CARBOXYLATE, CARBOXYLIC ACID GENERATOR, RESIST COMPOSITION AND METHOD FOR PRODUCING RESIST PATTERN

专利摘要:
An object of the present invention is to provide a carboxylate and a resist composition including the salt, which are capable of producing a resist pattern with satisfactory line edge roughness (LER). Disclosed are a carboxylate represented by formula (I) as defined in claim 1, a carboxylic acid generator and a resist composition including the carboxylate, wherein R1 represents a fluorine atom or a fluorinated alkyl group having 1 with 4 carbon atoms; R2, R3 and R4 each independently represent a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms or a hydrocarbon group having 1 to 12 carbon atoms, and -CH2- included in the hydrocarbon group may be replaced by -O- or -CO-; m2 and m3 represent an integer of 0 to 4 and m4 represents an integer of 0 to 5; and X0 represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and -CH2- included in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-.
公开号:BE1028011B1
申请号:E20215082
申请日:2021-02-04
公开日:2022-01-26
发明作者:Tatsuro Masuyama；Yukako Anryu；Koji Ichikawa
申请人:Sumitomo Chemical Co；
IPC主号:

专利说明:

[0001] The present invention relates to a carboxylate (carboxylic acid salt), a carboxylic acid generator, a resist composition and a method for producing a resist pattern.
[0002] [0002] Patent document 1 mentions a resist composition including a carboxylate represented by the following formula as a carboxylic acid generator. O 5 O+ 4 O 8 Patent document 2 mentions a salt represented by the following formula, and a resist composition comprising the salt as an acid generator.
[0003] [0003] Patent document 1: JP 2011-39502 A Patent document 2: JP 2019-168475 A Patent document 3: JP 2018-118962 A Description of the invention Problems to be solved by the invention
[0004] The present invention proposes to provide a carboxylate and a resist composition comprising the carboxylate capable of forming a resist pattern with a line edge roughness (LER) which is better than that of a resist pattern formed from the resist compositions comprising the aforementioned salts. Ways to solve problems
[0005] The present invention includes the following inventions.
[1] [1] A carboxylate represented by formula (I): (D) m2 hs R1 A — 02C——X® (I) + x S — (RS) ma (R)ma where, in formula (I), R* represents a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, R°, R3 and R* each independently represent a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms or a group hydrocarbon having 1 to 12 carbon atoms, and -CHz- included in the hydrocarbon group may be replaced by -O- or -CO-, m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R* may be the same or different, m3 represents an integer of 0 to 4, and when m3 is 2 or more, a plurality of R* may be the same or different, m4 represents an integer of 0 to 5, and when m4 is 2 or more, a plurality of R* may be the same or different, and X° represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and -CH>- included in the hydrocarbon group may be replaced. ace by -O-, -S-, -CO- or -SOz-.
[2] [2] The carboxylate according to [1], where R2, R and R* each independently represents a fluorine atom, an iodine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
[3] [3] The carboxylate according to [1] or [2], wherein X° is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (-CH>- included in the aliphatic hydrocarbon group may be replaced by - O-, -S-, -CO- or -SOz-), an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, a group represented by formula (aa) or a group represented by formula ( bb): a ga za ob (aa) where, in the formula (aa), X and XP each independently represent -O- or -S-, X!2 represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH>- included in the hydrocarbon group may be replaced by -O- , -S-, -CO- or -SO--,
[4] [4] The carboxylate according to [3], wherein X° is an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a fluorine atom or a hydroxy group (-CH>- included in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -S0;-), a group obtained by combining an alicyclic hydrocarbon group having 3 to 36 carbon atoms with a chain hydrocarbon group having 1 to 18 carbon atoms (- CH>- included in the alicyclic hydrocarbon group can be replaced by -O-, -S-, -CO- or -SO--; -CH>- included in the chain hydrocarbon group can be replaced by -O- or - CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group), an aromatic hydrocarbon group having 6 to 36 carbon atoms may have a fluorine atom or a hydroxy group, an represented by formula (aa) or a group represented by formula (bb).
[5] [5] A carboxylic acid generator comprising the carboxylate according to any one of [1] to [4].
[6] [6] A resist composition comprising the carboxylic acid generator according to [5], an acid generator other than the carboxylic acid generator and a resin having an acid labile group.
[7] [7] The resist composition according to [6], wherein the resin having an acid-labile group 5 comprises at least one member selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by the formula ( a1-2): The R24 The Ra5 = | = | Lan 22 „Join el nt! (a1-1) (a1-2) where, in formula (a1-1) and formula (a1-2), L°* and L22 each independently represent -O- or *-O- (CH2)k1- CO-O-, k1 represents an integer of 1 to 7, and * represents a bonding site at -CO-, R°* and R each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, R°° and R each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups, m1 represents an integer of 0 to 14, nl represents an integer of 0 to 10, and nl ' represents an integer from 0 to 3.
[8] [8] The resist composition according to [6] or [7], wherein the resin having an acid-labile group comprises a structural unit represented by the formula (a2-A):
[9] [9] A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to any one of [6] to [8] onto a substrate, (2) a step drying the applied composition to form a layer of composition, (3) a step of exposing the layer of composition,
[0006] [0006] It is possible to provide a resist pattern with satisfactory line edge roughness (LER) by using a resist composition comprising a carboxylate of the present invention. Mode for carrying out the invention
[0007] [0007] In the present description, “(meth)acrylic monomer” means at least one selected from the group consisting of a monomer having a “CH” structure; =CH-CO-” and a monomer having a structure “CH; =C(CH3)-CO-”. Similarly, “(meth)acrylate” and “(meth)acrylic acid” each mean “at least one selected from the group consisting of acrylate and methacrylate” and “at least one selected from the group consisting of acrylic acid and methacrylic acid". When a structural unit having "CHz=C(CH3)-CO-" or "CH2=CH-CO-" is cited as an example, a structural unit having both groups shall be cited as an example of similar way. In the groups mentioned in the present description, the groups capable of having a linear structure and a branched structure, may have the linear structure or the branched structure. "Derived" or <induced> means that a polymerizable C=C bond included in the molecule becomes a -C-C- group by polymerization. “Combined group” means a group in which two or more exemplified groups are bonded, and the valences of these groups can be changed appropriately depending on a form of bonding. When stereoisomers exist, all stereoisomers are included. In the present description, "solid content of the resist composition" means the total of the contents excluding the solvent (E) mentioned below which is removed from the total amount of the resist composition.
[0008] [0008] [Carboxylate represented by Formula (T)] The present invention relates to a carboxylate represented by formula (I) (hereinafter sometimes referred to as “carboxylate (T)” or “salt (I)”).
[0009] In formula (I), the fluorinated alkyl group having 1 to 4 carbon atoms as for Rt, R2, R and R* represents an alkyl group having 1 to 4 carbon atoms which has a fluorine atom, and examples thereof include a perfluoroalkyl group having 1 to 4 carbon atoms (a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl, a nonafluorobutyl group) and a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group and a 3,3,4,4,4-pentafluorobutyl group and the like. The number of carbon atoms of the fluorinated alkyl group is preferably 1 to 3, and more preferably 1 or 2. In the formula (I), examples of the halogen atom as for R* , R3 and R* include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In the formula (I), examples of the hydrocarbon group having 1 to 12 carbon atoms such as R2, R3 and R* include a chain hydrocarbon group such as an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and groups formed by combining these groups.
[0010] [0010] Examples of the group in which -CH>- included in the hydrocarbon group is replaced by -O- or -CO- include a hydroxy group
[0011] [0011]
[0012] [0012] In the formula (I), the iodine atom can be bonded to the ortho position, the meta position or the para position of the benzene ring with respect to S”. Of these, the iodine atom is preferably bonded to the meta position or the para position, and more preferably to the para position of the benzene ring with respect to S*. R* can be attached to the ortho position, the meta position or the para position of the benzene ring with respect to S*. Of these, R* is preferably bonded to the meta position or the para position, and more preferably to the para position, of the benzene ring relative to S*. R°, R} and R* can each be attached to the ortho position, the meta position or the para position of the benzene ring with respect to S*. Of these, R is preferably bonded to the meta or para position of the benzene ring relative to S*. When R* is bonded at the para position of the benzene ring to S*, R* is more preferably bonded to the meta position of the benzene ring to S*. R is preferably bonded to the ortho or meta position of the benzene ring relative to S*. When the iodine atom is bonded to the para position of the benzene ring relative to S*, R is more preferably bonded to the position ortho of the benzene ring to S*. R* is preferably bonded to the meta position or the para position, and more preferably at least to the para position of the benzene ring relative to S*.
[0013] [0013] Examples of the cation in the salt (I) include the cations represented by the following formula (I-c-1) to formula (I-c-20) and the like.
[0014] Among these, the cations represented by the formula (Ic-1) to the formula (Ic-6), the formula (Ic-13), the formula (Ic-14), the formula (Ic-17 ) and formula (Ic-18) are preferred, cations represented by formula (Ic-1) to formula (Ic-4), formula (Ic-13), formula (Ic-14), formula (Ic-17) and formula (Ic-18) are more preferred, cations represented by formula (Ic-1), formula (Ic-3), formula (Ic-13), formula (Ic- 14), Formula (Ic-17) and Formula (Ic-18) are more preferred, and the cations represented by Formula (Ic-1), Formula (Ic-13), Formula (Ic-14) , Formula (Ic-17) and Formula (Ic-18) are more preferred.
[0015] In the formula (I), examples of the hydrocarbon group represented by X° include an aliphatic hydrocarbon group (chain hydrocarbon groups, such as an alkyl group, an alkenyl group and an alkynyl group, and alicyclic hydrocarbon groups ), an aromatic hydrocarbon group and a group obtained by combining these groups. -CHz- included in the aliphatic hydrocarbon group can be replaced by -O-, -S-, -CO- or -SO>-.
[0016] The alicyclic hydrocarbon group or the group in which -CHz- in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO>- is preferably a group represented by any of formula (y1) to formula (y71), preferably a group represented by any one of formula (y1) to formula (y20), formula (y26), formula (y27), formula (y30 ), formula (y31) and formula (y39) to formula (y71), and more preferably a group represented by any one of formula (y3), formula (y4), formula (y9) , formula (y11), formula (y14), formula (y15), formula (y16), formula (y20), formula (y26), formula (y27), formula (y30), formula formula (y31), formula (y39), formula (y40), formula (y42), formula (y43), formula (y49) to formula (y58) and formula (y62) to formula ( y71). The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 36, more preferably 3 to 24, more preferably 3 to 18, and more preferably 3 to 16.
[0017] [0017] Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group and binaphthyl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, more preferably 6 to 18, more preferably 6 to 14, and more preferably 6 to 10.
[0018] The combined group represents: a group obtained by combining an alicyclic hydrocarbon group with a chain hydrocarbon group (-CHz- included in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S- , -CO- or -SOz-), a group obtained by combining a chain hydrocarbon group with an aromatic hydrocarbon group (-CH:- included in the chain hydrocarbon group may be replaced by -O-, -S-, - CO- or -SOz-), and a group obtained by combining an alicyclic hydrocarbon group with an aromatic hydrocarbon group (-CHz- included in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or - SOz-).
[0019] When -CH>- included in the hydrocarbon group represented by X' is replaced by -O-, -S-, -CO- or -SO--, the number of carbon atoms before replacement is taken as the total number of carbon atoms of the hydrocarbon group. When a substituent is attached to the hydrocarbon group represented by X°, the number of carbon atoms before replacement is taken as the total number of carbon atoms of the hydrocarbon group.
[0020] [0020]
[0021] [0021]
[0022] [0022] Examples of the hydrocarbon group represented by X! and Xx include an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a group obtained by combining two or more of these groups. These hydrocarbon groups may have a substituent. -CH2- included in these hydrocarbon groups can be replaced by -O-, -S-, -CO- or -SO--. The number of carbon atoms of the hydrocarbon group means the number of carbon atoms of the hydrocarbon group which has no substituent and which has not been replaced.
