SALT, DEACTIVATION AGENT, COMPOSITION OF RESIST AND METHOD FOR PRODUCING A PATTERN OF RESIST

专利摘要:
The present invention relates to a salt capable of producing a resist pattern with a satisfactory Mask Error Factor (MEF) and a resist composition comprising the salt. Described are a salt represented by formula (I) as defined in claim 1, a quencher or quencher and a composition including them wherein, in formula (I), R1 represents a halogen atom, a fluoride group alkyl or a hydrocarbon group, and -CH2- included in the hydrocarbon group may be replaced by -O- or -CO-; R2 and R3 each independently represent a halogen atom, an alkyl fluoride group or a hydrocarbon group, -CH2- included in the hydrocarbon group may be replaced by -O- or -CO-, or R2 and R3 may be linked to each other to form a single bond or an alkanediyl bridge with the carbon atoms to which R2 and R3 are attached, and -CH2- included in the alkanediyl bridge can be replaced by -O-, -S-, - CO-, -SO- or -SO2-; m1 represents an integer of 0 to 3; m2 and m3 represent an integer of 0 to 4; R4, R5 and R6 each independently represent a hydrogen atom or -X2-R7, wherein at least one of R4, R5 and R6 represents -X2-R7, X2 represents * -CO-O-, * -O -CO- or the like; and R7 represents a hydrocarbon group comprising a cyclic hydrocarbon group (-CH2-included in the group may be replaced by -O-, -S- or the like).
公开号:BE1027509A9
申请号:E20205595
申请日:2020-08-27
公开日:2021-07-27
发明作者:Koji Ichikawa；Yuki Takahashi；Katsuhiro Komuro
申请人:Sumitomo Chemical Co；
IPC主号:

专利说明:

[0001] The present invention relates to a salt, a quencher quencher including a salt and a resist composition, and a method for producing a resist pattern using the resist composition. BACKGROUND OF THE INVENTION
[0002] [0002] Patent document 1 mentions a resist composition including a salt having the following structural formula, a resin comprising a structural unit having a labile group in an acid medium, and an acid generator. Where S
[0003] [0003] Patent document 1: JP 2017-202993 A Patent document 2: JP 2018-066985 A Description of the invention Problems to be solved by the invention
[0004] An object of the present invention is to provide a salt capable of producing a resist pattern having a mask error factor (MEF) better than that of a resist pattern formed from of a resist composition including the aforementioned salts. Means for resolving problems
[0005] The present invention includes the following inventions.
[1] [1] A salt represented by the formula (I): Re (Rm x Te -0 + a (RE) m2 where in the formula (I), R * represents a halogen atom, an alkyl fluoride group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, and -CHz- included in the hydrocarbon group may be replaced by -O- or -CO-, R and R ° each independently represent an atom halogen, an alkyl fluoride group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, -CH2- included in the hydrocarbon group may be replaced by -O-, -CO-, or R2 and R * can be linked to each other to form a single bond or an alkanediyl bridge having 1 to 6 carbon atoms with the carbon atoms to which R 2 and R 2 are attached, and -CH> - included in the alkanediyl bridge can be replaced by - O-, -S-, -CO-, -SO- or -SOz- m1 represents an integer of 0 to 3, and when m1 is 2 or more, a plurality of R * can be the same or different from each other res, m2 represents an integer from 0 to 4, and when m2 is 2, or more, a plurality of R2 may be the same or different from each other, m3 represents an integer from 0 to 4, and when m3 is 2 or more , a plurality of R * may be the same or different from each other, R *, R ° and R ° each independently represent a hydrogen atom or -X -R /, wherein at least one of R * , R ° and R ° represents -X7-R7, X ”represents * -CO-O-, * -O-CO- or * -0-CO-0-, and * represents a benzene ring binding site, and R ”represents a hydrocarbon group including a cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group may have a substituent), and -CHz- included in the hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-.
[2] [2] The salt according to [1], where R * represents -X -R7.
[3] [3] A deactivation agent comprising a salt according to [1] or [2].
[4] [4] A resist composition comprising the deactivating agent according to
[3] [3], a resin including a structural unit having an acid labile group, and an acid generator.
[5] [5] The resist composition according to [4], wherein the resin comprising a structural unit including an acid labile group includes at least one resin selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by the formula (a1-2):
[6] [6] The resist composition according to [4] or [5], where the acid generator includes a salt represented by the formula (B1): 9 Z * O3S L B1 AN, (BT)
[7] [7] The resist composition according to any one of [4] to [6], further comprising an acid generating salt having an acidity lower than that of an acid generated by the acid generator.
