrylate, are used as the structural unit having the acid-sensitive group, it is advantageous for the resistance to dry etching of the resist that the ratio of the structural units is 15% in moles or more in all the structural units of the resin.
    When, in addition to the structural units having the acid-sensitive group, other structural units having the acid-stable group are contained in the resin, it is preferred that the sum of these structural units is in the range of 20 to 90%. in mole on the basis of all the structural units of the resin.
    In the case of a KrF lithography process, even if a structural unit derived from hydroxystyrene, in particular p-hydroxystyrene and m-hydroxystyrene, is used as one of the components of the resin, can obtain a resist composition having sufficient transparency. To obtain these resins, the corresponding acrylic or methacrylic ester monomer can be subjected to radical polymerization with acetoxystyrene and styrene, and then the acetoxy group of the structural unit derived from acetoxystyrene can be freed from acetyl using an acid.
    Specific examples of the structural unit derived from hydroxystyrene include the following structural units represented by formulas (6) and (7):
    The resin used for the present resist composition can be produced by carrying out the polymerization reaction of the corresponding monomer (s). The resin may also be produced by carrying out the oligomerization reaction of the corresponding monomer (s) and then proceeding to the 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 azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane) are exemplified as examples. -1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2'-azobis (2-methylpropionate) ) and 2,2'-azobis (2-hydroxymethylpropionitrile); an organic hydroperoxide, such as lauroyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate and 3,5,5-trimethylhexanoyl peroxide; and inorganic peroxide, such as potassium peroxodisulfate, ammonium peroxodisulfate and hydrogen peroxide. Among them, azo compounds are preferred and, more preferably, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) are preferred. 2,2'-azobis (2,4-dimethylvaleronitrile) and dimethyl-2,2'-azobis (2-methylpropionate), and 2,2'-azobisisobutyronitrile and 2,2 'are particularly preferred. azobis (2,4-diméthylvaléro nitrile).
    These radical initiators may be used alone or in the form of a mixture of two or more types of them. When using the mixture of two or more types of them, the mixing ratio is not particularly limited.
    The amount of radical initiator is preferably 1 to 20 mol% based on the molar amount of all monomers or oligomers.
    The polymerization temperature is usually from 0 to 150 ° C, preferably from 40 to 100 ° C.
    The polymerization reaction is usually carried out in the presence of a solvent and it is preferred to use a solvent which is sufficient to dissolve the monomer, radical initiator and the resulting resin.
    Examples that may be mentioned are 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 glycol ether ester solvent, such as propylene glycol monomethyl ether acetate; and an acyclic ester solvent, such as ethyl lactate. These solvents can be used alone or as a mixture.
    The amount of solvent is not limited and conveniently it is preferred that it be 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 monomers, it is preferred to use them in excess amount because of their tendency not to readily polymerize.
    At the end of the polymerization reaction, the produced resin can be isolated, for example, by adding a solvent, in which the present resin is insoluble or poorly soluble, to the resulting reaction mixture and filtering the precipitated resin. If necessary, the isolated resin can be purified, for example, by washing with a suitable solvent.
    The present resist composition preferably comprises 80 to 99.9% by weight of the resin component and 0.1 to 20% by weight of the sum of salt (I) and salt (II) on the basis of total amount of the resin component, salt (I) and salt (II).
    The quantitative ratio of salt (I) and salt (II) is usually from 9/1 to 1/9, preferably from 9/1 to 3/7, more preferably from 9/1 to 4/6.
    In the present resist composition, performance degradation due to acid inactivation that occurs due to a delay following exposure, can be reduced by adding an organic base compound, particularly an organic base compound containing nitrogen as a neutralizing agent.
    As specific examples of the nitrogen-containing organic base compound, there may be mentioned an amine compound represented by the following formulas:
    in which R11 and R12 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and the alkyl, cycloalkyl and aryl groups may be substituted by at least one group chosen from a hydroxyl group, an amino group which may be substituted with a C1-C4 alkyl group and a C1-C6 alkoxy group which may be substituted by a C1-C6 alkoxy group.