[0023] [0023] Examples of the aliphatic hydrocarbon group as for X* include a chain hydrocarbon group such as an alkanetriyl group, an alicyclic hydrocarbon group, or a group obtained by combining these groups.
[0024] The alicyclic hydrocarbon group can be monocyclic or polycyclic.
[0025] The hydrocarbon group represented by X'° has 1 to 24 carbon atoms, and may further have one or more substituents. Examples of the substituent include hydroxy group, halogen atom, cyano group, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, alkoxycarbonyl group having 2 to 13 carbon atoms, carbon, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an group obtained by combining these groups.
[0026] The hydrocarbon group represented by X! is preferably an alkanetriyl group having 1 to 6 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an alkanetriyl group having 1 to 6 carbon atoms, or groups represented by formula (w1-1) to formula (w1-11), and more preferably, an alkanetriyl group having 1 to 6 carbon atoms, a polycyclic hydrocarbon group such as a group represented by formula ( w1-1) or a group represented by formula (w1-3), or a monocyclic hydrocarbon group such as a group represented by formula (w1-2) or a group represented by formula (w1-6):
[0027] The number of carbon atoms of the hydrocarbon group represented by X° is preferably from 2 to 48, more preferably from 4 to 48, more preferably from 6 to 44, more preferably from 8 to 40, and more preferably from 10 to 38.
[0028] [0028] Examples of the substituent which the hydrocarbon group in X may have include hydroxy group, halogen atom, cyano group, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, carbon, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic having 6 to 10 carbon atoms, or a group obtained by combining these groups. Examples of the halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alicyclic hydrocarbon group, aromatic hydrocarbon group and the group obtained by combining these groups include the same groups than those mentioned above.
[0029] [0029] Examples of the hydrocarbon group in X“ include a straight or branched chain hydrocarbon group (e.g., alkanediyl group, etc.), a monocyclic or polycyclic alicyclic hydrocarbon group and an aromatic hydrocarbon group, and the hydrocarbon group can be obtained by combining two or more groups of these groups .
[0030] [0030] The hydrocarbon group in X is preferably: a chain hydrocarbon group having 2 to 18 carbon atoms (-CH>- included in the chain hydrocarbon group may be replaced by -O- or -CO-, and the chain hydrocarbon group may have a substituent ), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CHz- included in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO--, and the alicyclic hydrocarbon group may have a substituent), or a group obtained by combining a chain hydrocarbon group having 1 to 12 carbon atoms (-CHz- included in the chain hydrocarbon group may be replaced by -O- or -CO-) with a hydrocarbon group alicyclic having 3 to 18 carbon atoms (-CH>- included in the alicyclic hydrocarbon group can be replaced by -O-, -S-, -CO- or -SO--) (the group can have a substituent), of more preferably a chain hydrocarbon group having 4 to 18 carbon atoms (-CHz- included in the loosely chained hydrocarbon group t be replaced by -O- or -CO-, and the chain hydrocarbon group may have a substituent), or a group obtained by combining a chain hydrocarbon group having 1 to 12 carbon atoms (-CH>- included in the chain hydrocarbon group can be replaced by -O- or -CO-) with an alicyclic hydrocarbon group having 3 to 16 carbon atoms (-CH:- included in the alicyclic hydrocarbon group can be replaced by -O-, -S- , -CO- or -SO--) (the group may have a substituent), and more preferably a chain hydrocarbon group having 6 to 14 carbon atoms (-CHz- included in the chain hydrocarbon group may be replaced by -O- or -CO-, and the chain hydrocarbon group may have a substituent), or a group obtained by combining a chain hydrocarbon group having 1 to 12 carbon atoms (-CH>- included in the chain can be replaced by -O- or -CO-) with an alicyclic hydrocarbon group having 5 to 14 carbon atoms (-CH:- inclusive in the alicyclic hydrocarbon group can be replaced by -O-, -S-, -CO- or -SO--) (the group can have a substituent).
[0031] More specifically, the hydrocarbon group in X“ is preferably, for example, an alkanediyl group having 2 to 18 carbon atoms (-CH:- included in the alkanediyl group can be replaced by -O- or -CO- , and the alkanediyl group may have a substituent), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CHz- included in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO --, and the alicyclic hydrocarbon group may have a substituent), a group consisting of an alkanediyl group having 1 to 12 carbon atoms (-CH:- included in the alkanediyl group may be replaced by -O- or -CO- ) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CH:- included in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO>-) (the group may have a substituent), or a group consisting of an alkanediyl group having 1 to 12 carbon atoms (-CH:- included in the alkanediyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms and an alkyl group having 1 to 12 carbon atoms (-CH>- included in the alkyl group may be replaced by -O- or -CO-) (the group can have a substituent),
[0032] [0032] More precisely, X” is preferably a group represented by formula (X -1), a group represented by formula (X -2), a group represented by formula (X -3) or a group represented by formula (X2 -4): 0 RX * * A2 x* {€ Da. lo R1x 2 R3x D + + y + T x Ö y (X2-1) (X2-2) (X2-3) RX (X24) where RX, RX RX R*, R” and R% each independently represent a group alkyl having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group obtained by combining two or more of these groups, -CHz - included in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -S- -CO- or -SO--, and the alkyl group and the alicyclic hydrocarbon group may have a substituent, and * represents a binding site to X and X®, The combined group may be either one of those obtained by combining each of the alkyl group and the alicyclic hydrocarbon group mentioned above, or one of those obtained by combining two or more of one of them or both. In this case, the number of carbon atoms of the combined group is 39 or less, and preferably 37 or less.
[0033] [0033] Of these, RIX, R*, RX, R% R” and R% are preferably an alkyl group having 1 to 6 carbon atoms (-CHz- included in the alkyl group may be replaced by -O - or -CO-, and the alkyl group may have a substituent), an alicyclic hydrocarbon group having 5 to 12 carbon atoms (-CH:- included in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO--, and the alicyclic hydrocarbon group may have a substituent) or a group obtained by combining an alkyl group having 1 to 6 carbon atoms (-CH:- included in the alkyl group may be replaced by - O- or -CO-) with an alicyclic hydrocarbon group having 5 to 12 carbon atoms (-CHz- included in the alicyclic hydrocarbon group can be replaced by -O-, -S-, -CO- or -SOz-) ( the group may have a substituent), and more preferably a methoxy group, an adamantyl group (-CHz- included in the adamantyl group may be replaced by -O- or -CO-, and the adamantyl group may have a substituent) or a group obtained by combining an alkyl group having 1 to 6 carbon atoms (-CHz- included in the alkyl group may be replaced by -O- or -CO-) with an adamantyl group (the group may have a substituent).
[0034] [0034] In the formula (bb), examples of the alkanediyl group having 1 to 6 carbon atoms in LA and LB include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3- diyl, butane-1,4-diyl group, pentane-1,5-diyl group and hexane-1,6-diyl group; and branched alkanediyl groups such as propane-1,2-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1, 2-diyl, a 1-methylbutane-1,4-diyl group and a 2-methylbutane-1,4-diyl group. The number of carbon atoms of the alkanediyl group is preferably 1 to 4, and more preferably 1 to 3. Examples of the alkanediyl group which may have a fluorine atom include perfluoroalkanediyl groups such as a difluoromethylene group, a perfluoroethylene group, a perfluoropropanediyl group, a perfluorobutanediyl group and a perfluoropentanediyl group. When -CH:- included in the alkanediyl group is replaced by -O- or -CO-, the number of carbon atoms before replacement is taken as the total number of carbon atoms of the alkanediyl group. Alkanediyl group can have hydroxy group (a group in which -CHz- included in the methyl group is replaced by -O-), carboxy group (a group in which -CHz-CH>- included in the ethyl group is replaced by -O-CO-), an alkoxy group (a group in which -CHz- included at any position in the alkyl group is replaced by -O-), an alkoxycarbonyl group (a group in which -CH:- CH:- included at any position in the alkyl group is replaced by -O-CO-),
[0035] [0035]
[0036] [0036] Examples of the substituent which may belong to the hydrocarbon group as for RA include a halogen atom, a cyano group and an alkyl group having 1 to 12 carbon atoms (-CHz- included in the alkyl group may be replaced by - O-, -S-, -CO- or -S02-).
[0037] The hydrocarbon group in R is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent (-CHz- included in the alkyl group may be replaced by -O-, -S-, -CO- or -S0:-) or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (-CHz- included in the cyclic hydrocarbon group which may be replaced by -O-, -S-, -CO- or -SOz- ), and preferably a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 6 carbon atoms (-CH:- included in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO--).
[0038] [0038] Examples of the cyclic hydrocarbon group include cyclic hydrocarbon groups such as a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups.
[0039] [0039] The cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 6 carbon atoms, and -CHz>- included in the group cyclic hydrocarbon group can be replaced by -O-, -S-, -CO- or -SO--) is preferably: an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or a alkyl group having 1 to 4 carbon atoms (-CHz- included in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SOz-), or an aromatic hydrocarbon group having 6 to 18 atoms carbon group which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms, and more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy or an alkyl group having 1 to 4 carbon atoms (-CHz- included in the hydrocarbon group alicyclic can be replaced by -O- or -CO-).
[0040] [0040] Examples of the carboxylic acid anion in the carboxylate represented by the formula (I) include the carboxylic acid anions mentioned below.
[0041] [0041] Q H oO Q D © 5, y ter x A. (I-a-14) (l-a-15) (I-a-16)
[0042] [0042] 9 H,C _ > H3C - HsC _ 00 HO Q 0 DS X
[0043] [0043] of Se 9 OH 3e 07 © A A Ô (-a-34) Ô (l-a-35) (l-a-36) De Ag Ae Oo (l-a-37) Ö (I-a-38) (I-a-39)
[0044] [0044] 2% N H FA > GE. Fri, (La-43) dada) 9 (l-a-45)
[0045] [0045] F F F _ | F | A F F F O HO a. OH CEE 0 (|-a-55) - (I-a-56) (|-a-57)
[0046] [0046]
[0047] [0047] Specific examples of the carboxylate (I) include the salts obtained by optionally combining the cations and anions mentioned above. Specific examples of the carboxylate (I) are shown in the following table.
[0048] Of these, carboxylate (I) preferably includes carboxylate (I-1) to carboxylate (I-5), carboxylate (I-55) to carboxylate (1-59), carboxylate (I -109) to carboxylate (I-113), carboxylate (I- 163) to carboxylate (I-167), carboxylate (I-217) to carboxylate (I-221), carboxylate (I-271) to carboxylate salt (I-275), carboxylate (1-325) to carboxylate (1-329), carboxylate (I-379) to carboxylate (1-383), carboxylate (1-433) to carboxylate (I-437 ), carboxylate (I-487) to carboxylate (I-491), carboxylate (I-541) to carboxylate (I-545), carboxylate (I-595) to carboxylate (I-599), carboxylate ( I-649) to carboxylate (1-653), carboxylate (I-703) to carboxylate (I-707), carboxylate (I-757) to carboxylate (I-761), carboxylate (I-811) to carboxylate (I-815), carboxylate (I-865) to carboxylate (I-896), carboxylate (I-919) to carboxylate (I-923), carboxylate (I-973) to carboxylate (I- 977), carboxylate (I-1027) to carboxylate ( I-1031), carboxylate (I-1081) to carboxylate (I-1098), carboxylate (I-1120) to carboxylate (I-1137), carboxylate (I-1159) to carboxylate (I-1176), carboxylate (I-1198) to carboxylate (I-1215), carboxylate (I-1237) to carboxylate (I-1254), carboxylate (I-1276) to carboxylate (I-1293), carboxylate (1- 1315) to carboxylate (I-1332), carboxylate (I-1354) to carboxylate (I-1371), carboxylate (I-1393) to carboxylate (I-1410), carboxylate (I-1432) to carboxylate ( I-1449), carboxylate (I-1471) to carboxylate (I-1488), carboxylate (I-1510) to carboxylate (I-1527), carboxylate (I-1549) to carboxylate (I-1566), carboxylate (I-1588) to carboxylate (I-1605), carboxylate (I-1627) to carboxylate (I-1644), carboxylate (I-1666) to carboxylate (I-1683), carboxylate (I- 1705) to carboxylate (I-1722), carboxylate (I-1744) to carboxylate (I-1761), carboxylate (I-1783) to carboxylate (1-1800) and carboxylate (I-1822) to carboxylate ( I-1839).
[0049] <Method for producing the carboxylate salt (I)> The carboxylate (I) can be produced by reacting a salt represented by the formula (Ia) with a salt represented by the formula (Ib) in a solvent: ( RD m2 (R°)m2 > > ( CF3SO; RI O2C—X° O,C—X° SS + RD—N—RB —— SL ge, 79 (R3)m3 (R)ma (R3)mg (R °)ma (Ia) (TD) where all the symbols are identical to those defined above, RA RB and RC each independently represent a hydrocarbon group having 1 to 12 carbon atoms, or RA, RB and R“ can be combined together to form an aromatic ring, and RP represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
[0050] [0050] Examples of the salt represented by the formula (I-a) include the salts represented by the following formulas, which are readily available in the market, and can also be easily produced by a known production method. © 9 Oo” N + _ + _ + _ + _ KA} CF3S03 AK} CF,s0, | Ç ) CFsSO3 A} CF3S03 CFs F 9 9 7 { 9 | | + _ + + _ + _ (D'or; A} CF,SO7 a CF,S0; a. CFoSO, | | |
