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    • 专利摘要:
    The present invention provides a salt represented by the formula (I): wherein Q1 and Q2 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group T represents a methylene group or a carbonyl group, R represents a substituted adamantyl group by at least one group selected from the group consisting of C1-C4 alkyl, C1-C4 alkoxy, hydroxyl, hydroxymethyl, cyano and oxo, and A + is a counter-ion organic. The present invention further provides a chemically amplified positive resist composition comprising the salt represented by the above-mentioned formula (I).
    公开号:BE1018461A3
    申请号:E2008/0411
    申请日:2008-07-23
    公开日:2010-12-07
    发明作者:Ichiki Takemoto
    申请人:Sumitomo Chemical Co；
    IPC主号:
    专利说明:

    "SALT SUITABLE FOR AN ACID GENERATOR AND CHEMICAL AMPLIFIED POSITIVE RESERVE COMPOSITION CONTAINING THE SAME"
    FIELD OF THE INVENTION
    The present invention relates to a salt suitable for an acid generator used for a chemically amplified resist composition used in the fine processing of semiconductors, and to a chemically amplified positive resist composition containing it.
    BACKGROUND OF THE INVENTION
    A chemical amplification positive resin composition used for microfabrication of semiconductors using a lithographic process contains an acid generator comprising a compound that generates an acid by irradiation.
    In semiconductor microfabrication, it is desirable to form patterns having excellent patterning, and a chemical amplification resist composition is expected to provide such patterns.
    JP 2004-4561A discloses a chemical amplification resin composition containing the salt represented by the following formula:
    as an acid generator.
    SUMMARY OF THE INVENTION
    The present invention provides a salt suitable for an acid generator capable of providing chemically amplifying resist compositions having patterns having excellent shape, and a chemical amplification resist composition containing the salt.
    The present invention relates to the following: <1> A salt represented by formula (I):
    wherein Q1 and Q2 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group, T represents a methylene group or a carbonyl group, R represents an adamantyl group substituted with at least one group selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxyl, hydroxymethyl, cyano and oxo, and A + is an organic counterion, (2) The following salt <1>, in wherein Q1 and Q2 each independently represent a fluorine atom or a trifluoromethyl group, <3> The following salt <1>, wherein Q1 and Q2 represent fluorine atoms, <4> the following salt <1>, <2> or <3>, wherein the organic counterion is at least one cation selected from the group consisting of a cation represented by the formula (IIa):
    wherein P1, P2 and P3 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 (IIb):
    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 (IIc):
    wherein P6 and P7 are each independently C1-C12 alkyl or C3-C12 cycloalkyl, or P6 and P7 are linked to form a divalent C3-C12 hydrocarbon group which forms a ring with the adjacent S + and at least one -CH2- in the divalent acyclic hydrocarbon group may be substituted with -CO-, -O- or -S-, P6 represents a hydrogen atom, P9 represents a C1-C12 alkyl group, a group C3-C12 cycloalkyl 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- in the divalent acyclic hydrocarbon group may be substituted with -CO-, -O- or -S-, and a cation represented by the formula (IId):
    wherein P10, P1 ', P12, P'3, P14, P15, P's, P17, P18, P ", P20 and P21 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, B represents a sulfur or oxygen atom and k is 0 or 1, 5 <5> The following salt <1>, <2> or <3>, wherein the counter-ion organic is a cation represented by the formula (IIa), <6> The following salt <5>, wherein the cation represented by the formula (IIa) is a cation represented by the formula (IIc):
    Wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group; The salt according to any one of <1> to <6>, wherein R represents a hydroxyl or hydroxyl-substituted adamantyl group. The <8> salt of any one of <7> wherein the organic counterion is a cation represented by the formula (IIc):
    wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group. A chemical amplification positive reserve composition comprising a salt represented by the formula (I):
    wherein Q1 and Q2 each individually represent a fluorine atom or a C1-C6 perfluoroalkyl group, T represents a methylene group or a carbonyl group, R represents an adamantyl group substituted with at least one group selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxyl, hydroxymethyl, cyano and oxo, and A + is an organic counterion, and a resin containing a structural unit having a group acidolabile 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, <10> The chemical amplification positive reserve composition of <9>, in which Q1 and Q2 each independently represent a fluorine atom or a trifluoromethyl group, <11> The chemical amplification positive reserve composition of <9>, wherein Q1 and Q2 are fluorine atoms, <12> The chemically amplified positive reserve composition according to any one of <9> to <11>, wherein the resin contains a structural unit derived from a monomer having a group voluminous and acid-labile, <13> The chemically amplified positive reserve composition according to <12>, wherein the bulky and acidolabile group is a 2-alkyl-2-adamantyl ester or a 1- (1-adamantyl) ester group 1-alkylalkyl, <14> The chemical amplification positive reserve composition according to <12>, wherein the monomer having a bulky and acidolabile group is 2-alkyl-2-adamantyl acrylate, 2- (methacrylate) alkyl-2-adamantyl, 1- (1-adamantyl) -1-alkylalkyl acrylate, 1- (1-adamantyl) -1-alkylalkyl methacrylate, 2-alkyl-2-adamantyl 2-carboxylate 5-norbornene, 1- (1-adamantyl) -1-alkylalkyl-5-norbornene carboxylate, 2-alkyl-2-adamino-2-chloroacrylate tyl or 1- (1-adamantyl-1-alkylalkyl) -acryloacrylate, <15> The chemically amplified positive reserve composition according to <12>, wherein the monomer having a bulky and acidolabile group is acrylate. 2-alkyl-2-adamantyl, 2-alkyl-2-adamantyl methacrylate, 1- (1) adamantyl) -1-alkylalkyl acrylate and 1- (1-adamantyl) -1-alkylalkyl methacrylate <16> The chemically amplified positive reserve composition according to <12>, wherein the monomer having a bulky and acidolabile group is 2-alkyl-2-adamantyl acrylate and 2-alkyl-2-methacrylate adamantyl, <17> The chemically amplified positive reserve composition according to any one of <9> to <16>, wherein the chemical amplification positive reserve composition further comprises a basic compound.
    DESCRIPTION OF PREFERRED EMBODIMENTS
    The present invention provides a salt represented by formula (I):
    wherein Q 1 and Q 2 each independently represent a fluorine atom or a C 1 -C 6 perfluoroalkyl group T represents a methylene group or a carbonyl group, R represents an adamantyl group substituted by at least one group selected from the group consisting of an alkyl group C1 to C4) a C1 to C4 alkoxy group, a hydroxyl group, a hydroxymethyl group, a cyano group and an oxo group, and A + represents an organic counterion (hereinafter simply referred to as salt (I)).
    Examples of the C1-C6 perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, undecafluoropentyl and tridecafluoroheptyl, and the trifluoromethyl group is preferable.
    Q1 and Q2 preferably independently represent fluorine atom or trifluoromethyl group. More preferably, Q1 and Q2 are fluorine atoms.
    Examples of the C 1 -C 4 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Examples of the C1-C4 alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group and tert-butoxy group.
    R is preferably an adamantyl group substituted with a hydroxyl group or an oxo group.