    R13 and R14 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, and the alkyl, cycloalkyl, aryl and alkoxy groups may be substituted by at least one group chosen from a hydroxyl group; , an amino group, which may be substituted by a C1-C4 alkyl group and a C1-C6 alkoxy or R13 and R14 group, are joined to each other together with the carbon atoms to which they are attached. to form an aromatic ring, R 15 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or a nitro group, and the alkyl, cycloalkyl, aryl and alkoxy groups may be substituted by at least one a group selected from a hydroxyl group, an amino group which may be substituted by a C1-C4 alkyl group or a C1-C6 alkoxy group, R16 represents a n alkyl or cycloalkyl group and the alkyl and cycloalkyl groups may be substituted with at least one group chosen from a hydroxyl group, an amino group which may be substituted with a C1-C4 alkyl group and a C1-C6 alkoxy group, and W represents -CO-, -NH-, -S-, -SS-, an alkylene group of which at least one methylene unit may be replaced by -O-, or an alkenylene group of which at least one methylene unit may be replaced by 0-, and a quaternary ammonium hydroxide represented by the following formula:
    in which R 17, R 18, R 19 and R 20 independently represent an alkyl group, a cycloalkyl group or an aryl group and the alkyl, cycloalkyl and aryl groups may be substituted with at least one group chosen from a hydroxyl group, an amino group which may be substituted by a C1-C4 alkyl group and a C1-C6 alkoxy group.
    The alkyl group of the radicals R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 preferably contains about 1 to 10 carbon atoms, more preferably about 1 to 6 carbon atoms.
    Examples of the amino group which may be substituted by the C1-C4 alkyl group include amino, methylamino, ethylamino, n-butylamino, dimethylamino or diethylamino groups. Examples of the C1-C6 alkoxy group which may be substituted by a 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 C1-C4 alkyl group, and a C1-C6 alkoxy group which may be substituted by a C1-C6 alkoxy group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, 2 - (2-methoxyethoxy) ethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-aminoethyl, 4-aminobutyl and 6-aminohexyl.
    The cycloalkyl group found in the radicals R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 preferably contains about 5 to 10 carbon atoms. As 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 present in the radicals R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19 and R 20 preferably contains about 6 to 10 carbon atoms. Specific examples of the aryl group which may be substituted by at least one group selected from a hydroxyl group, an amino group which may be substituted by a C 1 -C 4 alkyl group, and a C 1 -C 6 alkoxy group include the phenyl group. and the naphthyl group.
    The alkoxy group found in the radicals R13, R14 and R15 preferably contains about 1 to 6 carbon atoms and specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and tert-butoxy groups. n-pentyloxy and n-hexyloxy.
    The alkylene and alkenylene groups of the substituent W contain, preferably, 2 to 6 carbon atoms. Specific examples of the alkylene group include ethylene, trimethylene, tetramethylene, methylenedioxy and ethylene-1,2-dioxy groups, and specific examples of the alkenylene group include ethene-1,2-diyl groups, 1-propene-1, 3-diyl and 2-butene-1,4-diyl.
    Specific examples of the amine compound include the compounds n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, aniline, 2-methyl-aniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline , 1-naphthylamine, 2-naphthylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,41-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino 3,3'-diethyldiphenylmethane, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, N-methylaniline, piperidine, diphenylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine , methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyl-diheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, thyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, N, N-dimethylaniline, 2,6-diisopropylaniline, imidazole, benzimidazole, pyridine, 4 methylpyridine, 4-methylimidazole, bipyridine, 2,2'-dipyridylamine, di-2-pyridylketone, 1,2-di (2-pyridyl) ethane, 1,1-di (4-pyridyl) ethane, 1,3-di (4-pyridyl) propane, 1,2-bis (2-pyridyl) ethylene, 1,2-bis (4-pyridyl) ethylene, 1,2-bis (4-pyridyloxy) ethane, 4, 4'-dipyridylsulfide, 4,4'-dipyridyl disulfide, 1,2-bis (4-pyridyl) ethylene, 2,2'-dipicolylamine and 3,3'-dipicolylamine.
    Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide compounds, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, (3-trifluoromethylphenyl) trimethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (what is referred to as "choline")
    A hindered amine compound having a piperidine backbone as described in JP 11-52575 A1 can also be used as a neutralizing agent.