[0051] [0051] The salt represented by the formula (Ib) can be synthesized with reference to the methods mentioned in JP 2011-39502 A, JP 2014-88367 A and JP 2013-200561 A, and examples thereof include following salts.
[0052] [Carboxylic acid generator] The carboxylic acid generator of the present invention is an acid generator including a carboxylate salt (I). The carboxylate (I) of the present invention can act as an acid generator in the resist composition. When carboxylate (I) is used as the acid generator in the resist composition, the acid generator may include only one or two or more carboxylate (I).
[0053] [Resist composition] The resist composition includes a carboxylic acid generator comprising the carboxylate (T) of the present invention, an acid generator (B) other than the carboxylic acid generator, and a resin having an acid-labile group (hereinafter sometimes referred to as "resin (A)"). The "acid-labile group" herein means a group having a leaving group which is removed by contact with an acid, thereby forming a group hydrophilic (for example, a hydroxy group or a carboxy group).
[0054] <Acid generator (B)> In the resist composition of the present invention, a ratio (mass ratio; carboxylate (T): acid generator (B)) of the content of carboxylate (I) to that of acid generator (B) is usually 1:99 to 100:0, preferably 1:99 to 99:1, more preferably 2:98 to 98:2, and more preferably 5: 95 to 95:5.
[0055] A nonionic or ionic acid generator can be used as acid generator (B). Examples of nonionic acid generator include sulfonate esters (eg, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (eg, disulfone, ketosulfone, sulfonyldiazomethane) and the like. Typical examples of the ionic acid generator include onium salts containing an onium cation (eg, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the onium salt anion include sulfonic acid anion, sulfonylimide anion, sulfonylmethide anion and the like.
[0056] [0056] Specific examples of the acid generator (B) include compounds generating acid upon exposure to radiation mentioned in JP 63-26653 A, JP 55-164824 A, JP 62-69263 A, JP 63-146038 A , JP 63-163452 A, JP 62-153853 A, JP 63-146029 A, US Patent No.
[0057] The acid generator (B) is preferably an acid generator containing fluorine, and more preferably a salt represented by the formula (B1) (hereinafter sometimes called “acid generator (B1) "): Qh + -0.S [61 21 OS AS, (B) des where, in the formula (B1), Q% and Q° each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon, LP represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CHz- included in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom included in the group divalent saturated hydrocarbon can be substituted with a fluorine atom or a hydroxy group,
[0058] [0058] Examples of the perfluoroalkyl group represented by Q1 and QP2 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group. and a perfluorohexyl group.
[0059] [0059] Examples of divalent saturated hydrocarbon group in LP include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, or the divalent saturated hydrocarbon group may be a group formed by combining two or more of these groups in combination.
[0060] The group in which -CH>- included in the divalent saturated hydrocarbon group represented by LP! is replaced by -O- or -CO- includes, for example, a group represented by any one of formula (b1-1) to formula (b1-3). In the groups represented by formula (b1-1) to formula (b1-3) and the groups represented by formula (b1-4) to formula (b1-11) which are specific examples thereof, * and ** represent a binding site, and * represents a -Y binding site.
[0061] [0061]
[0082] [0082] In the groups represented by the formula (b1-1) to the formula (b1-3), when -CHz- included in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of atoms of carbon before replacement is taken as the number of carbon atoms of the saturated hydrocarbon group.
[0063] [0063] LP is preferably a single bond.
[0064] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by L' is replaced by -O- or -CO- is preferably a group represented by formula (b1-1) or formula (b1 - 3).
[0065] [0065] Examples of the group represented by the formula (b1-1) include the groups represented by the formula (b1-4) to the formula (b1-8): 9 9 b11 1 b12 Ao tE, Ae ARE, (b1 -4) 1-5)” (b1-6) 9 N b16 AO AO TON 01 8-*
[0066] [0066] LPS is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
[0087] [0087] Examples of the group represented by the formula (b1-3) include the groups represented by the formula (b1-9) to the formula (b1-11). er LAS od LS LOS 06 a LS ls
[0068] [0068] In groups represented by formula (b1-9) to formula (b1-11), when a hydrogen atom included in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before the substitution is taken as the number of carbon atoms of the saturated hydrocarbon group.
[0069] [0069] Examples of the alkylcarbonyloxy group include acetyloxy group, propionyloxy group, butyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group and the like.
[0070] [0070] Examples of the group represented by the formula (b1-4) include the following: CH3
[0071] [0071] Examples of the group represented by the formula (b1-5) include the following:
[0072] [0072] Examples of the group represented by the formula (b1-6) include the following: 9 9 A À . Oe As VC HOT, ot oo otho; Soto Pdre Ade Ag ANN
[0073] [0073] Examples of the group represented by the formula (b1-7) include the following: oO CHs O O x VA, Ae A en Se Sese CR COTE Q 9 9 x Ay A ANG SA SAND
[0074] [0074] Examples of the group represented by the formula (b1-8) include the following:
[0075] [0075] Examples of the group represented by the formula (b1-2) include the following: 3 3 > Hz 4 Hs
[0076] [0076] Examples of the group represented by the formula (b1-9) include the following:
[0077] [0077] Examples of the group represented by the formula (b1-10) include the following:
[0078] [0078] Examples of the group represented by the formula (b1-11) include the following: Hs O LE otd otho otho: AA. YY.
[0079] [0079] Examples of the alicyclic hydrocarbon group represented by Y include groups represented by formula (Y1) to formula (Y11) and by formula (Y36) to formula (Y38).
[0080] The alicyclic hydrocarbon group represented by Y is preferably a group represented by any one of formula (Y1) to formula (Y20), formula (Y26), formula (Y27), formula (Y30 ), formula (Y31) and formula (Y39) to formula (Y43), more preferably a group represented by formula (Y11), formula (Y15), formula (Y16), formula (Y20) , formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43), and more preferably a group represented by formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43). When the alicyclic hydrocarbon group represented by Y is a spiro ring containing an oxygen atom such as formula (Y28) to formula (Y35), formula (Y39), formula (Y40), formula (Y42) or formula (Y43), the alkanediyl group between two oxygen atoms preferably has one or more fluorine atoms. Of the alkanediyl groups included in a ketal structure, it is preferred that a methylene group adjacent to the oxygen atom not be substituted with a fluorine atom.
[0081] [0081] Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an glycidyloxy, a -(CHz)ja-CO-OR®! or a group -(CH2);-O-CO-RE (where RP represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups, and -CHz- included in an alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SOz- or -CO-, a hydrogen atom included in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted by a hydroxy group or a fluorine atom, and j represents an integer of 0 to 4).
[0082] [0082] Examples of halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.
[0083] [0083] Examples of Y include the following.
[0084] [0084] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, more preferably a hydrocarbon group alicyclic having 3 to 18 carbon atoms which may have a substituent, more preferably an adamantyl group which may have a substituent, and -CH;- constituting the alicyclic hydrocarbon group or the adamantyl group may be replaced by -CO-, - S(0)>- or -CO-. Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or groups represented by formula (Y42) and formula (Y100) to formula (Y114).
[0085] [0085]
[0086] [0086] OH Oo ab! ‚ar " b1 qb SE OX a! ‚Q _ Oo ' 0:57 Sim Costs os7 LE OO 0 (B1-A-1) (B1-A-2) (B1-A-3) Qh Qb2 Qh Qb2 Ri2 a! Q»2
[0087] [0087]
[0088] [0088] om 2 Oo CH; at! a“ O CH3 _ O_ Ad - os SpA4 TY L O Ö 9 O TO O
[0089] [0089]
[0090] [0090] oO O
[0091] [0091] Q ° OH Q% O2 09 Q% to» 24 Id oe SE OX 9 9 (B1-A-57) (B1-A-56) + od O P o_Ê QU à» IF QT Qb ST A an Se O (B1-A-58) O (B1-A-59) R to RU each independently represent, for example, an alkyl group having 1 to 4 carbon atoms, and preferably a methyl group or a group ethyl. R is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms or a group obtained by combining these groups , and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L** is a single bond or an alkanediyl group having 1 to 4 carbon atoms. QP! and QP2 are the same as those defined above. Specific examples of the anion in the salt represented by the formula (B1) include anions mentioned in JP 2010-204646 A.
[0092] A preferred anion in the salt represented by formula (B1) includes anions represented by formula (B1a-1) to formula (B1a-38).
[0093] [0093]
[0094] [0094] df To Dr Que eos 9 OOOO — RFF = — F OS O3 Os ï (Bla-23) (Bla-24) (Bla-25) From A Ar X HO Se 0 Ò = ESF _ RFA — FF Os 035 Os (Bla-26) (Bla-27) 0 (Bla-28) 0, LF — FF O CH (Bla-31) (Bla-29) (Bla-30) O LF > Fe KF Ee © | A TG T° Cd ST
[0095] Of these, an anion represented by any one of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula (B1a-19) and formula (B1a-22) to formula (B1a-38) is preferred.
[0096] [0096] Examples of organic cation of Z1* include organic onium cation, organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation and organic phosphonium cation. Of these, an organic sulfonium cation and an organic iodonium cation are preferred, and an arylsulfonium cation is more preferred. Specific examples thereof include a cation represented by any one of formula (b2-1) to formula (b2-4) (hereinafter sometimes referred to as "cation (b2-1)" depending on the number of the formula).
[0102] [0102] (RES) 2 (RP) 2 b5 e= Dn we 0 © (RB15) © + =|= _ + a pDb12 Rr o be S b18 (b2-1) (b2-2) (b2-3) Pt A], 1241) (b2-4) In formula (b2-1) to formula (b2-4), RP* to RP each independently represent a chain hydrocarbon group having 1 to 30 carbon atoms, a group alicyclic hydrocarbon group having 3 to 36 carbon atoms or an aromatic hydrocarbon group having 6 to 36 carbon atoms, a hydrogen atom included in the chain hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 atoms carbon, an alicyclic hydrocarbon group having 3 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, a hydrogen atom included in the alicyclic hydrocarbon group may be substituted with a halogen atom, a group aliphatic hydrocarbon having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group, and a hydrogen atom included in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkyl fluoride group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, RP* and RP5 can be bonded to each other to form a ring with the sulfur atoms to which RP* and RP° are bonded, and -CHz- included in the ring can be replaced by -O -, -S- or -CO-,
[0097] Among the cation (b2-1) to the cation (b2-4), a cation (b2-1) is preferred. Examples of cation (b2-1) include the following cations. © CoHs & OS CgH13 CgH17 GG ade QL 545 95 95 5 O3 % (b2-c-1) (b2-c-2) (b2-c-3) (b2-c-4) (b2-c-5) (b2-c-6) (b2-c-7) (b2-c-8) Hs Hs Hs -C,Hg -C4Hg © © Ce ® ® (4 a. “4 Le in (ron {yy OP H aL tC,H (b2-c-14) (b2-c-9) (b2-c-10) (b2-c-1 1) (b2 C 12) (02-013)
[0098] [0098]
[0099] [0099] Examples of cation (b2-2) include the following cations and the like.
[0100] [0100] Examples of cation (b2-3) include the following cations and the like. Q 0 ® 0 0 £) A co oo (b2-c-31) (b2-c-32) (b2-c-33) (b2-c-34)
[0101] [0101] Examples of cation (b2-4) include the following cations and the like.
[0102] [0102] The acid generator (B) is a combination of the aforementioned anion and the aforementioned organic cation, and these may be optionally combined. The acid generator (B) preferably includes a combination of an anion represented by any one of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (Bla-16), formula (B1a-18), formula (Bla-19) and from formula (B1a-22) to formula (B1a-38) with a cation (b2-1), a cation (b2-3), a cation (b2-4).
[0103] [0103] The acid generator (B) preferably includes those represented by the formula (B1-1) to the formula (B1-56). Among these acid generators, those containing an arylsulfonium cation are preferred, and those represented by formula (B1-1) to formula (B1-3), formula (B1-5) to formula (B1-7) , formula (B1-11) to formula (B1-14), formula (B1-20) to formula (B1-26), formula (B1-29) and formula (B1-31) to formula (B1-56) are particularly preferred.
[0104] [0104] where your A
[0105] [0105] Oh. LT 0 DL 4 va, T° ee (81-22) 43 SS y LM 8 CA (B1-23) (B1-24)
[0106] [0106] |
[0107] [0107]
[0108] [0108] <Resin (A)> Resin (A) includes a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). It is preferred that resin (A) includes further a structural unit other than structural unit (a1) Examples of structural unit other than structural unit (a1) include a structural unit having no acid-labile group (hereinafter sometimes referred to as “structural unit(s)"), a structural unit other than the structural unit (a1) and the structural unit(s) (e.g. a structural unit having a halogen atom mentioned later (hereinafter sometimes referred to as “ structural unit (a4)"), a structural unit having a non-leaving hydrocarbon group mentioned later (hereinafter sometimes referred to as "structural unit (a5)") and other structural units derived from monomers known in the art.