    Examples of the anionic part of salt (I) include the following:

    Among them, the following anionic parts are preferable:

    The following anionic parts are more preferable:
    In the formula (I), A + represents an organic counterion. Examples of the organic counterion include a cation represented by the formula (IIa):
    wherein P1, P2 and P3 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 (Mb):
    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 (IIc):
    wherein P6 and P7 are each independently C1-C12 alkyl or C3-C12 cycloalkyl, 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- in the divalent acyclic hydrocarbon group may be substituted with -CO-, -O- or -S-, P8 is hydrogen, P9 is C1-C12 alkyl, a group C3-C12 cycloalkyl 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- in the divalent acyclic hydrocarbon group may be substituted with -CO-, -O- or -S-, and a cation is represented by the formula (IId):
    wherein P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20 and P21 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or an alkoxy group in C 1 to C 12, B is a sulfur or oxygen atom and k is 0 or 1.
    Examples of the C1-C12 alkyl group in the formulas (IIa), (IIb), (IIc) and (IId) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-propyl group, Butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl.
    Examples of the C1-C12 alkoxy group in the formulas (IIa), (IIb), (IIc) and (IId) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a n butoxy, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group and 2-ethylhexyloxy group.
    Examples of the C3-C12 cycloalkyl group in the formula (IIc) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a cyclodecyl group.
    Examples of the divalent C 3 to C 12 acyclic hydrocarbon group formed by the bonding of P 6 and P 7 in the formula (II) include a trimethylene group, a tetramethylene group and a pentamethylene group. Examples of the cyclic group formed with the adjacent S + and the divalent acyclic hydrocarbon group include a tetramethylenesulphonio group, a pentamethylenesulphonio group and an oxybisthylenesulphonio group.
    Examples of the aromatic group in the formula (Ile) include a phenyl group, a tolyl group, a xylyl group and a naphthyl group. Examples of the divalent acyclic hydrocarbon group formed by the bonding of P8 and P9 in the formula (IIc) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group and a pentamethylene group, and examples of the 2-oxocycloalkyl group. formed with the -CHCO-adjacent and the divalent acyclic hydrocarbon group include a 2-oxocyclopentyl group and a 2-oxocyclohexyl group.
    The cation represented by formula (IIa) or (IIc) is preferable, and the cation represented by formula (IIa) is more preferable.
    Examples of the cation represented by formula (IIa) include the following:

    Examples represented by formula (IIb) include the following:
    Examples of the cation represented by the formula (IIc) include the following:

    Examples of the cation represented by the formula (Md) include the following:


    As the organic counterion, a cation represented by the formula (IIc) is preferred:
    wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group.
    Examples of the C1-C4 alkyl group in the formula (IIc) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and a tert-butyl group.
    Examples of the cation represented by the formula (IIc) include the following:
    The salts represented by the formulas (IIa), (IIb), (IIIc) and (IIId) hereinafter are preferred as salt (I) to provide chemically amplified resist compositions giving excellently shaped units. pattern.
    The salts represented by the formulas (Ilia) and (IIIb) are more preferable as salt (I).
    Examples of the salt production process (I) include a process comprising reacting a salt represented by the formula (V):
    wherein Q1, Q2, T and R are as defined above, and M is Li, Na or K (and hereinafter simply referred to as salt (V)), with a compound represented by the formula (XI): A + Z (XI) wherein A + is as defined above and Z is F; Cl, Br, I, BF 4, AsF 6, SbF 6, PF 6 or ClO 4 (hereinafter simply called compound (XI)), in an inert solvent such as acetonitrile, water, methanol, chloroform and dichloromethane, at a temperature of 0 to 150 ° C, preferably 0 to 100 ° C. Two or more inert solvents can be mixed for use.
    Usually used as compound (XI) a commercially available compound.
    The amount of compound (XI) used is usually 0.5 to 2 moles per 1 mole of the salt (V). The salt (I) obtained can be extracted by crystallization or washing with water.
    The salt (V) can be produced by a process comprising the reaction of a compound represented by the formula (VI): ## STR2 ## wherein T and R are as defined above (and hereinafter simply called compound (VI)), with a salt represented by formula (IX):
    wherein Q1, Q2, T, R and M are as defined above (and hereinafter simply referred to as salt (IX)).
    The reaction of the compound (VI) and the salt (IX) is usually carried out by mixing the two in an aprotic solvent such as dichloroethane, toluene, ethylbenzene, monochlorobenzene, acetonitrile and Ν, Ν-dimethylfoimamide, at a temperature of 20 to 200 ° C, preferably 50 to 150 ° C. The reaction is usually conducted in the presence of an acid catalyst. Examples of the acid catalyst include an organic acid such as p-toluenesulfonic acid and an inorganic acid such as sulfuric acid.
    The reaction is preferably carried out with removal of the alcohol compound generated, for example by the Dean-Stark process so as to reduce the reaction time. The reaction can be carried out in the presence of a dehydrating agent. Examples of the dehydrating agent include 1,1'-carbonyldiimidazole, N, N'-dicyclohexylcarbodiimide, a 1-alkyl-2-halopyridinium salt, bis (2-oxo-3-oxazolidinyl) phosphinic chloride, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, di-2-pyridyl carbonate, di-2-pyridyl thionocarbonate and 6-methyl-2-nitric anhydride / 4- (dimethylamino) anhydride pyridine.
    The amount of salt (IX) used is usually 0.5 to 3 moles, preferably 1 to 2 moles per 1 mole of the compound (VI). The amount of acid catalyst used is usually from 0.001 to 5 moles per 1 mole of the compound (VI). The amount of dehydrating agent used is usually 0.5 to 5 moles per 1 mole of the compound (VI) and preferably 1 to 3 moles.
    When using as compound (VI) a compound represented by the formula (Via):
    wherein R is as defined above (and hereinafter simply referred to as the compound (Via)), the salt (V) in which T is a carbonyl group can also be produced by reacting the compound (Via) with a halogenation to prepare the corresponding acid halide compound and reaction of the corresponding acid halide compound with salt (IX).
    Examples of the halogenating agent include thionyl chloride, thionyl bromide, phosphorous trichloride, phosphorous pentachloride, and phosphorous tribromide. The reaction of the compound (Via) and the halogenating agent is usually carried out by mixing the two in an inert solvent such as an aprotic solvent (for example dichloroethane, toluene, ethylbenzene, monochlorobenzene, Ν, Ν-dimethylformamide, etc.) at a temperature of 20 to 200 ° C, preferably 50 to 150 ° C. The reaction is usually conducted in the presence of an amine compound.
    The reaction of the corresponding acid halide compound and salt (IX) is usually carried out by mixing the two in an inert solvent such as an aprotic solvent (e.g., dichloroethane, toluene, ethylbenzene, monochlorobenzene, and the like). , Ν, Ν-dimethylformamide, etc.) at a temperature of 20 to 200 ° C, preferably 50 to 150 ° C. The reaction is preferably conducted in the presence of a base. Basic examples include an organic base such as triethylamine and pyridine, and an inorganic base such as sodium hydroxide, potassium carbonate and sodium hydride. The amount of base used is usually from 0.001 to 5 moles per 1 mole of the corresponding acid halide compound, and preferably from 1 to 3 moles.
    When using as compound (VI) a compound represented by the formula (VIb): HO - CH 2 --R (VIb) wherein R is as defined above (and hereinafter simply called compound (VIb) ), the salt (V) in which T is a methylene group can also be produced by converting the compound (VI) to a compound represented by the formula (Life): L - CH2 - R (Life) in which R is such that defined above and L represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulphonyloxy group or a trifluoromethanesulphonyloxy group (and hereinafter simply called a compound (Life)), and reaction of the compound (Life) with the salt (IX).