    Concerning the formation of the units having a better resolution, it is preferred to use quaternary ammonium hydroxide as a neutralizing agent.
    When the basic compound is used as a neutralizing agent, the present resist composition preferably comprises 0.01 to 1% by weight of the basic compound based on the total amount of the resin component, salt (I) and salt (II).
    The present resist composition may contain, if necessary, a small amount of various additives, such as a sensitizer, a dissolution inhibitor, other polymers, a surfactant, a stabilizer and a dye, as long as the of the present invention is not blocked.
    The present resist composition is usually in the form of a liquid resist composition, wherein the aforementioned ingredients are dissolved in a solvent, and the liquid resist composition is applied to a substrate, such as a silicon wafer, by a conventional method, such as the centrifugal coating method. The solvent used is sufficient to dissolve the aforementioned ingredients, is characterized by an adequate drying rate and generates a uniform and smooth coating after evaporation of the solvent. The solvents generally used in the art can be used here.
    Examples of the solvent include a glycol ether ester, such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; an acyclic ester, such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; a ketone, such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; and a cyclic ester, such as γ-butyro-lactone. These solvents can be used alone or two or more can be mixed for use.
    A resist film applied to the substrate, then dried, is subjected to pattern-forming exposure, then heat-treated to facilitate an unlocking reaction, and then developed with an alkaline developer. The alkaline developer used may be any of the various aqueous alkaline solutions used in the art. In general, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly referred to as "choline") will often be used.
    It is understood that the embodiments described here are examples in all aspects and are not restrictive. It is believed that the scope of the present invention is not determined by the foregoing descriptions, but by the appended claims, and that the invention includes all variants with equivalent meanings and ranges equivalent to those of the claims.
    The present invention will be specifically described by examples, which are not intended to limit the scope of the present invention. The symbols and terms "%" and "part (s)" used to represent the content of any component and the amount of any material used in the following Examples and Comparative Examples are on a weight basis unless otherwise stated. The weight average molecular weight of any material used in the following examples is a value obtained by gel permeation chromatography [type HLC-8120GPC, Column (three columns): TSK Multipore HXL-M gel, solvent: tetrahydrofuran, manufactured by TOSOH CORPORATION] using styrene as a standard standard material. The structures of the compounds are determined by NMR (type GX-270 or type EX-270, manufactured by JEOL LTD) and by mass spectrometry (liquid chromatography type 1100, manufactured by AGILENT TECHNOLOGIES LTD., Mass spectrometry: type LC / MSD or LC / MSD TOE, manufactured by AGILENT TECHNOLOGIES LTD.).
    EXAMPLE OF SALT SYNTHESIS 1
    (1) 230 parts of a 30% aqueous solution of sodium hydroxide are added to a mixture of 100 parts of methyl difluoro (fluorosulfonyl) acetate and 250 parts of deionized water in an ice bath. The resulting mixture is heated to reflux at 100 ° C for 3 hours. After cooling, the cooled mixture is neutralized with 88 parts of concentrated hydrochloric acid and the resulting solution is concentrated to obtain 164.8 parts of sodium salt of difluorosulfoacetic acid (containing an inorganic salt, purity: 62.8%) .
    (2) 5.0 parts of sodium difluorosulfoacetate (purity: 62.8%), 2.6 parts of 4-oxo-1-adamantanol and 100 parts of ethylbenzene are mixed and 0.8 parts of concentrated sulfuric acid. The resulting mixture is refluxed for 30 hours. After cooling, the mixture is filtered to give solids which are washed with tert-butyl methyl ether to give 5.5 parts of the salt represented by the above formula (a). Its purity is 35.6%, which has been calculated by means of the 1 H-NMR analysis result. 1H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): d (ppm) 1.84 (d, 2H, J = 13.0 Hz), 2.00 (d, 2H, J = 11.9 Hz), 2, 29 at 2.32 (m, 7H), 2.54 (s, 2H).