[0109] [0109] <Structural unit (a1)> The structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter sometimes referred to as “monomer (a1).
[0110] [0110] Examples of the alkyl group for R2%, R22 and R°° include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group and analogues.
[0111] [0111]
[0112] [0112]
[0113] [0113] Specific examples of group (2) include the following groups. * represents a binding position. ANA 10 ee AD PP) eh , C © | AK Y 0 TO A T° we © mea TCD , Ar PER spa IE PASS IS TE WO OO YO oe
[0114] The monomer (al) is preferably a monomer having an acid-labile group and an ethylenically unsaturated bond, and more preferably a (meth)acrylic monomer having an acid-labile group.
[0115] Among the (meth)acrylic monomers having an acid-labile group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferably cited by way of example. When a resin (A) including a structural unit derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in a resist composition, it is possible to improve the resolution of a resist pattern.
[0116] [0116] The structural unit derived from a (meth)acrylic monomer having a group (1) is preferably a structural unit represented by the formula (a1-0) (hereinafter sometimes referred to as structural unit (a1-0) , a structural unit represented by the formula (a1-1) (hereinafter sometimes referred to as structural unit (a1-1)) or a structural unit represented by the formula (a1-2) (hereinafter sometimes referred to as structural unit (a1 -2) ).The structural unit is preferably at least one structural unit selected from the group consisting of a structural unit (a1-1) and a structural unit (a1-2).These structural units can be used alone, or two or more structural units may be used in combination Ls Ra01 Ls Ra4 Ls Ra5 C St C St C El
[0117] [0117] R20! R°* and R°° are hydrogen or methyl, and more preferably methyl.
[0118] The structural unit (a1-0) includes, for example, a structural unit represented by any one of formula (a1-0-1) to formula (a1-0-18) and a structural unit wherein a methyl group corresponding to R*° in the structural unit (a1-0) is substituted by a hydrogen atom and is preferably a structural unit represented by any one of the formula (a1-0-1 ) to the formula (a1-0-10), the formula (a1-0-13) and the formula (a1-0-14).
[0119] [0119] The structural unit (a1-1) includes, for example, structural units derived from the monomers mentioned in JP 2010-204646 A. Among these structural units, a structural unit represented by any one of the formula (a1-1-1) to the formula (a1-1-7) and a structural unit in which a methyl group corresponding to R** in the structural unit (a1-1) is substituted by a hydrogen atom are preferred, and a structural unit represented by any one of formula (a1-1-1) to formula (a1-1-4) is more preferred. + Hs Le Hs Le Hs Le Hs Le H3 Lt Hz I Hz 2 N (a1-1-1) (a1-1-2) (a1-1-3) (a1-1-5) (a1-1-6 ) (a1-1-7) (a1-1-4)
[0120] [0120] Examples of structural unit (a1-2) include a structural unit represented by any one of formula (a1-2-1) to formula (a1-2-12) and a structural unit in which a methyl group corresponding to R® in the structural unit (a1-2) is substituted by a hydrogen atom and a structural unit represented by any one of formula (a1-2-2), formula (a1-2 -5), formula (a1-2-6) and formula (a1-2-10) to formula (a1-2-12) is preferable.
[0121] When the resin (A) comprises a structural unit (a1-0), its content is generally from 5 to 60 mol%, preferably from 5 to 50 mol%, and more preferably from 10 to 40 mol%, on the base of all the structural units of the resin (A).
[0122] [0122] In the structural unit (a1), examples of the structural unit having a group (2) include a structural unit represented by the formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1- 4)>):
[0123] [0123] Examples of halogen atom in R232 and R233 include fluorine atom, chlorine atom and bromine atom.
[0124] [0124] Examples of *-X°*-(a2%2-X232),e- include *-O-, *-CO-O-, *-O-CO-, *-CO-0-A332- CO-0-, *-0-CO-A332-0-, *-0-A332-CO-0-, *-CO-0-A%32-0- CO- and *-0-CO-A232- 0-CO-. Of these, *-CO-O-, *-CO-0-A332-CO-0- or *-O-A332-CO-O- are preferable.
[0125] [0125] Examples of the alkanediyl group in A include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2- diyl, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
[0126] [0126] A is preferably a single bond, *-CO-O- or *-CO-O- A232-CO-O-, more preferably a single bond, *-CO-O- or *-CO-O -CHz-CO-O-, and more preferably a single bond or *-CO-O-.
[0127] la is preferably 0, 1 or 2, more preferably 0 or 1, and more preferably 0.
[0128] [0128] R33* is preferably a hydrogen atom, and R335 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a methyl group or an ethyl group. The hydrocarbon group of R°° is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group obtained by combining these groups, and more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group of R®® are preferably unsubstituted. The aromatic hydrocarbon group in R° is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.
[0129] [0129]
[0130] [0130]
[0131] [0131] The halogen atom includes a fluorine atom and a chlorine atom and is preferably a fluorine atom is preferred. Examples of the alkyl group having 1 to 6 carbon atoms optionally having a halogen atom include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl, a fluoromethyl group and a trifluoromethyl group. In the formula (a1-5), R°® is preferably a hydrogen atom, a methyl group or a trifluoromethyl group, L° is preferably an oxygen atom, De L” and L53, Vun is preferably -O- and the other is preferably -S-, s1 is preferably 1, sl' is preferably an integer from 0 to 2, and zt is preferably a single bond or *-CHz-CO-O-.
[0132] [0132] Examples of the structural unit (a1-5) include structural units derived from the monomers mentioned in JP 2010-61117 A.
[0133] [0133] The structural unit (a1) also includes, for example, a structural unit represented by the formula (a1-OX) (hereinafter sometimes referred to as structural unit (a1-0X)): Rx! tone} LO (a1-OX)
[0134] [0134]
[0135] [0135] Examples of the structural unit (a1-OX) include structural units in the following and in which a methyl group corresponding to R* in the structural unit (a1-OX) is substituted by a hydrogen atom. The structural unit (a1-OX) is preferably one structural unit (a1-OX-1) to one structural unit (a1-OX-3).
[0136] The structural unit (a1) also includes the following structural units. er al tal ta tal ter X OO DD" € (a1-3-1) (a1-3-2) (a1-3-3) (a1-3-4) © (a1-3-5) (a1- 3-6) (a1-3-7) When the resin (A) includes the structural units mentioned above, the content is preferably 5 to 60 mol% mol%, more preferably 5 to 50 mol%, more preferably 10 to 40 mol%, based on all structural units of resin (A).
[0137] [0137] <Structural Unit(s)> The structural unit(s) derives from a monomer having no acid-labile group (hereinafter referred to as "monomer(s)"). It is possible to use as the monomer from which the structural unit(s) derives, a monomer having no acid-labile group known in the resist field.
[0138] <Structural Unit (a2)> The hydroxy group belonging to the structural unit (a2) may be either an alcoholic hydroxy group or a phenolic hydroxy group.
[0139] [0139] In the structural unit (a2), examples of the structural unit having a phenolic hydroxy group include a structural unit represented by the formula (a2-A) (hereinafter sometimes referred to as "structural unit (a2-A )»): R2a50
[0140] [0140] Examples of the halogen atom in R®° and R°* include a fluorine atom, a chlorine atom and a bromine atom.
[0141] [0141] Examples of *-X2*!-(a252-X°52)p- include *-O-, *-CO-O-, *-0-CO-, *-CO-O-A3 - CO-O-, *-O-CO-A3 -O-, *-OA°* -CO-O-, *-CO-0-A°**-0- CO- and *-O-CO -A®%*-0-CO-. Of these, *-CO-O-, *-CO-O-A®%*-CO-O- or *-O-A°°-CO-O- is preferred.
[0142] Examples of structural unit (a2-A) include structural units derived from monomers mentioned in JP 2010-204634 A and JP 2012-12577 A.
[0143] [0143] Examples of the structural unit having an alcoholic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as “structural unit (a2-1)” ).
[0144] In the formula (a2-1), L°* is preferably -O- or -O-(CH2); -CO- O- (fl represents an integer from 1 to 4), and more preferably - O-, R31* is preferably a methyl group, R2!5 is preferably a hydrogen atom, RS is preferably a hydrogen atom or a hydroxy group, and o1 is preferably an integer from 0 to 3, and more preferably 0 or 1.
[0145] [0145] The structural unit (a2-1) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646 A. A structural unit represented by any one of the formula (a2-1-1) to the formula (a2-1-6) is preferred, a structural unit represented by any one of the formula (a2-1-1) to the formula (a2-1-4) is more preferred, and a structural unit represented by formula (a2-1-1) or formula (a2-1-3) is more preferred.
[0146] [0146] <Structural unit (a3)> The lactone ring belonging to the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring or an α-valerolactone ring, or a condensed ring one monocyclic lactone ring and the other ring. Preferably, a γ-butyrolactone ring, an adamantanelactone ring or a bridged ring including a γ-butyrolactone ring structure (eg, a structural unit represented by the following formula (a3-2)) is exemplified. The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3) or the formula (a3-4). These structural units may be included alone, or two or more structural units may be included: not R219 fe fe | | - - - CH tt tet or =} =S 24 / xa3 a6 La7 (Rp (‘es T$ (R223) (RS) O (R222) a 5 O
[0147] [0147] Examples of the aliphatic hydrocarbon group in R°*, R222, R223 and R°°° include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec -butyl and a tert-butyl group.
[0148] [0148] Examples of alkanediyl group in L® and L® include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4 group -diyl, pentane-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane group - 1,2-diyl, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
[0149] In formula (a3-1) to formula (a3-3), preferably, L°* to L°° are each independently -O- or a group in which k3 is an integer from 1 to 4 in *-O-(CH2)(3-CO-O-, more preferably -O- and *-O-CH2-CO-O-, and more preferably an oxygen atom, RAS at R°2! are preferably a methyl group, preferably, R°° and R223 are each independently a carboxy group, a cyano group or a methyl group, and preferably, p1, q1 and r1 are each independently an integer from 0 to 2, and preferably still 0 or 1.
[0150] [0150] In the formula (a3-4), R** is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or a group ethyl, and more preferably a hydrogen atom or a methyl group, R225 is preferably a carboxy group, a cyano group or a methyl group,
[0151] Examples of structural unit (a3) include structural units derived from monomers mentioned in JP 2010-204646 A, monomers mentioned in JP 2000-122294 A and monomers mentioned in JP 2012-41274 A. structure (a3) is preferably a structural unit represented by any one of formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula ( a3- 2-2), the formula (a3-3-1), the formula (a3-3-2) and the formula (a3-4-1) to the formula (a3-4-12), and the units structural groups in which the methyl groups corresponding to R°1$, R°1°, R220 and R°°* in the formula (a3-1) to the formula (a3-4) are substituted with hydrogen atoms in the structural units above.
[0152] [0152] <Structural unit (a4)> Examples of structural unit (a4) include the following structural units: 41 HR
[0153] [0153] Examples of the chain saturated hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group.
[0154] [0154] Examples of structural unit (a4) include a structural unit represented by at least one selected from the group consisting of formula (a4-0), formula (a4-1), formula (a4-2) , the formula (a4-3) and the formula (a4-4):
[0155] [0155] Examples of the alkanediyl group in L* include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group and butane-1,4-diyl group; and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl.
[0156] [0156] Examples of perfluoroalkanediyl group in L“ include difluoromethylene group, perfluoroethylene group, perfluoropropane-1,1-diyl group, perfluoropropane-1,3-diyl group, perfluoropropane-1,2-diyl group, a perfluoropropane-2,2-diyl group, a perfluorobutane-1,4-diyl group, a perfluorobutane-2,2-diyl group, a perfluorobutane-1,2-diyl group, a perfluoropentane-1,5-diyl group, a perfluoropentane-2,2-diyl group, a perfluoropentane-3,3-diyl group, a perfluorohexane-1,6-diyl group, a perfluoro-hexane-2,2-diyl group, a perfluorohexane-3,3- diyl, a perfluoroheptane-1,7-diyl group, a perfluoroheptane-2,2-diyl group, a perfluoroheptane-3,4-diyl group, a perfluoroheptane-4,4-diyl group, a perfluorooctane-1,8- diyl, a perfluorooctane-2,2-diyl group,
[0157] [0157] L is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
[0158] [0158] Examples of the structural unit (a4-0) include the following structural units, and structural units in which a methyl group corresponding to R*° in the structural unit (a4-0) is substituted with a d hydrogen in the following structural units: Hz Hz Hz Hs Hz Hz tof or Ste fe St Fo F F3 F F3 Fo F2 Fa HF, FH F3 F2H (a4-0-5) (a4-0-6) (a4-0 -1) (a4-0-2) (a4-0-3) (a4-0-4)
[0159] [0159]
[0160] [0160] Examples of the saturated hydrocarbon group in R** include a chain saturated hydrocarbon group and a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and the groups obtained by combining these groups.
[0161] [0161] Examples of the chain saturated hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group.
[0162] [0162] Examples of the substituent belonging to R°* include at least one selected from the group consisting of a halogen atom and a group represented by the formula (a-g3). Examples of halogen atom — include fluorine atom, chlorine atom, bromine atom and iodine atom, and fluorine atom is preferred: x ——a43_ p a45 (a-g3) where, in the formula (a-g3), X represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-,