    The compound (Life) can be produced by reaction of the compound (VIb) with thionyl chloride, thionyl bromide, phosphorous trichloride, phosphorous pentachloride, phosphorous tribromide, mesyl chloride, tosyl chloride or trifluoromethanesulfonic anhydride, in an inert solvent such as an aprotic solvent (for example dichloroethane, toluene, ethylbenzene, monochlorobenzene, Ν, Ν-dimethylformamide etc.) at a temperature of -70 to 200 ° C, preferably from -50 to 150 ° C. The reaction is preferably conducted in the presence of a base. Basic examples include an organic base such as triethylamine and pyridine, and an inorganic base such as sodium hydroxide, potassium carbonate and sodium hydride. The amount of base used is usually from 0.001 to 5 moles per 1 mole of the compound (VIb) and preferably from 1 to 3 moles.
    The reaction of the compound (Life) and the salt (IX) is usually carried out by mixing the two in an inert solvent such as an aprotic solvent (for example dichloroethane, toluene, ethylbenzene, monochlorobenzene, Ν, Ν-dimethylformamide etc.) at a temperature of -70 to 200 ° C, preferably 50 to 150 ° C. The reaction is preferably conducted in the presence of a base. Basic examples include an organic base such as triethylamine and pyridine, and an inorganic base such as sodium hydroxide, potassium carbonate and sodium hydride. The amount of base used is usually from 0.001 to 5 moles per 1 mole of the corresponding acid halide compound, and preferably from 1 to 3 moles.
    The salt (V) can also be produced by reacting the compound (VI) with a compound represented by the formula (X):
    wherein Q1 and Q2 are as defined above (and hereinafter simply referred to as compound (X)), followed by reaction with an MOH (for example LiOH, NaOH, KOH, AgOH).
    The salt (IX) can be produced by a process comprising the hydrogenation of a compound represented by the formula (XI):
    wherein Q1, Q2 and M are as defined above and Ra represents a C1-C4 alkyl group such as L1AIH4.
    The present chemically amplified positive resist composition will now be illustrated.
    The present chemically amplified positive reserve composition comprises salt (I) and a resin containing a structural unit having an acid-labile group and which is itself insoluble or poorly soluble in an aqueous alkaline solution but becomes soluble in an aqueous alkaline solution. the action of an acid.
    The salt (I) is usually used as an acid generator, and the acid generated by irradiation of the salt (I) acts catalytically towards the acidolabile groups in the resin, cleaves the acidolabile groups and the resin becomes soluble in an aqueous alkaline solution. Such a composition is suitable for a chemical amplification positive reserve composition.
    The resin used for the present composition contains a structural unit which has the acidolabile group and is itself insoluble or poorly soluble in an aqueous alkaline solution, but the acidolabile group is cleaved with an acid.
    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, "-COO (CH 3) 3" can be described as "a structure having a carboxylic acid tert-butyl ester", or be abbreviated to "tert-butyl ester group".
    Examples of the acidolabile group include a structure having a carboxylic acid ester group, such as an alkyl ester group, wherein a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, an alicyclic ester group in which a carbon atom 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. The "quaternary carbon atom" means "a carbon atom bound to four substituents other than hydrogen atoms".
    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-acetoxyethoxy) ethyl ester, 1- [2- (1-adamantyloxy) ethoxy] ethyl ester, 1- [2- (1-adamantane-carbonyloxy) ethoxy] ethyl ester, tetrahydro-2-furyl ester and tetrahydro-2-pyranyl ester, an alicyclic ester group in which a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, such as an isobornyl ester group, 1-alkylcycloalkyl ester, 2-alkyl-2-adamantyl ester and 1- (1-adamantyl) -1-alkylalkyl ester. At least one hydrogen atom of the adamantyl group may be 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 norborenecarboxylic acid ester , a structural unit derived from a tricyclodecenecarboxylic acid ester and a structural unit derived from a tetracyclodecene carboxylic acid ester. The structural units derived from the acrylic acid ester and the methacrylic acid ester are preferable.
    The resin used for the present composition can be obtained by conducting the polymerization reaction of a monomer or monomers having the acidolabile group and an olefinic double bond.
    Of the monomers, those having a bulky and acidolabile group such as an alicyclic ester group (eg, a 2-alkyl-2-adamantyl ester group and a 1- (1-adamantyl) -1-alkylalkyl ester) are preferred because an excellent resolution is obtained when the resin obtained is used in the present composition.
    Examples of such monomers containing the bulky and acidolabile group include a 2-alkyl-2-adamantyl acrylate, a 2-alkyl-2-adamantyl methacrylate, a 1- (1-adamantyl) -1-alkylalkyl acrylate, a 1- (1-adamantyl) -1-alkylalkyl methacrylate, a 2-alkyl-2-adamantyl 5-norbornene-2-carboxylate, a 1- (1-adamantyl) -5-norbornene-2-carboxylate alkylalkyl, a 2-alkyl-2-adamantyl α-chloroacrylate and a 1- (1-adamantyl) -1-alkylalkyl α-chloroacrylate.
    Especially when using 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate or 2-alkyl-2-adamantyl Γ-chloroacrylate as a monomer for the resin component in the present composition, there is a tendency to obtain a resist composition having an excellent resolution. Typical examples are 2-methyl-2-adamantyl acrylate, 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 Γα-chloroacrylate and 2-ethyl-2-adamantyl α-chloroacrylate. When, in particular, 2-ethyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-isopropyl-2-adamantyl acrylate or 2-isopropyl-2-methacrylate are used. Adamantyl for the present composition tends to provide a resist composition with an excellent degree of sensitivity and heat resistance. In the present invention, two or more types of monomers having a group or groups dissociated by the action of an acid can be used together if necessary.
    The 2-alkyl-2-adamantyl acrylate can be usually produced by reacting a 2-alkyl-2-adamantanol or a metal salt thereof with an acrylic halide, and 2-alkyl-2-methacrylate. Adamantyl can usually be produced by 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 an acid-stable monomer, in addition to the aforementioned structural units having the acidolabile group. Here, the term "structural unit derived from an acid-stable monomer" means a "non-dissociated structural unit by an acid generated by the salt (I)".
    Examples of such 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 a dicarboxylic anhydride unsaturated aliphatic such as maleic anhydride and itaconic anhydride, a structural unit derived from 2-norbornene, a structural unit derived from acrylonitrile or methacrylonitrile, a structural unit derived from an alkyl acrylate or a methacrylate alkyl, wherein a carbon atom adjacent to the oxygen atom is a secondary or tertiary carbon atom, a structural unit derived from 1-adamantyl acrylate or 1-adamantyl methacrylate, a structural unit derived from a styrene monomer such as p-hydroxystyrene and m-hydroxystyrene, a structural unit derived from acryloyloxy-γ-butyrolactone or methacrylo yloxy-γ-butyrolactone having a lactone ring which may be substituted by an alkyl group, and the like. Here, the 1-adamantyloxycarbonyl group is the acid stable group although the carbon atom adjacent to the oxygen atom is the quaternary carbon atom, and the 1-adamantyloxycarbonyl group may be substituted by at least one group. hydroxyl.