    (3) To 5.4 parts of the salt represented by the formula (a) obtained according to (2) (purity: 35.6%) is added a mixed solvent consisting of 16 parts of acetonitrile and 16 parts of deionized water. A solution prepared by mixing 1.7 parts of triphenylsulfonium chloride, 5 parts of acetonitrile and 5 parts of deionized water is added to the resulting mixture. After a stirring step of 15 hours, the mixture obtained is concentrated and extracted with 142 parts of chloroform. The organic layer obtained is washed with deionized water and concentrated. The resulting concentrate is washed with 24 parts of tert-butyl methyl ether and the solvent is removed by decantation to give 1.7 parts of the salt represented by the above formula (b) as a white solid, which is denotes by Bl.
    1H-NMR (dimethylsulfoxide-d6, internal standard: tetramethylsilane): d (ppm) 1.83 (d, 2H, J = 12.7 Hz), 2.00 (d, 2H, J = 12.0 Hz), 2, 29 at 2.32 (m, 7H), 2.53 (s, 2H), 7.75 to 7.91 (m, 15H).
    MS (ESI (+) spectrum): M + 263.2 (C18H15S + = 263.09) MS (ESI (-) spectrum): M-323.0 (C12H13F2O6S- = 323.04).
    EXAMPLE OF SALT SYNTHESIS 2
    (1) 230 parts of a 30% aqueous sodium hydroxide solution are added to a mixture of 100 parts of methyl difluoro (fluorosulfonyl) acetate and 150 parts of deionized water in an ice bath. The resulting mixture is heated to reflux at 100 ° C for 3 hours. After cooling, the cooled mixture is neutralized with 88 parts of concentrated hydrochloric acid and the resulting solution is concentrated to give 164.4 parts of sodium salt of difluorosulfoacetic acid (containing an inorganic salt, purity: 62.7%) .
    (2) 1.9 parts of sodium salt of difluorosulfoacetic acid (purity: 62.7%), 9.5 parts of N, N-dimethylformamide and 1.0 part of 1,1'-carbonyldiimidazole are mixed together and the resulting solution is stirred for 2 hours. The solution is added to the solution prepared by mixing 1.1 parts of the compound represented by the above formula (c), 5.5 parts of N, N-dimethylformamide and 0.2 part of sodium hydride, all with stirring for 2 hours. The resulting solution is stirred for 15 hours to obtain the salt-containing solution represented by the above formula (d).
    (3) 17.2 parts of chloroform and 2.9 parts of an aqueous solution of triphenylsulfonium chloride are added to the solution containing the salt represented by the above formula (d). The resulting mixture is stirred for 15 hours and then separated into an organic layer and an aqueous layer. The aqueous layer is extracted with 6.5 parts of chloroform to obtain a chloroform layer. The chloroform layer and the organic layer are mixed and washed with deionized water. The organic layer obtained is concentrated. The resulting residue is mixed with 5.0 parts of tert-butyl methyl ether and the resulting mixture is filtered to give 0.2 part of the salt represented by the above formula (e) as a white solid, which we denote by B2. 1H-NMR (dimethylsulfoxide-internal standard tetramethylsilane): d (ppm) 1.38-1.51 (m, 12H), 2.07 (s, 2H), 3.85 (s, 2H), 4 , 41 (s, 1H), 7.75 to 7.89 (m, 15H) MS (ESI (+) spectrum): M + 263, 07 (C18H15S + = 263, 09) MS (ESI (-) spectrum): M - 339, 10 (C13H17F206S · = 339, 07) EXAMPLE OF SYNTHESIS OF RESIN 1
    The monomers used in this resin synthesis example are the following monomers M1, M2 and M3:
    The monomer M1, the monomer M2 and the monomer M3 are dissolved in an amount of methyl isobyl ketone corresponding to twice the amount of all the monomers to be used (molar ratio of the monomers; monomer M1: monomer M2: monomer M3 = 5: 2.5 : 2.5). 2,2'-Azobisisobutyronitrile was added to the solution as an initiator in a ratio of 2 mol% to the molar amount of all the monomers and the resulting mixture was heated at 80 ° C for about 8 hours. The reaction solution is poured into a large amount of heptane to cause precipitation. The precipitate is isolated and washed twice with a large amount of heptane for purification. As a result, a copolymer having a weight average molecular weight of about 9200 is obtained. This copolymer has the following structural units. It is designated Al resin:
    EXAMPLE OF SYNTHESIS OF RESIN 2
    The monomers used in this resin synthesis example are the following monomers M1, M2 and M4:
    The monomer M1, the monomer M2 and the monomer M4 are dissolved in an amount of 1,4-dioxane corresponding to 1.28 times the amount of all the monomers to be used (molar ratio of the monomers: monomer Monomonomer M2: monomer M4 = 50 : 25: 25). 2,2'-Azobisisobutyronitrile is added to the solution as an initiator in a ratio of 3 mol% based on the molar amount of all monomers. The solution obtained is added to a quantity of 1,4-dioxane corresponding to 0.72 times the amount of all the monomers to be used at 88 ° C. for 2 hours. The resulting mixture is stirred at the same temperature for 5 hours. The reaction solution is cooled and then poured into a large amount of a mixed solvent of methanol and water to precipitate. The precipitate is isolated and washed twice with a large amount of methanol for purification. As a result, a copolymer having a weight average molecular weight of about 8500 is obtained. This copolymer has the following structural units. It is designated resin A2:
    EXAMPLES 1 TO 4 AND COMPARATIVE EXAMPLES 1 TO 3 Acid Generator Acid Generator B1:
    B2 acid generator:
    Cl acid generator:
    C2 acid generator:
    C3 acid generator:
    Resin Resins Al and A2
    Neutralizing agent Q1: 2,6-diisopropylaniline
    Solvent Y1: Propylene Monomethyl Ether Acetate-145 parts Glycol 2-Heptanone 20.0 parts
    Monomethyl ether propylene glycol 20.0 parts γ-Butyrolactone 3.5 parts
    The following components are mixed and dissolved, then filtered on a fluororesin filter having a pore diameter of 0.2 μm, to prepare the resist liquid.
    Resin (typical type and quantity are described in Table I) Acid generator (nature and quantity are described in Table I)
    Neutralizing agent (nature and quantity are described in Table I)
    Solvent (nature is described in Table I)
    Silicon wafers are each coated with material "ARC-29A", which is an organic antireflective coating composition available from Nissan Chemical Industries, Ltd., and is then fired under the following conditions: 205 ° C , 60 seconds, to form an organic anti-reflective coating with a thickness of 780 Å. Each of the resist liquids prepared in the manner mentioned above is applied by the centrifugal coating method to the anti-reflective coating, so that the resulting film thickness reaches 0.15 μm after drying. The silicon wafers thus coated with the respective resist liquids are each precooked on a direct hot plate at a temperature indicated in column "PB" of Table I for 60 seconds. Using an ArF stepper system ("FPA-5000AS3" manufactured by CANON INC., NA = 0.75, 2/3 annular), each slice thus formed with the respective resist film is subjected to exposure according to a pattern of lines and spaces, the amount of exposure being gradually changed.
    After exposure, each slice is subjected to post-exposure firing on a plate heated to a temperature shown in the "PEB" column of Table I for 60 seconds, followed by development by a 60 second attack with 2.38% by weight aqueous solution of tetramethylammonium hydroxide.
    Each of the dark field patterns developed on the organic antireflective coating substrate after the development phase is examined under a scanning electron microscope, the results of the observation being shown in Table II. The term "dark field pattern" as used herein refers to a pattern obtained by exposing and developing through a reticle comprising a chromium-based surface (light-protecting portion) and linear glass layers (light transmitting portion) formed in the chromium surface and aligned with each other. As a result, the dark field pattern is such that after the exposure and development steps, the resist layer surrounding the pattern of lines and spaces remains on the substrate.
    Effective Sensitivity (ES): It is expressed as the amount of exposure, such as the line pattern and the space pattern becomes 1: 1, after exposure through a pattern mask of lines and spaces of 100 nm and have proceeded to the development.
    Line Edge Roughness (LER): Each of a wall surface of a pattern developed on the organic antireflective coating substrate after the development step, was observed with a scanning electron microscope. When the surface of the wall has the same appearance as that of Comparative Example 1, its evaluation is marked by the symbol "Δ", when the surface of the wall is smoother than that of Comparative Example 1, its evaluation. is marked with the symbol "O" and when the surface of the wall is rougher than that of Comparative Example 1, its evaluation is marked by the symbol "X".