[0163] [0163] Examples of the aliphatic hydrocarbon group in A include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group; monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* represents a bonding site). » D 0 LD --6D-C-C05-CED Examples of the group formed by combination include a group obtained by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, and include an alkanediyl group -alicyclic hydrocarbon group, alicyclic hydrocarbon group-alkyl group, alkanediyl group-alicyclic hydrocarbon group-alkyl group and the like.
[0164] [0164] R°*2 is preferably a saturated hydrocarbon group optionally having a halogen atom, and more preferably an alkyl group having a halogen atom and/or a saturated hydrocarbon group having a group represented by the formula ( a-g3). When R** is a saturated hydrocarbon group having a halogen atom, a saturated hydrocarbon group having a fluorine atom is preferred, a perfluoroalkyl group or a perfluorocycloalkyl group is more preferred, a perfluoroalkyl group having 1 to 6 carbon atoms is more preferred, and a perfluoroalkyl group having 1 to 3 carbon atoms is particularly preferred. Examples of perfluoroalkyl group include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group and perfluorooctyl group. Examples of perfluorocycloalkyl group include perfluorocyclohexyl group and the like. When R * is a saturated hydrocarbon group having a group represented by formula (a-g3), the total number of carbon atoms of R°* is preferably 15 or less, and more preferably 12 or less, including the number of carbon atoms included in the group represented by the formula (a-g3). When it has the group represented by the formula (a-g3) as a substituent, their number is preferably 1.
[0165] [0165] When R°* is a saturated hydrocarbon group having the group represented by formula (a-g3), R°° is more preferably a group represented by formula (a-g2): 4 —A946_ yad4__na47 (a -g2) where, in the formula (a-g2), A°*° represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, X21* represents **-O-CO- or **-CO-O- (** represents a binding site to A2), A27 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, the total number of carbon atoms of A °°, A and X°** is 18 or less, and at least one of A°* and A°* has at least one halogen atom, and * represents a bonding site to a carbonyl group.
[0166] The number of carbon atoms of the saturated hydrocarbon group of A°*° is preferably 1 to 6, and more preferably 1 to 3.
[0167] [0167]
[0168] [0168] Examples of alkanediyl group in A * include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane- 1,5-diyl and a hexane-1,6-diyl group; and branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
[0169] [0169] Examples of the divalent saturated hydrocarbon group represented by A22 A°° and A ** in the group represented by formula (a-g1) include a linear or branched alkanediyl group and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. , and hydrocarbon groups obtained by combining an alkanediyl group with a divalent alicyclic saturated hydrocarbon group. Specific examples thereof include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1- methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like.
[0170] [0170] In the group represented by the formula (a-g1), examples of the group in which X** is -O-, -CO-, -CO-O- or -O-CO- include the following groups. In the following examples, * and ** each represent a binding site, and ** represents a binding site at -O-CO-R°*, TN ex A Sa AN ea x st ON on ee 5; © 50 NH oo VU OT OT as TT O akk O ak O. *# x, xr © O. 4 FX ES se SA Ss
[0171] [0171] Examples of the structural unit represented by the formula (a4-1) include the following structural units, and the structural units in which a methyl group corresponding to A°* in the structural unit represented by the formula (a4- 1) in the following structural units is substituted with a hydrogen atom.
[0172] [0172] Hs Hs Hg Hs Hs Hs T er: er: er: er: er: O O O O
[0173] The structural unit represented by formula (a4-1) is preferably a structural unit represented by formula (a4-2). Hs R® 0 O Laa (a4-2) Oo
[0174] [0174] Examples of the alkanediyl group as for L** include the same groups as mentioned for A3*!.
[0175] [0175] The structural unit represented by the formula (a4-2) includes, for example, the structural units represented by the formula (a4-1-1) to the formula (a4-1-11). A structural unit in which a methyl group corresponding to RË in the structural unit (a4-2) is substituted with a hydrogen atom is also exemplified as a structural unit represented by (a4-3):
[0176] [0176] H, RP
[0177] [0177] Examples of the alkanediyl group in L° include those which are the same as those mentioned in the alkanediyl group of A°**. divalent chain saturated hydrocarbon optionally having a fluorine atom and a divalent alicyclic hydrocarbon group optionally having a fluorine atom, and more preferably a perfluoroalkanediyl group.
[0178] [0178] Examples of saturated hydrocarbon group and saturated hydrocarbon group optionally having a fluorine atom for AF* include the same groups as mentioned for R°#2. Preferred among these groups are fluorinated alkyl groups such as trifluoromethyl group , a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a group
[0179] [0179] In the formula (a4-3), L° is preferably an ethylene group.
[0180] [0180] The structural unit represented by the formula (a4-3) includes, for example, structural units represented by the formula (a4-1"-1) to the formula (a4-1'-11). structural unit in which a methyl group corresponding to R” in a structural unit (a4-3) is substituted with a hydrogen atom is also exemplified as a structural unit represented by (a4-3).
[0181] It is also possible to cite by way of example, as structural unit (a4), a structural unit represented by the formula (a4-4):
[0182] [0182] Examples of the saturated hydrocarbon group of R2* include those which are the same as the saturated hydrocarbon group represented by R°*2, RP2 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and more preferably an alkyl group having 1 to 6 atoms carbon having a fluorine atom. In the formula (a4-4), A ! is preferably -(CH>)j1-, more preferably an ethylene group or a methylene group, and more preferably a methylene group.
[0183] [0183] The structural unit represented by the formula (a4-4) includes, for example, the following structural units and the structural units in which a methyl group corresponding to R* in the structural unit
[0184] <Structural unit (a5)> Examples of the non-leaving hydrocarbon group belonging to the structural unit (a5) include groups having a linear, branched or cyclic hydrocarbon group. Of these, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. The structural unit (a5) includes, for example, a structural unit represented by the formula (a5-1): 51 H
[0185] The alicyclic hydrocarbon group in R° can be monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon group includes, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group. The polycyclic alicyclic hydrocarbon group includes, for example, an adamantyl group and a norbornyl group.
[0186] [0186] Examples of the divalent saturated hydrocarbon group in L” include a divalent chain saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and a divalent chain saturated hydrocarbon group is preferred.
[0187] [0187] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by L°° is replaced by -O- or -CO- includes, for example, the groups represented by the formula (L1-1) at formula (L1-4). In the following formulas, * and ** represent a binding site, and * represents a binding site to an oxygen atom. ST LS 4 WA en A Or” WL Ds (L1-1) (L1-2) us © (L1-4) In the formula (L1-1), X represents *-O-CO- or *-CO-O - (* represents a binding site to L*), L* represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms, L* represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms , and the total number of carbon atoms of L* and L* is 16 or less.
[0188] [0188] Lt is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
[0189] [0189]
[0190] The group represented by formula (L1-2) includes, for example, the following divalent groups. A, A H, 4 Hs „OD do" Aho” ho Aho”
[0191] The group represented by formula (L1-3) includes, for example, the following divalent groups. Hs 0 0 N POT AA DN. A Ô xx H 3
[0192] The group represented by the formula (L1-4) includes, for example, the following divalent groups. O xx NDA AT As Ar > O xx pe Jo” * $ J dT POS L- L°° is preferably a single bond or a group represented by the formula (L1-1).
[0193] [0193] Examples of the structural unit (a5-1) include the following structural units and the structural units in which a methyl group corresponding to R° in the structural unit (a5-1) is substituted with a hydrogen atom in the following structural units.
[0194] [0194] <Structural unit (ST)> The resin (A) may further include a structural unit which is decomposed by exposure to radiation to generate an acid (hereinafter sometimes referred to as "structural unit (ST)"). Specific examples of the structural unit (IT) include the structural units mentioned in JP 2016-79235 A, and a structural unit having a sulfonate group or a carboxylate group and an organic cation in a side chain or a structural unit having a group sulfonio and an organic anion in a side chain are preferred.
[0195] [0195] The structural unit having a sulfonate group or a carboxylate group and an organic cation in a side chain is preferably a structural unit represented by the formula (II-2-A"):
[0196] [0196] Examples of the halogen atom represented by RS include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0197] [0197] X represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X* represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X° represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.
[0198] [0198] Examples of ZA' in formula (II-2-A") include those which are identical to the cation Z1* in the acid generator (B1).
[0199] The structural unit represented by the formula (II-2-A") is preferably a structural unit represented by the formula (II-2-A): Rili3
[0200] [0200] The structural unit represented by the formula (II-2-A) is preferably a structural unit represented by the formula (II-2-A-1):
[0201] [0201] The structural unit represented by the formula (II-2-A-1) is more preferably a structural unit represented by the formula (II-2-A-2):
[0202] [0202] The structural unit represented by the formula (II-2-A") includes, for example, the following structural units, the structural units in which a group corresponding to the methyl group of RIB is substituted by an alkyl group having 1 to 6 carbon atoms optionally having a hydrogen atom, a halogen atom (for example, a fluorine atom) or a halogen atom (for example, a trifluoromethyl group, etc.) and the structural units mentioned in WO 2012/050015 A. ZA” represents an organic cation.
[0203] [0203] The structural unit having a cation having a sulfonio group and an organic anion in a side chain is preferably a structural unit represented by the formula (II-1-1):
[0204] [0204] Examples of the structural unit including a cation in the formula (II-1-1) include the following structural units and the structural units in which a group corresponding to the methyl group of R"* is substituted by an atom of hydrogen, a halogen atom (for example, a fluorine atom) or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom (for example, a trifluoromethyl group etc.).
[0205] [0205] Examples of the organic anion represented by A include a sulfonic acid anion, a sulfonylimide anion, a sulfonyl methide anion and a carboxylic acid anion. The organic anion represented by A' is preferably a sulfonic acid anion, and more preferably an anion contained in the salt represented by the above-mentioned formula (B1).
[0206] [0206] Examples of the sulfonylimide anion represented by A include the following.
[0207] [0207] Examples of the sulfonyl methide anion include the following.
[0208] [0208] Examples of the carboxylic acid anion include the following. O Oo 0 D _ co HA HEA ons Os
[0209] [0209] Examples of the structural unit represented by the formula (II-1-1) include structural units represented by the following formulas. Hs Hs Hs Hz Ha Hz { + Jo KF ì FF FE Hg OT od © 048 OC OD OD
[0210] The resin (A) may include structural units other than the aforementioned structural units, and examples of the structural units include the structural units well known in the art.
[0211] The resin (A) is preferably a resin composed of a structural unit (a1) and a structural unit (s).
[0212] The respective structural units constituting the resin (A) may be used singly, or two or more structural units may be used in combination. By using a monomer from which these structural units are derived, it is possible to produce these structural units by a known polymerization process (eg, a radical polymerization process). The content of respective structural units included in the resin (A) can be adjusted depending on the amount of monomer used in the polymerization.
[0213] <Resin other than resin (A)> The resist composition of the present invention may include the resin other than resin (A) in combination.
[0214] [0214] The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less. , based on the solid component of the resist composition. When including resins other than resin (A), the total content of resin (A) and resins other than resin (A) is preferably 80% by mass or more and 99% by mass or less, and more preferably 90 mass% or more and 99 mass% or less, based on the solid component of the resist composition. The solid component of the resist composition and the content of the resin can be measured by a known analytical means such as liquid chromatography or gas chromatography.
[0215] [0215] <Solvent (E)> The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more and 99% by mass or less. The content of the solvent (E) can be measured, for example, by a means of analysis known as liquid chromatography or gas chromatography.