    Specific examples of the structural unit derived from the acid-stable monomer include a structural unit derived from 3-hydroxy-1-adamantyl acrylate, a structural unit derived from 3-hydroxy-1-adamantyl methacrylate, a structural unit derived from of 3,5-dihydroxy-1-adamantyl acrylate, a structural unit derived from 3,5-dihydroxy-1-adamantyl methacrylate, a structural unit derived from α-acryloyloxy-γ-butyrolactone, a structural unit derived from α-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 the formula (A)
    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, p represents an integer from 0 to 3 and, when p represents 2 or 3, the R 3 can be identical or different from one another, a structural unit represented by the formula (B):
    wherein R2 is hydrogen or methyl, R4 is methyl, trifluoromethyl or halogen, q is enter from 0 to 3, and when q is 2 or 3, R4 is may be identical 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, as a structural unit represented by the formula (C):
    wherein R5 and R6 each independently represent a hydrogen atom, a C1-C3 alkyl group, a C1-C3 hydroxyalkyl group, a carboxyl group, a cyano group or a -COOU group wherein U represents a residue of alcohol, or R5 and R6 may be bonded together to form a carboxylic anhydride residue represented by -C (= O) 0C (= O), a structural unit derived from an unsaturated aliphatic dicarboxylic anhydride, as a structural unit shown by the formula (D):
    a structural unit represented by the formula (E):
    and the like.
    In particular, the resin furthermore has at least one structural unit chosen from the group formed by the structural unit derived from 3-hydroxy-1-adamantyl acrylate, the structural unit derived from 3-hydroxy-1-methacrylate. adamantyl, the structural unit derived from 3,5-dihydroxy-1-adamantyl acrylate, the structural unit derived from 3,5-dihydroxy-1-adamantyl methacrylate, the structural unit derived from α-acryloyloxy- γ-butyrolactone, the structural unit derived from α-methacryloyloxy-γ-butyrolactone, the structural unit derived from β-acryloyloxy-γ-byturolactone, the structural unit derived from β-methacryloyloxy-γ-butyrolactone, the unit The structural unit represented by formula (A) and the structural unit represented by formula (B), in addition to the structural unit having the acidolabile group, is preferable from the point of view of the stickiness of the resist to a support and the resolution of the reservation.
    For example, 3-hydroxy-1-adamantyl acrylate, 3-hydroxy-1-adamantyl methacrylate and 3,5-dihydroxy-1-adamantyl methacrylate can be produced by reaction of the corresponding hydroxyadamantane with acrylic acid, methacrylic acid or its acid halide, and they are also commercially available.
    In addition, acryloyloxy-γ-butyrolactone and methacryloyloxy-γ-butyrolactone having the lactone ring which may be substituted by the alkyl group may be produced by reaction of the corresponding Γα- or β-bromo-γ-butyrolactone with acrylic acid or methacrylic acid, or by reaction of Γα- or the corresponding β-hydroxy-γ-butyrolactone with the acrylic halide or the methacrylic halide.
    Specifically, for example, as monomers to give structural units represented by the formulas (A) and (B) are an alicyclic lactone acrylate and an alicyclic lactone methacrylate having the hydroxyl group described later, and mixtures thereof. These esters may for example be produced by reacting the corresponding alicyclic lactone having the hydroxyl group with acrylic acid or methacrylic acid, and the production method is for example described in JP 2000-26446 A.
    Examples of acryloyloxy-γ-butyrolactone and methacryloyloxy-γ-butyrolactone having the lactone ring which may be substituted by the alkyl group include Γα-acryloyloxy-γ-butyrolactone, Γα-methacryloyloxy-γ-butyrolactone, β-acryloyloxy-β, β-dimethyl-γ-butyrolactone, α-methacryloyloxy-β, β-dimethyl-butyrolactone, Γα-acryloyloxy-α-methyl-γ-butyrolactone, α-methacryloyloxy-α-methyl- γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone and p-methacryloyloxy-α-methyl-γ-butyrolactone.
    In the case of KrF lithography, even if a structural unit derived from hydroxystyrene such as p-hydroxystyrene and m-hydroxystyrene is used as one of the components of the resin, it is possible to obtain a reserve composition with sufficient transparency. To obtain such copolymerization resins, the acrylic or methacrylic ester monomer can be polymerized, by a radical route, with acetoxystyrene and styrene, after which the acetoxy group of the structural unit derived from acetoxystyrene can be deacetylated with an acid.
    The resin containing a structural unit derived from 2-norbornene shows a strong structure because the alicyclic group is directly present on its main chain and exhibits 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 and in addition to the corresponding 2-norbornene. . The structural unit derived from 2-norbornene is formed by opening its double bond, and may be represented by the above-mentioned formula (C). 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 bonds, and can be represented by the formula (D) respectively. and formula (E) above.
    In R 5 and R 6, examples of the C 1 -C 3 alkyl group include a methyl, ethyl and n-propyl group, and examples of the C 1 -C 3 hydroxyalkyl group include a hydroxymethyl group and a 2-hydroxyethyl group.
    In R 5 and R 6, the group -COO 2 is an ester formed from the carboxyl group, and the alcohol residue corresponding to U, for example, 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 substituents on the C1-C6 alkyl group, there will be mentioned 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 (C) may include 2-norbornene, 2-hydroxy-5-norbornene, 5-norbornene-2-carboxylic acid, 2- 5-norbornene carboxylate, 5-norbornene-2-carboxylic acid, 5-nobornene 2-carboxylate, 5-methanol-2-methanol and 5-norbornene-2,3-dicarboxylic anhydride.
    When U, in the group -COOU, is the acidolabile group, the structural unit represented by the formula (C) is a structural unit having the acidolabile group, even if it has the norbornene structure. Examples of monomers yielding a structural unit having an 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-methyl-2-carboxylate) methylcyclohexyl) -1-methylethyl-5-norbornene, 1- (4-hydroxylcyclohexyl) -1-methylethyl-5-norbornene 2-carboxylate, 1-methyl-1- (4-oxocyclohexyl) ethyl 2-carboxylate 5-norbornene, 1- (1-adamantyl) -1-methylethyl-5-norbornene-2-carboxylate and the like.
    The resin used in the present composition preferably contains the structural unit (s) having the acidolabile group generally in a proportion of 10 to 80 mol% in all the structural units of the resin, although the proportion varies according to the type of radiation for the pattern forming exposure, the type of acidolabile group, and the like.
    When the structural units in particular derived from 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate, 1- (1-adamantyl) -1-alkylalkyl acrylate or methacrylate of 1- (1-adamantyl) -1-alkylalkyl are used as structural units possessing the acidolabile group, it is advantageous for dry etch resistance of the resist that the proportion of the structural units is 15% molars or more in all structural units of the resin.
    When, in addition to the structural units possessing the acidolabile group, other structural units having the acid-stable group are present in the resin, it is preferable that the sum of these structural units is of the order of 20 to 90 mol% , on the basis of all the structural units of the resin.
    The resin used for the present composition can be produced by a polymerization reaction of the corresponding monomer or monomers. The resin can also be produced by oligomerization of the corresponding monomer or monomers), followed by polymerization of the obtained oligomer.
    The polymerization reaction can usually be conducted in the presence of a radical initiator.