[8] [8] The resist composition according to any one of [4] to [7], further comprising a resin comprising a structural unit having a fluorine atom.
[9] [9] A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to any one of [4] to [8] on a substrate, (2) a step of drying the applied composition 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. the heated composition layer.
[0006] It is possible to produce a resist pattern with a satisfactory mask error factor (MEF) by using a resist composition including a salt of the present invention. Mode for implementing the invention
[0007] As used herein, the term "(meth) acrylate" means "at least one of: acrylate and methacrylate". Terms such as "acid
[0008] [0008] [Salt represented by formula (1)] The salt of the present invention relates to a salt represented by formula (I) (hereinafter sometimes called "salt (T)">): Re (Rm “> Te -Q + a. (R2) m2 where in formula (I) all the symbols are the same as defined above.
[0009] In formula (I), examples of the halogen atom in Rt, R2 and R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0010] Examples of the hydrocarbon group including a cyclic hydrocarbon group in R 'in the formula (I) 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, groups obtained by optionally combining a cyclic hydrocarbon group 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 with a hydrocarbon chain group having 1 to 6 carbon atoms (alkyl group, alkenyl group, alkynyl group) and the like.
[0011] The alicyclic hydrocarbon group can be a monocyclic, polycyclic or spiro ring, or can be saturated or unsaturated. Examples of the alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group and cyclododecyl group; and polycyclic cycloalkyl groups such as a decahydronaphthyl group, a norbornyl group and an adamantyl group. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 16, more preferably 5 to 16, and more preferably 6 to 16.
[0012] Examples of an alkyl group include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a. hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 9, more preferably 1 to 6, and more preferably 1 to 4.
[0013] Examples of the combined group include: A group obtained by combining an alicyclic hydrocarbon group with an aromatic hydrocarbon group (-CH> - included in the combined group can be replaced by -O-, -S-, -CO- or -SO--), a group obtained by combining an alicyclic hydrocarbon group with a chain hydrocarbon group (alkyl group, alkenyl group, alkynyl group) (-CH> - included in the combined group can be replaced by -O-, -S-, -CO- or -S0 ;-) and a group obtained by combining an - aromatic hydrocarbon group with a chain hydrocarbon group (alkyl group, alkenyl group, alkynyl group) (-CH; - included in the combined group can be replaced by -O-, -S-, -CO- or -S0; -). In combination, two or more alicyclic hydrocarbon groups, aromatic hydrocarbon groups and chain hydrocarbon groups (alkyl group, alkenyl group, alkynyl group, etc.) can be used in combination. Any group can be linked to X2. In the groups mentioned above, groups having different valences (alkanediyl group, alkanetriyl group, cycloalkanediyl group, cycloalkanetriyl group, etc.) can be included. The total number of carbon atoms of the hydrocarbon group including the cyclic hydrocarbon group in R ’is, for example, 3 to 24 and is preferably 4 to 18, and more preferably 5 to 16.
[0014] [0014] Specific examples of the combined group include: alicyclic hydrocarbon group-chain hydrocarbon group- * (-CH> - included in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO> -) such as adamantylmethyl group, adamantylethyl group, cyclohexylmethyl group and cyclohexylethyl group, chain hydrocarbon group-alicyclic hydrocarbon group- * (-CH> - included in chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or - SO> -) such as a methyladamantyl group, a methylcyclohexyl group and a dimethylcyclohexyl group, chain hydrocarbon group-aromatic hydrocarbon group- * (-CH> - included in the chain hydrocarbon group can be replaced by -O-, -S-, -CO- or -S0 ;-) such as a tolyl group and a xylyl group, chain hydrocarbon group- alicyclic hydrocarbon group-chain hydrocarbon group - * (-CH> - included in chain hydrocarbon group and alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO, -) such as methylcyclohexylmethyl group, aromatic hydrocarbon group-chain hydrocarbon group- * (-CH > - included in the chain hydrocarbon group can be replaced by -O-, -S-, -CO- or -SO> -) such as benzyl group and phenethyl group, chain hydrocarbon group-aromatic hydrocarbon group- chain hydrocarbon group- * (-CHz- included in the chain hydrocarbon group can be replaced by -O-, -S-, -CO- or -S0: -}, such as a tolylmethyl group, aromatic hydrocarbon group- alicyclic hydrocarbon group- * (-CH> - included in the alicyclic hydrocarbon group can be replaced by -0-, -S-, -CO- or -SO, -) such as a phenyladamantyl group, and alicyclic hydrocarbon group-group _aromatic hydrocarbon- * (-CH> - included in the alicyclic hydrocarbon group can be replaced by -0-, -S-, -CO- or -SO, -) such as a cyclohexylphen group yl and an adamantylphenyl group. * represents a binding site at X °.