[0216] [0216] <Deactivating agent (C) ("quencher")> Examples of deactivating agent (C) include an organic compound containing basic nitrogen, or an acid-generating salt having an acidity lower than that of an acid generated from an acid generator (B) (excluding the carboxylate represented by the formula (T)). When the resist composition includes the quenching agent, the content of the quenching agent (C) is preferably about 0.01 to 15% by weight, more preferably about 0.01 to 10% by weight. , more preferably about 0.01 to 7% by weight, and more preferably about 0.1 to 3% by weight, based on the amount of the solid component of the resist composition. Examples of the basic nitrogen-containing organic compound include an amine and an ammonium salt. Examples of amine include aliphatic amine and aromatic amine. Examples of aliphatic amine include primary amine, secondary amine and tertiary amine. Examples of amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline , diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine , ethyldipentylamine, ethyldihexylamine, — ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, la = dicyclohexylmethylamine, la = tris[2-(2-
[0217] [0217] The acidity in an acid-generating salt having a lower acidity than an acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). Regarding the acid-generating salt having a lower acidity than an acid generated from the acid generator (B), the acid dissociation constant of an acid generated from the salt usually satisfies the inequality following: -3 < pKa, preferably -1 < pKa < 7, and more preferably 0 < pKa < 5.
[0218] [0218] Examples of the weak acid inner salt (D) include the following salts. 007 700 _ + 007 oo” do 0 00 Ho 670 007 oo” oo oo 007 007 HOO odio Br CI 007 oo oo 00° oo no, Soo dio Fo Ho dig a 09 oo 007 007 oo GO oO SEO SOA NN
[0219] [0219] <Other components> The resist composition of the present invention may also include components other than the components mentioned above (hereinafter sometimes referred to as "other components (F)"). The other components (F) do not are not particularly limited and it is possible to use various additives known in the art of resists, for example sensitizers, dissolution inhibitors, surfactants, stabilizers and colorants.
[0220] <Preparation of resist composition> The resist composition of the present invention can be prepared by mixing a carboxylate (I), a resin (A) and an acid generator (B), resins other than resin (A), a solvent (E), a deactivating agent (C) and other components (F). The mixing order of these components is any order and it is not particularly limited. It is possible to select, as the temperature during mixing, an appropriate temperature of 10 to 40°C, depending on the kind of the resin, the solvent solubility (E) of the resin and the like. It is possible to choose, as mixing time, an appropriate time of 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited and it is possible to use mixing with agitation.
[0221] [0221] <Method for producing a resist pattern> The method for producing a resist pattern of the present invention includes: (1) a step of applying the resist composition of the present invention to a substrate, (2) a step of drying the applied composition to form a layer of composition, (3) a step of exposing the layer of composition, (4) a step of heating the exposed layer of composition, and (5) a step of development of the heated composition layer.
[0222] [0222] (Application) The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) or resist composition for UVE exposure, in particular an electron beam (EB) resist composition or resist composition for UVE exposure, and the composition of resist is useful for fine processing of semiconductors.
[0223] The present invention will be described more specifically by means of examples. The percentages and the parts expressing the contents or the amounts used in the examples are by weight unless otherwise indicated. The weight average molecular weight is a value determined by gel permeation chromatography. The analysis conditions of gel permeation chromatography are as follows. Column: TSKgel Multipore IIXL-M x 3+guard column (manufactured by TOSOH CORPORATION) Eluent: tetrahydrofuran Flow rate: 1.0 mL/min Detector: RI detector Column temperature: 40°C Injection amount: 100 µl Standards molecular weight: standard polystyrene (manufactured by TOSOH CORPORATION) The structures of the compounds were confirmed by measuring a molecular ion peak by mass spectrometry (liquid chromatography: Model 1100, manufactured by Agilent Technologies, Inc., mass spectrometry: Model LC/MSD, manufactured by Agilent Technologies, Inc.). The value of this molecular ion peak in the following examples is indicated by “MASS”.
[0224] [0224] Example 1: Synthesis of salt represented by the formula (1-2) CF: CF3 — © CF3SO3 + Jus Oo: LS ee + ce | Ö 3903 1 © T CF3 CFs (I-2-a) (1-2-b) (I-2) 0.67 part of a salt represented by the formula (I-2-a), 0.30 part of a salt represented by formula (I-2-b) and 10 parts of chloroform were mixed, followed by stirring at 23°C for 12 hours. To the mixture thus obtained, 5 parts of a 5% oxalic acid aqueous solution were added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 5 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated to obtain 0.64 part of a salt represented by the formula (I-2). MASS (ESI spectrum (+)): M* 525.0 MASS (ESI spectrum (-)): M° 193.1
[0225] [0225] Example 2: Synthesis of salt represented by the formula (I-4) CF EE CF FE
[0226] [0226] Example 3: Synthesis of salt represented by formula (1-5)
[0227] [0227] Example 4: Synthesis of salt represented by the formula (I-110)
[0228] [0228] Example 5: Synthesis of salt represented by the formula (I-1084) Kf AJ Le 94 + Kor > gd © Fo H (1-1084-a) (1-1084-b) (1-1084-c) A solution obtained by mixing 4.49 parts of pyridine, 14.67 parts of a compound represented by formula (I-1084-b) and 25 parts of tetrahydrofuran was added dropwise at 0°C to a solution obtained by mixing 10 parts of a compound represented by formula (I-1084-a) and 10 parts of tetrahydrofuran. The resulting mixture was stirred at 23°C for 1 hour. To the mixed reaction solution, 30 parts of ion-exchanged water was added, followed by extraction with ethyl acetate. The extracted organic layer was concentrated under reduced pressure and n-heptane was added, followed by stirring for 1 hour. The mixed solution was allowed to stand and the supernatant was removed, followed by drying to obtain 22.91 parts of a salt represented by the formula (1-1084-c).
[0229] [0229] Example 6: Synthesis of the salt represented by the formula (I-652)
[0230] [0230] Example 7: Synthesis of the salt represented by the formula (I-706)
[0231] [0231] Example 8: Synthesis of the salt represented by the formula (I-868) Fr © ‚F
[0232] [0232] Synthesis Example 1: Synthesis of salt represented by the formula (IX-4) F3 CF3
[0233] [0233] MASS (ESI spectrum (+)): M* 467.1 MASS (ESI spectrum (-)): M° 193.1
[0234] Synthesis Example 2: Synthesis of the salt represented by the formula (IX-5) ÇFa CF3 9 =. 0 Of AA OT SX © ; C (IX-5-a) (172-b) (IX-5) 0.41 part of a salt represented by the formula (IX-5-a), 0.30 part of a salt represented by the formula (I-2-b) and 10 parts of chloroform were mixed, followed by stirring at 23°C for 12 hours. To the mixture thus obtained, 5 parts of a 5% oxalic acid aqueous solution were added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 5 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated to obtain 0.49 part of a salt represented by the formula (IX-5).
[0235] [0235] MASS (ESI spectrum (+)): M* 331.1 MASS (ESI spectrum (-)): M° 193.1
[0236] [0236] Synthesis Example 3: Synthesis of the salt represented by the formula (IX-6) | | Y don't. Bu Ots A LM©; © (IX-6-a) (77279) (IX-6) 0.47 part of a salt represented by formula (IX-6-a), 0.30 part of a salt represented by formula (I -2-b) and 10 parts of chloroform were mixed, followed by stirring at 23°C for 12 hours. To the mixture thus obtained, 5 parts of a 5% oxalic acid aqueous solution were added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 5 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated to obtain 0.51 part of a salt represented by the formula (IX-6).
[0237] [0237] MASS (ESI spectrum (+)): M* 389.0 MASS (ESI spectrum (-)): M° 193.1
[0238] [0238] Synthesis Example 4: Synthesis of salt represented by formula (IX-7)
[0239] [0239] MASS (ESI spectrum (+)): M* 317.1 MASS (ESI spectrum (-)): M° 193.1
[0240] [0240] Synthesis Example 5: Synthesis of a Salt Represented by Formula (IX-8)
[0241] [0241] MASS (ESI spectrum (+)): M* 281.1 MASS (ESI spectrum (-)): M° 193.1
[0242] [0242] Resin Synthesis The compounds (monomers) used in the synthesis of a resin (A) are illustrated below. In the following, these compounds are referred to as "(a1-1-3) monomer" according to the formula number. on HL CH= CH, ’ ae ons,
[0243] Synthesis Example 6 [Synthesis of Resin A1] A monomer (a1-4-2), a monomer (a1-1-3) and a monomer (a1-2-6) were used as monomers, these monomers were mixed in a molar ratio of 38:24:38 [monomer (a1-4-2): monomer (a1-1-3): monomer (a1-2-6)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile was added as an initiator in the amount of 7 mol% based on the total molar number of all monomers, and then the mixture was then polymerized by heating at 85°C for about 5 hours. To the polymerization reaction solution thus obtained, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added in an amount of 2.0 times the total mass of all monomers, thereby was followed by stirring for 6 hours and further isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and recovery to obtain resin A1 (copolymer) having a mass average molecular weight of about 5.3 x 10° with a yield of 78%. This A1 resin has the following structural units.
[0244] [0244] Synthesis Example 7 [Synthesis of Resin A2] A monomer (a1-4-2) and a monomer (a1-2-6) were used as monomers, these monomers were mixed in a molar ratio of 38 :62 [monomer (a1-4-2):monomer (a1-2-6)], and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile was added as an initiator in the amount of 7 mol% based on the total molar number of all monomers, and then the mixture was then polymerized by heating at 85°C for about 5 hours. To the polymerization reaction solution thus obtained, an aqueous solution of p-toluenesulfonic acid (2.5% by mass) was added in an amount of 2.0 times the total mass of all monomers, which was followed by stirring for 6 hours and further isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and collection to obtain resin A2 (copolymer) having a mass-average molecular weight of approximately 5.4 x 10° with an efficiency of 89%. This A2 resin has the following structural units.
[0245] [0245]
[0246] Synthesis Example 9 [Synthesis of Resin A4] A monomer (a1-2-6), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (a1-2-6) were used. a1-4-13) as monomers, these monomers were mixed in a molar ratio of 53:3:12:32 [monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4 -2: monomer (a1-4-13)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitria and azobis (2,4 dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the total molar number of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. To the polymerization reaction solution thus obtained, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added in an amount of 2.0 times the total mass of all monomers, thereby was followed by stirring for 12 hours and further isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and recovery to obtain resin A4 (copolymer) having a mass average molecular weight of approximately 5.1 x 103 with 79% yield. This A4 resin has the following structural units. tot ten trg, tc To O O
[0247] [0247] <Preparation of Resist Composition> As shown in Table 2, the following components were mixed and the mixture thus obtained was filtered through a fluororesin filter having a pore diameter of 0.2 µm to prepare resist compositions.
[0248] <Resin> A1 to A4: Resin A1 to Resin A4 <Acid generator (B)> B1-25: salt represented by formula (B1-25); synthesized by method mentioned in JP 2011-126869 A F°0 OS ost O
[0249] [0249] (Evaluation of electron beam resist composition exposure, alkaline development) Each 6 inch (15.24 cm) diameter silicon wafer was treated with hexamethyldisilazane and then baked on a direct hot plate at 90°C for 60 seconds. A resist composition was applied by centrifugal application (“spin coating”) on the silicon wafer so that the thickness of the layer of composition became 0.04 μm. The coated silicon wafer was then prebaked on the direct hot plate at the temperature shown in the "PB" column of Table 2 for 60 seconds to form a composition layer.
[0250] [0250] Evaluation of the line edge roughness (LER): The line edge roughness was determined by measuring a roughness width of the unevenness of the wall surface of the resist patterns produced by the effective sensitivity to using a scanning electron microscope. The results are shown in Table 3.
[0251] [0251] (Evaluation of resist composition exposure to electron beam, organic solvent development) Each 6 inch (15.24 cm) diameter silicon wafer was treated with hexamethyldisilazane then baked on a direct hot plate at 90°C for 60 seconds. A resist composition was applied by centrifugal application (“spin coating”) on the silicon wafer so that the thickness of the layer of composition became 0.04 μm. The coated silicon wafer was then prebaked on the direct hot plate at the temperature shown in the "PB" column of Table 2 for 60 seconds to form a composition layer.
[0252] [0252] Evaluation of line edge roughness (LER): Line edge roughness was determined by measuring a roughness width of the unevenness of the wall surface of the resist patterns produced by the effective sensitivity to using a scanning electron microscope. The results are shown in Table 4.
[0253] [0253] A carboxylate and a resist composition comprising the carboxylate of the present invention exhibit satisfactory line edge roughness, and are therefore suitable for semiconductor fine processing.