    The radical initiator is not limited, and examples thereof include: an azo compound such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1 ' azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis azobis (2-methylpropionate) dimethyl 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'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobisisobutyronitrile -azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate) are more preferable, and 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) ) are particularly preferable.
    These radical initiators may be used alone or in the form of a mixture of two or more of them. When using a mixture of two or more of them; the proportion of mixing is not particularly limited.
    The amount of radical initiator is preferably 1 to 20 mol%, based on the total molar amount of monomer or oligomer.
    The polymerization temperature is usually from 0 to 150 ° C, and preferably from 40 to 100 ° C.
    The polymerization reaction is usually conducted in the presence of a solvent and it is preferred to use a solvent sufficient to dissolve the monomer, the radical initiator and the resulting resin. Examples thereof are a hydrocarbon solvent such as toluene, an ether solvent such as 1,4-dioxane and tetrahydrofuran, a ketone solvent such as methylisobonutyl ketone, an alcohol solvent such as isopropyl alcohol, a cyclic ester solvent such as γ-butyrolactone, a glycol ether ester 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 mixed with each other.
    The amount of solvent is not limited, and in practice it is preferably 1 to 5 parts by weight relative to all the monomers or oligomers.
    When using as monomers an alicyclic compound having an olefinic double bond and an unsaturated aliphatic dicarboxylic anhydride, it is preferable to use them in excess in view of their tendency not to polymerize easily.
    At the end of the polymerization reaction, the resin produced can be isolated, for example, by adding to the reaction mixture obtained a solvent in which the present resin is insoluble or poorly soluble and filtration of the precipitated resin. If necessary, the isolated resin can be purified, for example by washing with a suitable solvent.
    The present resist composition preferably comprises from 80 to 99.9% by weight of the resin component and from 0.1 to 20% by weight of the salt (I), based on the total amount of the resin component and the salt. (I).
    In the present resin composition, it is possible to reduce a deterioration in performance caused by acid inactivation, which occurs as a result of post-exposure delay, by addition of an organic basic compound, particularly a nitrogenous organic basic compound, as a deactivator.
    Specific examples of the basic organic nitrogen compound include an amine compound represented by the following formulas:
    in which R 11 and R 12 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and the alkyl, cycloalkyl or aryl group may be substituted by at least one group selected from a hydroxyl group, a group amino which may be substituted by a C1-C4 alkyl group and a C1-C6 alkoxy group which may be substituted by C1-C6 alkoxy, 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 or alkoxy group 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 C1-C6 alkoxy group, or R13 and R14 bond together with the carbon atoms to which they are bonded to form an aromatic ring, R15 represents a hydrogen atom, an alkyl group, a cyclic group, oalkyl, an aryl group, an alkoxy group or a nitro group, and the alkyl, cycloalkyl, aryl and alkoxy group which may be substituted by at least one group selected from a hydroxyl group, an amino group which may be substituted by an alkyl group C1 to C4 and a C1 to C6 alkoxy group, R16 is 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 a C1-C4 alkyl group and C1-C6 alkoxy group, 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 R17, R18, R19 and R20 independently represent 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 hydroxyl group, an amino group which may be substituted by a C1-C4 alkyl group and a C1-C6 alkoxy group.
    The alkyl group in R 11, R 12, R 13, R 14, R 15, R 16, R 17 R 18, R 19 and R 20 preferably has from 1 to 10 carbon atoms, and more preferably has from 1 to 6 carbon atoms.
    Examples of the amino group which may be substituted by the C 1 -C 4 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-aminoethyl.
    The cycloalkyl group in R11, R12, R13, R14, R15, R16, R17, R4 and R4 preferably has from about 5 to 10 carbon atoms. Specific examples of the cycloalkyl group which may be substituted by at least one group selected from a hydroxyl group, an amino group which may be substituted by a C 1 -C 4 alkyl group and a C 1 -C 6 alkoxy group include cyclopentyl, cyclohexyl groups. cycloheptyl and cyclooctyl.
    The aryl group in R 11, R 12, R 13, R 14, R 15, R 16, R 17 R 18, R and R preferably has from about 6 to 10 carbon atoms. 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 1-4 alkyl group and a C 1-6 alkoxy group include phenyl and naphthyl groups.
    The alkoxy group in R13, R14 and R15 preferably has 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 in 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-dimethyldiphenylmethane, 4,4'-diamino-3,13-diethyl-diphenylmethane, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, N-methylaniline, piperidine, diphenylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylami ne, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine , triisopropanolamine, Ν, Ν-dimethylaniline, 2,6-diisopropylaniline, imidazole, benzimidazole, pyridine, 4-methylpyridine, 4-methylimidazole, bipyridine, 2,2'-dipyridylamine, di-2-pyridyl ketone, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,3-di (4-pyridyl) propane, 1,2-di- bis (2-pyridyl) ethylene, 1,2-bis (4-pyridyl) ethylene, 1,2-bis (4-pyridyloxy) ethane, 4,4-dipyridyl sulfide, 4,4-disulphide dipyridyl, 1,2-bis (4-pyridyl) ethylene, 2,2'-dipicolylamine and 3,3'-dipicolylamine.
    Examples of quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, (3-trifluoromethylphenyl) hydroxide trimethylammonium and (2-hydroxyethyl) trimethylammonium hydroxide (called "choline").
    A sterically hindered amine having a piperidine backbone as disclosed in JP 11-52575 A1 may also be used as the quencher.
    As regards the formation of higher resolution patterns, quaternary ammonium hydroxide is preferably used as a quencher.
    When the basic compound is used as a deactivate, the present resist composition comprises from 0.01 to 1% by weight of the basic compound, based on the total amount of the resin component and the salt (I).
    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 effect of present invention is not prevented.
    The present resin composition is usually 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 process conventional such as a centrifugal coating. The solvent used is sufficient to dissolve the aforementioned ingredients, has a suitable drying rate, and gives a uniform and smooth coating after evaporation of the solvent. Solvents generally employed in the art can be used.
    Examples of solvents include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate, acyclic esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate, ketones such as acetone, methyl isobutyl ketone, 2-heptatone and cyclohexanone, and a cyclic ester such as γ-butyrolactone. These solvents can be used alone and two or more of them can be mixed for use.
    The resist film applied to the substrate and then dried is subjected to patterning exposure, then subjected to a heat treatment to facilitate an unlocking reaction, and then developed with an alkaline developer. The alkaline developer may be any of the various alkaline solutions used in the art. In general, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly known as "choline") is often used.
    It should be understood that the embodiments disclosed herein are examples in all respects and are not limiting. It should be understood that the present invention is not determined by the foregoing descriptions, but by the appended claims, and includes all variations of the equivalent meanings and ranges of the claims.
    The present invention will be described more specifically by examples, which are not to be construed as limiting the scope of the present invention. The "%" and "part (s)" used to represent the content of any component and the amount of any material to be used in the following examples are on a weight basis unless otherwise specified.
    The weight average molecular weight of any material in the following examples is a value found by gel permeation chromatography (HLC-8120GPC type, column (total 3 columns): TSK Multipore HXL-M gel manufactured by TOSOH CORPORATION, solvent: tetrahydrofuran) using polystyrene as a control reference material.