[0015] When -CH> - included in the hydrocarbon group in R 'is replaced by -O-, -S-, -CO- or -SO--, the number of carbon atoms before replacement is the total number of carbon atoms of the hydrocarbon group. The number can be 1, 2 or more.
[0016] Examples of the substituent which may belong to the cyclic hydrocarbon group include a halogen atom, a cyano group and an alkyl group having 1 to 12 carbon atoms (-CH> - included in the alkyl group may be replaced by - O-, -S -, -CO- or -SO -> -).
[0017] The cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group can have a substituent, and - CH>; - included in the cyclic hydrocarbon group can be replaced by - O-, -S-, -SOz - or -CO-) is: preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the alicyclic hydrocarbon group may have a substituent, and -CH> - included in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -SO-- or -CO-), or an aromatic hydrocarbon group having 6 to 18 carbon atoms (the aromatic hydrocarbon group may have a substituent), more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms. carbon (the alicyclic hydrocarbon group may have at least one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a hydroxy group and a fluorine atom, and -CH> -
[0018] The hydrocarbon group including a cyclic hydrocarbon group having 3 to 18 carbon atoms in R '(the cyclic hydrocarbon group may have a substituent and -CH> - included in the hydrocarbon group may be replaced by -O-, -S -, -SO> - or -CO-) is: preferably a hydrocarbon group including an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the alicyclic hydrocarbon group may have a substituent, and -CH> - included in the hydrocarbon group may be replaced by -O-, -S-, -SO-- or -CO-), or a hydrocarbon group including an aromatic hydrocarbon group having 6 to 18 carbon atoms (the aromatic hydrocarbon group may have a substituent, and - CHz- included in the hydrocarbon group may be replaced by -O-, -S-, -SO> - or -CO-), more preferably a hydrocarbon group including an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the group Alicyclic hydrocarbon may have at least one selected from the group consisting of to an alkyl group having 1 to 4 carbon atoms, a hydroxy group and a fluorine atom, and -CH> - included in the hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO- ), or a hydrocarbon group including an aromatic hydrocarbon group having 6 to 18 carbon atoms (the aromatic hydrocarbon group may have at least one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a hydroxy group and a fluorine atom, and -CH> - included in the hydrocarbon group can be replaced by -O-, -S-, -SO> - or -CO-),
[0020] [0020] i-18) €, PAG ET € _ 2 = f N and ss, De ”3% E € ig hg A Ë BR, Ë ï Fe, A 4 N WON EP 8.03 A te
[0023] <Method for the synthesis of salt (I)> Salt (I) can be produced by mixing a salt represented by formula (Ia) in the presence of a basic catalyst in a solvent: Re (Rm Re (Rm O 9 zo DO O3S — CF3 Ha SO SA + S "kJ I - LT le> AR 2 VR me (RÈ) m2 me (Ia) (I) where all symbols are as defined above. Examples of the base include sodium hydroxide, potassium hydroxide and the like.
[0024] The salt represented by formula (Ia) can be produced by reacting a compound represented by formula (Ib) with a compound represented by formula (Ic) in the presence of trifluoromethanesulfonic acid and trifluoroacetic anhydride in a solvent: pt fi Ïf RE Pin si Cr; Kd CF-S04H 1 5 Gwe. PR ae ie a € 'LS Fe cu ope er * a Last EN iig ire} {Tat where all the symbols are as defined above.
[0025] <Deactivation agent, "Quencher"> The quencher of the present invention includes a salt (I). The quencher may contain one salt (I), or two or more salts (I).
[0026] [0026] <Deactivating agent (or quencher) (C)> Examples of the deactivating agent (C) include a basic organic compound containing nitrogen and an acid generating salt having an acidity lower than that of an acid generated by an acid generator (B) mentioned later (excluding a salt represented by formula (T)). It is particularly preferable to include a salt generating a carboxylic acid having an acidity lower than that of an acid generated by the acid generator (B) such as a weak acid internal salt (hereinafter sometimes referred to as " weak acid internal salt (D) ”).
[0027] Examples of amines 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, la trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldildicycloldicylamine, methyldyldicycloldohexylamine, methyldildicldicyclohexylamine, methyldildicycloldoldohexylamine, methyldildicycloldoldicylamine, methyldildicycloldoldohexylamine, methyldildicycloldoldohexylamine, methyldildicycloldoldohexylamine. ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, - ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, la = dicyclohexylmethylamine, la = tris [2- (2-
[0028] Examples of ammonium salt include tetramethylammonium hydroxide: = tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide , 3- (trifluoromethyl) phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate and choline.