    As is apparent from Table II, the resist compositions of the examples, which are in accordance with the present invention, provide a good resist configuration for resolution and smoothing of the wall surface.
    The present composition provides a good resistance pattern in terms of resolution and roughness of line edges and is particularly suitable for ArF excimer laser lithography, KrF excimer laser lithography and ArF dip lithography.
    权利要求:
    Claims (20)
    [1]
    A chemically amplified resist composition comprising: (A) A salt represented by formula (I):

    [2]
    2. A chemically amplified resist composition according to claim 1, wherein Q1 and Q2 each independently represent a fluorine atom or a trifluoromethyl group.
    [3]
    3. Chemically amplified resist composition according to claim 1, wherein Q1 and Q2 are fluorine atoms.
    [4]
    4. A chemically amplified resist composition according to claim 1, wherein Q3 represents a trifluoromethyl group, a pentafluoroethyl group or a nonafluorobutyl group.
    [5]
    The chemically amplified resist composition of claim 1, wherein Q4 is a trifluoromethyl group or a pentafluoroethyl group.
    [6]
    The chemically amplified resist composition of claim 1, wherein E - is an anion represented by the formula (11-1).
    [7]
    A chemically amplified resist composition according to claim 1, wherein A + and a '+ are the same or different and each independently represents a cation represented by the formula (Id), (Ic) or (If):

    [8]
    The chemically amplified resist composition of claim 1 wherein A + and A> + are the same or different and each independently represents a cation represented by the formula (Ig):

    [9]
    The chemically amplified resist composition of claim 1, wherein A + and A + are the same or different and each independently represents a cation represented by the formula (Ih):

    [10]
    The chemically amplified resist composition of claim 1, wherein R21 is a group represented by the formula:

    [11]
    11. Chemically amplified resist composition according to claim 10, wherein the group represented by the formula:

    [12]
    Chemically amplified resist composition according to claim 10, wherein A + is a cation represented by the formula (Ih):

    [13]
    13. Chemically amplified resist composition according to claim 12, wherein the group represented by the formula:

    [14]
    The chemically amplified resist composition of claim 1, wherein A> + is a cation represented by the formula (Ih):

    [15]
    The chemically amplified resist composition according to claim 1, wherein A + and a '+ are the same or different and each independently represents a cation represented by the formula (Ih):

    [16]
    The chemically amplified resist composition according to claim 1, wherein the quantitative ratio of the salt represented by the formula (I) to the salt represented by the formula (II) is from 9/1 to 1/9.
    [17]
    17. Chemically amplified resist composition according to claim 1, wherein the resin contains a structural unit derived from a monomer having a bulky and acid-sensitive moiety.
    [18]
    The chemically amplified resist composition of claim 17, wherein the bulky and acid-sensitive moiety is a 2-alkyl-2-adamantyl ester moiety or a 1- (1-adamantyl) -1-alkyl alkyl ester moiety.
    [19]
    19. Chemically amplified resist composition according to claim 18, wherein the monomer having a bulky and acid-sensitive moiety is a 2-alkyl-2-adamantyl acrylate compound, 2-alkyl-2-adamantyl methacrylate, acrylate of 1 - (1-adamantyl) -1-alkylalkyl, 2-alkyl-2-adamantyl 1- (1-adamantyl) -1-alkylalkyl, 5-norbornene-2-carboxylate methacrylate, 5-norbornene-2-carboxylate 1 - (1-adamantyl) -1-alkylalkyl, 2-alkyl-2-adamantyl α-chloroacrylate or 1- (1-adamantyl) -1-alkylalkyl α-chloroacrylate.
    [20]
    The chemically amplified resist composition of claim 1, wherein the resist composition further comprises a basic compound. f
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    同族专利:
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    法律状态:
    优先权:
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    JP2007074369A|JP5012122B2|2007-03-22|2007-03-22|Chemically amplified resist composition|
    JP2007074369|2007-03-22|
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