    The structures of the salts obtained were determined by NMR (type GX-270 or type EX-270, manufactured by JEOL LTD) and mass spectrometry (liquid chromatography type 1100 manufactured by AGILENT TECHNOLOGIEZ Ltd., mass spectrometry: LC / MSD type or LC / MSD TOF type manufactured by AGILENT TECHNOLOGIES LTD.).
    EXAMPLE 1 SYNTHESIS OF SALT
    (1) 10.4 grams of lithium aluminum hydride were mixed with 120 ml of anhydrous tetrahydrofuran. To the resulting mixture was added a solution prepared by mixing 62.2 g of a salt of the above-mentioned formula (a) and 900 ml of anhydrous tetrahydrofuran dropwise and in an ice bath (below 7 ° C).
    hours. Ethyl acetate was added to the resulting mixture to decompose the excess lithium aluminum hydride, and then the resulting mixture was added dropwise with 50 ml of 6N hydrochloric acid. The resulting mixture was concentrated. The residue obtained was purified by chromatography on silica gel (chloroform / methanol = 5/1) to give 84.7 g of the salt of the above-mentioned formula (b) (content: 60%).
    1 H NMR: (dimethyl sulfoxide - internal standard d6: tetramethylsilane): δ (ppm) 3.81 (m, 2H), 5.28 (t, 1H, J = 6.2 Hz).
    13 C NMR (dimethyl sulfoxide): δ (ppm) 120.5 (t, J = 276 Hz), 60.1.
    19 F NMR (dimethyl sulfoxide, internal standard: fluorobenzene): δ (ppm) 111.9; (2) 4.5 grams of 4-oxoadamantane-1-carboxylic acid were dissolved in 90 ml of anhydrous tetrahydrofuran. A solution prepared by mixing 3.77 g of 1,1'-carbonyldiimidazole and 45 ml of anhydrous tetrahydrofuran was added dropwise to the resulting solution at room temperature. The resulting mixture was stirred at room temperature for 4 hours. The mixture was added dropwise to a mixture of 7.87 g of the salt of the above-mentioned formula (b) obtained in (1) above and 50 ml of anhydrous tetrahydrofuran at a temperature of 54 to 60 ° C for 0.5 hours. The resulting mixture was refluxed for 18 hours. After cooling, the reaction mixture was filtered to remove insolubles, and the insolubles were washed with chloroform. The resulting filtrate was concentrated and gave 10.36 g of residue. The residue was purified by silica gel chromatography (chloroform / methanol) to give 4.97 g of the above salt of formula (c) (yield: 59.4%).
    1H NMR: (dimethyl sulfoxide - d6, internal standard: tetramethylsilane): δ (ppm) 1.89 - 1.92 (m, 2H), 2.02 - 2.04 (m, 2H), 2.07 2.18 (m, 7H), 2.46 (s, 2H), 4.57 (t, 2H, J = 15.3 Hz).
    19F NMR (dimethylsulfoxide - internal standard ds .: fluorobenzene): δ (ppm) 110.6.
    (3) One gram of the salt of the above-mentioned formula (c) obtained in the above-mentioned (2) was dissolved in 20 g of chloroform. 6.3 g of aqueous triphenylsulfonium chloride solution (concentration: 13.1%) were added to the solution at room temperature. The resulting mixture was stirred overnight at room temperature. The mixture was extracted with chloroform and the resulting organic layer was washed with water and dried over anhydrous magnesium sulfate. The organic layer was filtered and the resulting filtrate was concentrated to give 1.36 g of the salt of the above-mentioned formula (b), designated B1. Yield: 81.6%.
    1H NMR (dimethyl sulfoxide - d6, internal standard: tetramethylsilane): δ (ppm) 1.95 - 1.98 (m, 2H), 2.04 - 2.06 (m, 2H), 2.15 - 2.24 (m, 7H), 2.56 (s, 2H), 4.77 (t, 2H, J = 15.3 Hz), 7.70-7.80 (m, 15H).
    13 C NMR (dimethyl sulfoxide - d6): δ (ppm) 26.9, 37.3, 38.0, 39.7, 40.2, 45.5, 61.9, 118.8 (t, J) = 279 Hz), 124.1, 130.9, 131.4, 134.5, 174.5, 216.3.
    19 F NMR (dimethyl sulfoxide - d6, internal standard: fluorobenzene): δ (ppm) 110.7.
    MS (ESI (+) spectrum): M + 263.2 (C16H15S + = 263.09) MS (ESI (-) spectrum): M '337.0 (C13H15F2O6S' = 337.06) EXAMPLE 2 SALT SYNTHESIS
    (1) 3.51 grams of 3-hydroxyadamantane-1-carboxylic acid was dissolved in 75 ml of anhydrous tetrahydrofuran. To the resulting solution was added dropwise and at room temperature a solution prepared by mixing 2.89 g of 1,1'-carbonyldiimidazole and 50 ml of anhydrous tetrahydrofuran. The resulting mixture was stirred at room temperature for 4 hours. The mixture was added dropwise to a mixture of 6.04 g of the salt of formula (b) above, obtained in Example 1 of salt synthesis (1) and 50 ml of anhydrous tetrahydrofuran, at a temperature of 54 to 60 ° C, in the space of 25 minutes. The resulting mixture was refluxed for 18 hours. After cooling, the reaction mixture was filtered to remove insolubles, and the insolubles were washed with chloroform. The filtrate obtained was concentrated to give 6.72 g of the residue. The residue was purified by silica gel chromatography (chloroform / methanol) to give 2.99 g of the salt of formula (e) above (yield: 35.8%).
    (2) One gram of the above-mentioned salt of formula (e) obtained in (1) above was dissolved in 30 g of chloroform. 6.3 g of aqueous triphenylsulfonium chloride solution (concentration: 13.1%) were added to the solution at room temperature. The resulting mixture was stirred overnight at room temperature. The mixture was extracted with chloroform and the resulting organic layer was washed with water and dried over anhydrous magnesium sulfate. The organic layer was filtered and the resulting filtrate was concentrated to give 1.6 g of the above-mentioned salt of formula (f), designated B2. Yield: 96.2%.
    1H NMR (dimethyl sulfoxide - internal standard d6: tetramethylsilane): δ (ppm) 1.54 (s, 2H), 1.63-1.70 (m, 4H), 1.73-1.80 (m , 4H), 1.83 (s, 2H), 2.18-2.19 (m, 2H), 2.35 (s, 1H), 4.73 (t, 2H, J = 15.3 Hz). 7.68-7.78 (m, 15H).
    13 C NMR (dimethyl sulfoxide - d6): δ (ppm) 30.0, 34.8, 37.4, 44.0, 45.9, 61.7, 119.0 (t, J = 279 Hz) , 124.3; 131.0, 131.5, 134.5, 175.3.
    19 F NMR (dimethyl sulfoxide - d6, internal standard: fluorobenzene): δ (ppm) 110.6.
    EXAMPLE 3 SYNTHESIS OF SALT
    One gram of the salt of the above-mentioned formula (c), obtained in the above-mentioned example 1 salt synthesis (2), was dissolved in 20 g of chloroform. 0.8 g of phenacyltetrahydrothiophenium bromide was added to the solution at room temperature. The resulting mixture was stirred overnight at room temperature. The mixture was extracted with chloroform and the resulting organic layer was washed with water and dried over anhydrous magnesium sulfate. The organic layer was filtered and the filtrate concentrated to give 0.9 g of the salt of the above-mentioned formula (g), designated B3. Yield: 59.3%.