权利要求:
Claims (22)
[1]
1. A carboxylate represented by the formula (I): (D) m2 k, A _ > oc x0 (I)
LL (RÈò)ms (ROma where, in the formula (I), R* represents a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, R2, R3 and R* each independently represent a halogen atom , a fluorinated alkyl group having 1 to 4 carbon atoms or a hydrocarbon group having 1 to 12 carbon atoms, and -CHz- included in the hydrocarbon group may be replaced by -O- or -CO-, m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R* may be the same or different, m3 represents an integer of 0 to 4, and when m3 is 2 or more, a plurality of R* may be the same or different , m4 represents an integer of 0 to 5, and when m4 is 2 or more, a plurality of R* may be the same or different, and X° represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and - CHz- included in the hydrocarbon group can be replaced by -O-, -S-, -CO- or -S0;-.
[2]
2. The carboxylate according to claim 1, wherein R* represents a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
[3]
3. The carboxylate according to claim 1, in which R2, R* and R* each independently represent a fluorine atom, an iodine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a hydroxy group or an alkoxy group having 1 to 3 carbon atoms.
[4]
4. The carboxylate according to claim 1, wherein R2, R* and R* each independently represent a fluorine atom, an iodine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
[5]
5. The carboxylate according to claim 1, wherein m2 and m3 each independently represents an integer from 0 to 2 and m4 represents an integer from 0 to 3.
[6]
6. The carboxylate according to claim 1, wherein the iodine atom is bonded to the meta position or the para position of the benzene ring relative to S*.
[7]
7. The carboxylate of claim 1, wherein R* is bonded at the meta or para position of the benzene ring to S*.
[8]
8. The carboxylate according to claim 1, wherein R and R* are each independently bonded to the meta position or the para position of the benzene ring relative to S*, and R° is bonded to the ortho position or the meta position of the benzene ring relative to S*.
[9]
9. The carboxylate according to claim 1, wherein the cation is represented by any one of formula (I-c-1) to formula (I-c-20):
Fa F3 F F X A of CF3 F (I-e-1) (I-c-2) (I-c-3) (I-c-4) F3 F > x F3 F of ot © Oo | + | + O Ö. > “0 CF3 F CF3 Ê (I-c-5) (I-c-6) (I-c-7) (I-c-8)
H H 0 Rod As On — > + | Q N + — > + + > +
OH OH (I-c-9) (I-c-10) (I-e-11) (I-e-12) y © GT 2 | + | + | | | La Lea (I-c-16) (I-e-13) (I-c-14) (I-c-15) F F F3 F F 3
F | + | F Ï F | Te, Im (I-e-17) (I-c-18) (I-e-19) (I-e-20)
[10]
10. The carboxylate according to claim 1, wherein X° is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (-CH>- included in the aliphatic hydrocarbon group can be replaced by -O-, -S -, -CO- or -SOz-), an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, a group represented by formula (aa) or a group represented by formula (bb): a ga ze xp (aa) where, in the formula (aa), X and XP each independently represent -O- or -S-, X!2 represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH>- included in the hydrocarbon group may be replaced by -O- , -S-, -CO- or -SO--, x represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and -CH>- included in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -S0;-, and * represents a carbon atom binding site of -COO';
O “——[A ee (bb) where, in the formula (bb), LA represents an alkanediyl group having 1 to 6 carbon atoms which may have a fluorine atom, LP represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and -CH:- included in the alkanediyl group may be replaced by -O-, -S-, -CO- or -SOz-, RA represents a hydrocarbon group having 1 to 36 carbon atoms which may have a substituent, and -CH>- included in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and * represents a carbon-binding site of -COO-.
[11]
11. The carboxylate according to claim 10, wherein X° is an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a fluorine atom or a hydroxy group (-CHz- included in the alicyclic hydrocarbon group may be replaced by - O-, -S-, -CO- or -S0--), a group obtained by combining an alicyclic hydrocarbon group having 3 to 36 carbon atoms with a chain hydrocarbon group having 1 to 18 carbon atoms (-CH: - included in the alicyclic hydrocarbon group can be replaced by -O-, -S-, -CO- or -SO>-; - CHz- included in the chain hydrocarbon group can be replaced by -O- or -CO-, and the alicyclic hydrocarbon group or the chain hydrocarbon group may have a fluorine atom or a hydroxy group), an aromatic hydrocarbon group having 6 to 36 carbon atoms may have a fluorine atom or a hydroxy group, a group represented by the formula (aa) or a group represented by formula (bb).
[12]
12. The carboxylate according to claim 10, wherein X° is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom or a hydroxy group (-CHz- included in the alicyclic hydrocarbon group may be replaced by - O-, -S-, -CO- or -SOz-), a group obtained by combining an alicyclic hydrocarbon group having 3 to 18 carbon atoms with a chain hydrocarbon group having 1 to 12 carbon atoms (-CH:- included in the alicyclic hydrocarbon group can be replaced by -O-, -S-, -CO- or -SO>-; -CH: included in the chain hydrocarbon group can be replaced by -O- or -CO-, and the alicyclic hydrocarbon group or the chain hydrocarbon group may have a fluorine atom or a hydroxy group), an aromatic hydrocarbon group having 6 to 18 carbon atoms may have a fluorine atom or a hydroxy group.
[13]
13. The carboxylate according to claim 10, wherein X° is a group represented by formula (aa), and in formula (aa), X! is an alkanetriyl group having 1 to 6 carbon atoms capable of having a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms capable of having a substituent, and x is a chain hydrocarbon group having 2 to 18 carbon atoms (-CH>- included in the chain hydrocarbon group may be replaced by -O- or -CO-, and the chain hydrocarbon group may have a substituent), a alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CH:- included in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO> -, and the alicyclic hydrocarbon group may have a substituent), or a group obtained by combining a chain hydrocarbon group having 1 to 12 carbon atoms (-CHz- included in the chain hydrocarbon group may be replaced by -O- or -CO-) with an alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CHz- included in the alicyclic hydrocarbon group can be replaced by -O-, -S-, -CO- or -SO--, and the alicyclic hydrocarbon group can have a substituent).
[14]
14. The carboxylate according to claim 10, wherein X° is a group represented by formula (bb), and in formula (bb), RA is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent (-CHz- included in the alkyl group may be replaced by -O-, -S-, -CO- or -SO2-) or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (-CHz- included in the cyclic hydrocarbon group which may be replaced by -O-, -S-, -CO- or -S02-).
[15]
15. The carboxylate according to claim 1, wherein the carboxylic acid anion is a carboxylic acid anion represented by any one of formula (I-a-1) to formula (I-a-93):
Fos X A =>
H (1-a-1) (1-a-2) (1-a-3) (1-a-4) (1-a-5) EK; 5 Fel ' eN © © H 9 9 H (ar6) (ra7) (la-8) (I-a-9) > A it 5 > A; Wo (l-a-10) (la-11) (l-a-12) (l-a-13) a: ore Fa
H to © (I-a-14) (I-a-15) (l-a-16) My pes © 7 (I-a-17) (I-a-18) (I-a-19) H + ) $ ç Hac _ aa. f; D H © O Ö Ô (l-a-22) (l-a-20) (l-a-21)
O O O o w ad Q
X
HH "9 999 (1-a-25) (|-a-26) HO 9 Q 0 een A H3C. _ HO ë LA ° (la-27) H = TL (Ia-28) (la-29) ( la-30) Oo Do { J 07 yo 0 va) (la-32) (la-33) 3 zo y 5 9 OH (la-34) & (la-35) (la-36) Ar ea ge 0° Don a O (Ia-37) (Ia-38) (Ia-39) pa 2e A 9 > rh AH © D
Ö (I-a-40) 9 (l-a-41) 0 (I-a-42)
Q H Q H to | ) 4 s s A s > X = 06 ke ON -a-43 (ad) (-a-44) © (|-a-45)
Q H H 1 29 0 s 9 5 ok Oo Oo” Ô 70 © (l-a-46) (l-a-47) (l-a-48)
HO HO H 9 Oo 7] ES aD ON eN (l-a-51) (l-a-50) (l-a-48);
QHQ
Q H ie H O > N 7 OH _, Le } a on Ö to (I-a-52) (I-a-53) (l-a-54)
F F F _ | F FE A F F F Oo - O OC 5 0 o DA 2 DA shih M 2C ET 0 ERS OH FE FO (|-a-55) - (-a-56) (|-a-57)
F EE ee Ff 5 FE ©
F F - 0 shih hij se EE F0 FE 0 FO > 6-0
O O (|-a-58) (|-a-59) (|-a-60) F F F LI _ F F F 0; _ F F F ° = O hij OH hij sy "FO "FO (-a-61) (-a-62) (I-a-63) F_F FO F Eet F Oo F F _ _ Se NAT se
PE PO D FO FO (|-a-64) (l-a-65) (l-a-66) FLF Eef _ Del A Ay sy OET a. OF a. (l-a-69)
FF
F F F F _ Eh = Oo Ay F 5 O OC SUMMER O,C F F F F F 0 F O 9 OH F F (I-a-70) (I-a-71) (-a-72)
FF LEI F = O F OF — 0 ohh _ F ih F F F X Dy IT 6
F O (-a-73) (l-a-74) (l-a-75)
AA - O O,C 0 0 AD De Ar (|-a-76) F (l-a-77) (l-a-78)
F
O O = O Tk F 9 Ief 7 x PT oh
FO F (l-a-79) (l-a-80) (|-a-81) 1 9 FL FELO F 9 O sch NN IT se HA F NAH 2 7 o
O F F F F F (l-a-82) (l-a-83) (l-a-84) FF Ec Ff F
F_ELF_F°; _ 0 E NA F 0.C oc” 02C FLF F FIF 106 FO FO
F O OH F F OH F ik (l-a-85) (l-a-86) (l-a-87)
Oh ee ho ee. _ O O _ O ze AO FL OF 0 Fo o © O O,C a. (l-a-88) (l-a-89) 0 (La-90) (l-a-91) O — Â + O of
O FF © _ FRE Ge O,C O,C
O O (l-a-92) (l-a-93)
[16]
16. A carboxylic acid generator comprising the carboxylate according to claim 1.
[17]
17. A resist composition comprising the carboxylic acid generator according to claim 16, an acid generator other than the carboxylic acid generator and a resin having an acid labile group.
[18]
18. The resist composition according to claim 17, wherein the resin having an acid-labile group comprises at least one member selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by the formula ( a1-2): a4 a Le . Hz R° C ar
OO La” La2 Joan pot ea nf" (a1-1) (a1-2) where, in formula (a1-1) and formula (a1-2), L°* and L° each independently represent -O- or *-O- (CHz):1-CO-O-, k1 represents an integer from 1 to 7, and * represents a binding site to -CO-, R* and R°° each independently represent an atom of hydrogen, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, R°° and R each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups, m1 represents an integer of 0 to 14, nl represents an integer from 0 to 10, and nl ' represents an integer from 0 to 3.
[19]
19. The resist composition according to claim 17, wherein the resin having an acid-labile group comprises a structural unit represented by the formula (a2-1) Ra14 H2
VS
Y 85 (a2-1) OK! | — (CH3)o1
OH Ra16 where, in formula (a2-1), L°* represents -O- or *-O-(CHz)z-CO-O-, k2 represents an integer from 1 to 7, and * represents a site of bond to -CO-, R2!* represents a hydrogen atom or a methyl group, R°15 and RE each independently represent a hydrogen atom, a methyl group or a hydroxy group, and 01 represents an integer from 0 to 10.
[20]
20. The resist composition according to claim 17, wherein the resin having an acid labile group comprises a structural unit represented by the formula (a2-A): R250
HA
I | (a2-A)
OH ( RS) where, in the formula (a2-A), R°59 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, R ®1 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group, A20 represents a single bond or * -X°°- ( a82-x252) 5", and * represents a bonding site to carbon atoms to which -R° is bonded, A2 represents an alkanediyl group having 1 to 6 carbon atoms,
x°°!1 and X252 each independently represent -O-, -CO-O- or -O-CO- nb represents 0 or 1, and mb represents an integer from 0 to 4, and when mb is an integer from 2 or Further, a plurality of R* may be the same or different from each other.
[21]
21. The resist composition according to claim 17, wherein the resin having an acid-labile group comprises a structural unit according to any one of formula (a3-1), formula (a3-2), formula (a3-3) and the formula (a3-4): Ra18 R319 R320 ju Font + Fort tet Test es 421 / xas |/as 17 (Rp ('as XS ea (RP 0 Den, 5 , 7
O Ö (a3-1) (a3-2) (a3-3) (a3-4) where, in the formula (a3-1), the formula (a3-2), the formula (a3-3) and the formula (a3-4), L°*, L° and L® each independently represent -O- or a group represented by *-O-(CHz)3-CO-O- , where k3 represents an integer from 1 to 7 , L represents -O-, *-OL°8-0-, *-OL°8-CO-O-, *-OL°8-CO-OL°°- CO-O- or *-OL°8-0- CO-L°°-0-, L® and L°° each independently represent an alkanediyl group having 1 to 6 carbon atoms, * represents a bonding site to a carbonyl group, RAS R°19 and R220 each independently represent a hydrogen atom or a methyl group, R22* represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, X°* represents -CHz- or an oxygen atom,
R°21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R322 R223 and R°°° each independently represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, p1 represents an integer from 0 to 5, q1 represents an integer from 0 to 3, rl represents an integer from 0 to 3, w1 represents an integer from 0 to 8, and when pl, q1, rl and/or wl is/are 2 or more, a plurality of R°*, R322 R°° and/or R°°° may be the same or different from each other.
[22]
22. A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to any one of claims 17 to 21 to a substrate, (2) a step of drying the composition applied to form a composition layer, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and (5) a step of developing the composition layer heated.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