    1H NMR (dimethyl sulfoxide - d6, internal standard: tetramethylsilane): δ (ppm) 1.93 - 1.96 (m, 2H), 2.01 - 2.03 (m, 2H), 2.07 - 2.08 (m, 2H), 2.13 (m, 4h), 2.14 (m, 1H), 2.28 - 2.33 (m, 4H), 2.46 -2.52 (m, 4H), 2.54 (s, 2H), 3.66 - 3.79 (m, 4H), 4.58 (t, 2H, J = 15.3 Hz), 5.56 (s, 2H), 7.47 (m, 2H), 7.61 (m, 1H), 8.01 (d, 2H, J = 6.8 Hz).
    13 C NMR (dimethyl sulfoxide - d6): δ (ppm) 27.0, 28.5, 37.3, 38.1, 39.8, 40.3, 45.6, 52.8, 61.2 , 118.7 (t, J = 278 Hz), 129.0, 133.5, 135, 174, 191, 216.4.
    19 F NMR (dimethyl sulfoxide - d6, internal standard: fluorobenzene): δ (ppm) 110.3.
    MS (ESI (+) spectrum): M + 207; 1 (C12H15OS + = 207.08) MS (ESI (-) spectrum: M '337; O (C₁ uH₂O OS' = 337.06).
    EXAMPLE 4 OF SYNTHESIS OF SALT
    One gram of the salt of formula (e) above was dissolved in 20 g of chloroform. 0.8 g of phenacyltetrahydrothiophenium bromide was added to the solution at room temperature. The resulting mixture was stirred overnight at room temperature. The mixture was extracted with chloroform and the resulting organic layer was washed with water and dried over anhydrous magnesium sulfate. The organic layer was filtered and the resulting filtrate concentrated to give 0.6 g of the salt of the above-mentioned formula (h), designated B4. Yield: 40.0%.
    1H NMR (dimethyl sulfoxide - d6, internal standard: tetramethylsilane): δ (ppm) 1.65 (m, 4H), 1.72 (m, 4H), 1.80 (s, 2H), 2.04 (m, 2H), 2.19 (s, 1H), 2.29 - 2.37 (m, 4H), 2.48 - 2.58 (m, 4H), 3.81 - 3.86 (m). , 4H), 4.57 (t, 2H, J = 14.9 Hz), 5.89 (s, 2H), 7.47 (m, 2H), 7.61 (m, 1H), 8.01 (d, 2H, J = 6.8 Hz).
    EXAMPLE 5 SYNTHESIS OF SALT
    0.5 gram of the salt of formula (c) above was dissolved in a mixture of 20 g of chloroform and 10 g of water. 0.65 g of tris (4-tert.-butylphenyl) sulfonium chloride was added to the solution at room temperature. The resulting mixture was stirred overnight at room temperature. The mixture was extracted with chloroform and the resulting organic layer was washed with water and dried over anhydrous magnesium sulfate. The organic layer was filtered and the filtrate obtained was concentrated to give 0.91 g of the salt of formula (i) above, referred to as B5. Yield: 85.0%.
    1H NMR (CDCl3, internal standard: tetramethylsilane): δ (ppm) 1.33 (s, 27H), 1.95 - 1.98 (m, 2H), 2.04 - 2.06 (m, 2H) , 2.17-2.19 (m, 3H), 2.24 (s, 4H), 2.57 (s, 2Ha, 4.80 (t, 2H, J = 15.3Hz), 7.69; (m, 15H).
    13 C NMR (CDCl 3) δ (ppm) 27.1, 30.8, 35.4, 37.5, 38.2, 39.9, 40.4, 45.7, 62.2, 118 , 7 (t, J = 278 Hz), 121.3, 128.5, 130.8, 158.5, 174.6, 216.6; 19 F NMR (dimethyl sulfoxide - d6, internal standard: fluorobenzene): δ (ppm) 110.5.15 - 2.24 (m, 7H), 2.58 (s, 2H), 4.79 (t, 2H, J = 15.3 Hz), 7.70 (m, 15H).
    EXAMPLE 6 OF SYNTHESIS OF SALT
    (1) 1 g of the above-mentioned compound of formula (j) and 2.47 g of pyridine were dissolved in 5 ml of anhydrous dichloromethane. To the resulting solution was added the dichloromethane solution prepared by mixing 2.37 g of trifluoromethanesulfonic anhydride and 5 ml of dichloromethane dropwise at a temperature of 3 to 5 ° C. The resulting mixture was stirred at 3 to 5 ° C for 2 hours. Dichloromethane was added to the resulting mixture, and the resulting solution was washed with acidified water, aqueous sodium hydrogencarbonate solution and water. The solution was dried over anhydrous magnesium sulfate. The mixture was filtered and the resulting filtrate was concentrated to give the residue. The resulting residue was purified by silica gel chromatography (hexane / ethyl acetate) to give 1.19 g of the above-mentioned compound of formula (k). Yield: 74.8%.
    1H NMR (CHCl 3, internal standard: tetramethylsilane) δ (ppm-1.48-2.07 (m, 13H), 3.95 (s, 4H), 4.1 (s, 2H).
    (2) Three milliliters of anhydrous dimethyl sulfoxide and 228.5 mg of sodium hydride were heated to 60 ° C. To the mixture was added 0.62 g of the above-mentioned salt of formula (b) and the resulting mixture was maintained at 60 ° C for 1 hour. The prepared solution was added dropwise to the mixture by mixing 1 g of the above-mentioned compound of formula (k) with 9 ml of anhydrous dimethylsulfoxide and stirring the resulting mixture at 60 ° C for 5 hours. After cooling the reaction mixture, the reaction mixture was purified by silica gel chromatography (chloroform / methanol) to give 0.28 g of the salt of the above-mentioned formula (I). Yield: 25.6%.
    1H NMR (standard internal CDCl3: tetramethylsilane): δ (ppm) 1.69 - 1.96 (m, 11H), 2.39 (s, 2H), 3.22 (s, 2H), 3.95 (t, 2H, J = 15.5 Hz).
    (3) 10 grams of chloroform were mixed with 0.2 grams of the salt of formula (1) above. 1.5 g of aqueous triphenylsulfonium chloride solution (concentration: 12.8%) were added to the resulting solution at room temperature. The resulting mixture was stirred at room temperature for three days. The mixture was extracted with chloroform and the resulting organic layer was washed with water and dried over anhydrous magnesium sulfate. The organic layer was filtered, and the filtrate was concentrated to give 0.24 g of the salt of formula (m) above, referred to as B6. Yield: 80.0%.
    1H NMR (CDCl3, internal standard: tetramethylsilane): δ (ppm) 1.70 - 2.07 (m, 11H), 2.43 (s, 2H), 4.06 (t, 2H, J = 15 , 8 Hz), 7.64 -7.74 (m, 15H).
    EXAMPLE 1 RESIN SYNTHESIS
    2-Ethyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, 5-methacryloyloxy-2,6-norbornane-carbolactone and α-methacryloyloxy-γ-butyrolactone were dissolved ( molar proportion of monomers = 2: 0.5: 0.5: 1) in 1,4-dioxane. To the solution was added as initiator; 2,2'-azobisisobutyronitrile, and the resulting mixture heated to about 85 ° C for about 5 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. A copolymer having a weight average molecular weight of about 10,000 and a degree of dispersion of about 1.7 is thus obtained. This copolymer is called the resin R1.
    EXAMPLES 1 TO 2 AND COMPARATIVE EXAMPLE 1. <Resin> Resin R1 <Acid Generator> B1 Acid Generator:
    B2 acid generator:
    C1 acid generator:
    <Deactivator> Deactivator Q1: 2,6-Diisopropylaniline <Solvent>
    Solvent Y1: propylene glycol monomethyl ether acetate 51.5 parts 2-heptanone 35.0 parts γ-butyrolactone 3.5 parts
    The following components were mixed to give a solution, and the solution was further filtered on a fluororesin filter having a pore diameter of 0.2 μm, to prepare a liquid reserve.
    Resin (type and quantity described in Table 1) Acid generator (type and quantity described in Table 1) Deactivator (type and quantity described in Table 1)
    Solvent (type and quantity described in Table 1)
    Table 1
    Silicon wafers were each coated with "ARC-29A-8", which is an antireflective organic coating composition available from Nissan Chemical Industries, Ltd., and then fired at 205 ° C and 60 seconds to form an organic anti-reflective coating with a thickness of 780 Å.
    Each of the liquid reserves prepared as above was centrifugally applied to the antireflective coating so that the resulting film thickness was 0.15 μm after drying. After applying each of the liquid reserves, the silicone wafers thus coated with the respective liquid reserves were precooked on a direct hot plate at a temperature of 125 ° C. for 60 seconds. Using an ArF excimer stepper ("FPA-5000AS3" manufactured by CANON Inc., NA = 0.75, annulus 2/3), each slab on which the respective resist film was formed was exposed to a pattern. lines and spaces, while gradually changing the amount of exposure.
    After exposure, each slab was subjected to post-exposure cooking on a hot plate at a temperature of 125 ° C for 60 seconds, followed by paddle development for 15 seconds with a solution of 2.38% d. tetramethylammonium hydroxide.
    Each of the dark area patterns developed on the organic anti-reflective layer substrate after development was observed with a scanning electron microscope and measured line widths to calculate the LWR (line edge roughness). These results are shown in Table 2. The term "dark area pattern" as used herein refers to a pattern obtained by exposure and development via a reticle comprising a chromium base surface (light blocking portion) and layers. of linear glass (light transmitting portion) formed on the chromium surface and aligned with each other. Therefore, the dark area portion is such that, after exposure and development, a 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 (light-blocking part) and the space pattern (part of light transmitting) become 1: 1 after exposure through a mask. lines and spaces of 100 nm and development.
    Resolution: it is expressed by the minimum size of the pattern of spaces giving the pattern of spaces separated by the line pattern to the amount of exposure of the reactive sensitivity.
    LWR: the lower the LWR value, the better the pattern of its reserve pattern.
    Table 2
    The results shown in Table 2 show that the resist patterns obtained in Examples 1 to 2 have excellent patterning because the LWRs of Examples 1 to 2 are inferior to those of Comparative Example 1.
    EXAMPLE 3
    The dark-zone pattern developed on the organic anti-reflective coating substrate after development is observed in the same manner as in Example 1, except that the B3 acid generator is used at the same time. place of the acid generator B1.
    EXAMPLE 4
    The dark-zone pattern developed on the organic anti-reflective coating substrate after development is observed in the same manner as in Example 1, except that the B4 acid generator is used at place of the acid generator B1.
    EXAMPLE 5
    The dark area pattern developed on the organic anti-reflective coating substrate after development is observed in the same manner as in Example 1, except that the B5 acid generator is used at the same time. place of the acid generator B1.
    The salt represented by formula (I) is suitable for an acid generator capable of providing chemical amplification positive reserve composition giving excellent patterning.
    EXAMPLE 6
    The dark zone pattern developed on the organic anti-reflective coating substrate after development is observed in the same manner as in Example 1, except that the acid generator B6 is used at the same time. place of the acid generator B1.
    权利要求:
    Claims (17)
    [1]
    1. Salt represented by formula (I):

    [2]
    The salt of claim 1, wherein Q 1 and Q 2 each independently represent a fluorine atom or a trifluoromethyl group.
    [3]
    3. Salt according to claim 1, wherein Q1 and Q2 represent fluorine atoms.
    [4]
    The salt of claim 1, wherein the organic counterion is at least one cation selected from the group consisting of a cation represented by the formula (IIa):

    [5]
    The salt of claim 1, wherein the organic counterion is a cation represented by the formula (IIa).
    [6]
    The salt of claim 5, wherein the cation represented by the formula (IIa) is a cation represented by the formula (Ile):

    [7]
    7. The salt of claim 1, wherein R is an adamantyl group substituted with a hydroxyl group or an oxo group.
    [8]
    8. Salt according to claim 7, in which the organic counterion is a cation represented by the formula (IIc):

    [9]
    9. Chemical amplification positive reserve composition comprising a salt represented by the formula (I):

    [10]
    The chemical amplification positive resist composition of claim 9, wherein Q 1 and Q 2 each independently represent a fluorine atom or a trifluoromethyl group.
    [11]
    The chemical amplification positive resist composition of claim 9, wherein Q1 and Q2 are fluorine atoms.
    [12]
    The chemical amplification positive resist composition of claim 9, wherein the resin contains a structural unit derived from a monomer having a bulky and acidolabile group.
    [13]
    The chemical amplification positive resist composition of claim 12, wherein the bulky and acidolabile group is a 2-alkyl-2-adamantyl ester group or a 1- (1-adamantyl) -1-alkylalkyl ester group.
    [14]
    The chemical amplification positive resist composition of claim 12, wherein the monomer having a bulky and acidolabile group is 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate, 1-1-adamantyl-1-alkylalkyl acrylate, 1-1-adamantyl-1-alkylalkyl methacrylate, 2-alkyl-2-adamantyl-5-norbornene 2-carboxylate, 2-carboxylate of 10 adamantyl-1-alkylalkyl-o-norbornenb, 2-alkyl-2-adamantyl α-chloroacrylate or 1- (1-adamantyl) -1-alkylalkyl α-chloroacrylate.
    [15]
    15. The chemically amplified positive reserve composition of claim 12, wherein the monomer having a bulky and acidolabile group is 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate, 1- (1-adamantyl) -1-alkylalkyl acrylate and 1- (1-adamantyl) -1-alkylalkyl methacrylate.
    [16]
    The chemical amplification positive resist composition of claim 12, wherein the monomer having a bulky and acidolabile group is 2-alkyl-2-adamantyl acrylate and 2-alkyl-2-adamantyl methacrylate.
    [17]
    The chemical amplification positive resist composition of claim 9, wherein the chemical amplification positive resist composition further contains a basic compound.
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    同族专利:
    公开号 | 公开日
    US20090042128A1|2009-02-12|
    TW200911743A|2009-03-16|
    US7611822B2|2009-11-03|
    KR20090012110A|2009-02-02|
    GB2452806B|2010-04-28|
    GB0813440D0|2008-08-27|
    JP2009046479A|2009-03-05|
    CN101353319A|2009-01-28|
    TWI438182B|2014-05-21|
    KR101547568B1|2015-08-26|
    GB2452806A|2009-03-18|
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    法律状态:
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    JP2007193184|2007-07-25|
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