JP2011039502A|2009-07-14|2011-02-24|Sumitomo Chemical Co Ltd|Resist composition|

---

JP2019168475A|2016-08-08|2019-10-03|Jsr株式会社|Chemical amplification type resist material and resist pattern formation method|

---

JP2018118962A|2017-01-20|2018-08-02|住友化学株式会社|Salt, acid generator, resist composition and method for producing resist pattern|

---

US20190315684A1|2018-04-12|2019-10-17|Sumitomo Chemical Company, Limited|Salt, acid generator, resist composition and method for producing resist pattern|

---

DE2150691C2|1971-10-12|1982-09-09|Basf Ag, 6700 Ludwigshafen|Photosensitive mixture and use of a photosensitive mixture for the production of a planographic printing plate|

---

US3779778A|1972-02-09|1973-12-18|Minnesota Mining & Mfg|Photosolubilizable compositions and elements|

---

DE2922746A1|1979-06-05|1980-12-11|Basf Ag|POSITIVELY WORKING LAYER TRANSFER MATERIAL|

---

US5073476A|1983-05-18|1991-12-17|Ciba-Geigy Corporation|Curable composition and the use thereof|

---

JPS6269263A|1985-09-24|1987-03-30|Toshiba Corp|Photosensitive composition|

---

JPS62153853A|1985-12-27|1987-07-08|Toshiba Corp|Photosensitive composition|

---

JPS6326653A|1986-07-21|1988-02-04|Tosoh Corp|Photoresist material|

---

JPS63146029A|1986-12-10|1988-06-18|Toshiba Corp|Photosensitive composition|

---

JPS63146038A|1986-12-10|1988-06-18|Toshiba Corp|Photosensitive composition|

---

GB8630129D0|1986-12-17|1987-01-28|Ciba Geigy Ag|Formation of image|

---

DE3914407A1|1989-04-29|1990-10-31|Basf Ag|RADIATION-SENSITIVE POLYMERS AND POSITIVE WORKING RECORDING MATERIAL|

---

JP3763693B2|1998-08-10|2006-04-05|株式会社東芝|Photosensitive composition and pattern forming method|

---

KR101148750B1|2006-06-20|2012-05-22|도시바 미쓰비시덴키 산교시스템 가부시키가이샤|Texture material measuring device and texture material measuring method|

---

JP5487784B2|2008-08-07|2014-05-07|住友化学株式会社|Chemically amplified positive resist composition|

---

TW201033735A|2008-12-11|2010-09-16|Sumitomo Chemical Co|Resist composition|

---

JP5523854B2|2009-02-06|2014-06-18|住友化学株式会社|Chemically amplified photoresist composition and pattern forming method|

---

JP5609569B2|2009-11-18|2014-10-22|住友化学株式会社|Salt and resist composition for acid generator|

---

US8460851B2|2010-01-14|2013-06-11|Sumitomo Chemical Company, Limited|Salt and photoresist composition containing the same|

---

JP5691585B2|2010-02-16|2015-04-01|住友化学株式会社|Resist composition|

---

JP5807334B2|2010-02-16|2015-11-10|住友化学株式会社|Method for producing salt and acid generator|

---

JP5505371B2|2010-06-01|2014-05-28|信越化学工業株式会社|Polymer compound, chemically amplified positive resist material, and pattern forming method|

---

JP5608009B2|2010-08-12|2014-10-15|大阪有機化学工業株式会社|Homoadamantane derivative, method for producing the same, and photoresist composition|

---

US9182664B2|2010-10-13|2015-11-10|Central Glass Company, Limited|Polymerizable fluorine-containing sulfonate, fluorine-containing sulfonate resin, resist composition and pattern-forming method using same|

---

TWI525066B|2011-04-13|2016-03-11|住友化學股份有限公司|Salt, photoresist composition, and method for producing photoresist pattern|

---

JP6212873B2|2012-02-23|2017-10-18|住友化学株式会社|Resist composition and salt|

---

JP6207065B2|2012-10-01|2017-10-04|住友化学株式会社|Salt, resist composition and method for producing resist pattern|

---

JP6592896B2|2014-01-10|2019-10-23|住友化学株式会社|Resin and resist composition|

---

JP6423681B2|2014-10-14|2018-11-14|住友化学株式会社|Resin, resist composition and method for producing resist pattern|

---

KR20180118962A|2017-04-24|2018-11-01|주식회사 만도|Steering control system and method thereof in a vehicle|

---

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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JP2020018903|2020-02-06|

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