[0029] The acidity in a salt generating an acid having an acidity lower than that of an acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). generating an acid having an acidity lower than that of an acid generated from the acid generator (B), the acid dissociation constant of an acid generated from the salt usually responds to the following inequality: - 3 <pKa, preferably -1 <pKa <7, and more preferably 0 <pKa <5.
[0030] Examples of the weak acid internal salt (D) include the following salts. 007,700 _; 007 oo ”do 00 040 SO HO 007 oo” oo oo 007 007 HO Gio Br CI 007 oo "oo 007 00 ° NO" A00 de do Ho SIJ SO oo 007 007 oo D 50 SOA SOA GO; O HORT
[0031] When the salt (I) and the quencher (C) are included as deactivating agent, a ratio between the content of salt (T) and that of the quencher (C) (mass ratio; salt (I ): quencher (C)) is generally between 1:99 and 99: 1, preferably between 2:98 and 98: 2, more preferably between 5:95 and 95: 5, more preferably between 10:90 and 90:10 and more preferably between 15:85 and 85:15.
[0032] <Resist composition> The resist composition of the present invention includes a deactivating agent including a salt (I), a resin comprising a structural unit having an acid labile group (hereinafter sometimes referred to as "resin ( A) ”) and an acid generator (hereinafter sometimes referred to as“ acid generator (B) ”). The“ acid labile group ”means a group having a leaving group which is removed by contact with an acid. , thus forming a hydrophilic group (eg, a hydroxy group or a carboxy group) The resist composition of the present invention preferably comprises a solvent (hereinafter sometimes referred to as "solvent (E)").
[0033] <Deactivation agent (Quencher)> In the resist composition of the present invention, the salt (I) content is usually 0.001 to 20% by mass, preferably 0.005 to 15% by mass, and of more preferably from 0.01 to 10% by weight, based on the solids content of the resist composition. When the deactivating agent comprises the deactivating agent (C), the content of deactivating agent (C) is preferably from 0.01 to 20% by mass, more preferably from 0.01 to 15% by mass, more preferably still. from about 0.01 to 10% by mass, more preferably from 0.01 to 5% by mass, and more preferably from 0.01 to 3% by mass, based on the solids content of the composition of resist.
[0034] <Resin A> The resin (A) includes a structural unit having a labile group in an acid medium (hereinafter sometimes called "structural unit (a1)"). It is preferable that the resin (A) further includes a structural unit other than the 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 l structural unit (a1) and structural unit (s) (for example, a structural unit having a halogen atom mentioned later (hereinafter sometimes referred to as "structural unit (a4)")), a structural unit having a later mentioned non-leaving hydrocarbon group (hereinafter sometimes referred to as "structural unit (a5)") and other structural units derived from monomers known in the art.
[0035] <Structural Unit (a1)> The structural unit (a1) is derived from a compound comprising a labile group in an acidic medium (hereinafter sometimes called "monomer (a1)"). The labile group in an acid medium contained in the resin (A) is preferably a group represented by formula (1) (hereinafter also called group (1)) and / or a group represented by formula (2) (in the following also called group (2)): O Ral * O 0 RI (1) where in formula (1), R ° * R ° and R® each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms or an group obtained by combining these, or R ° * and R are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms with the carbon atom to which R * and R * are bonded , ma and na each represent an integer of 0 or 1, and at least one of these represents 1, and * represents a binding site. O rat HE Oo] ARS (2) na 'Raz where, in formula (2), R ° * and R ° each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ° * represents a hydrocarbon group having 1 to 20 carbon atoms, or R2 and R ° * are linked to each other to form a heterocyclic group having 3 to 20 carbon atoms with X and with the carbon atom to which R and R ° * are attached, and -CH> - included in the hydrocarbon group and the heterocyclic group may be replaced by -O- or -S-, X represents an oxygen atom or a sulfur atom, na 'represents 0 or 1, and * represents a binding site.
[0036] Examples of the alkyl group for R ° *, R22 and R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group and the like. .
[0037] Examples of the hydrocarbon group for R °, R ° 2 and R ° include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and groups obtained by combining these groups.
[0038] Examples of group (1) include the following groups. A group where, in formula (1), R ° *, R22 and R® are alkyl groups, ma = O and na = 1. The group is preferably a tert-butoxycarbonyl group.
[0039] Specific examples of group (2) include the following groups. * 20 represents a binding site.
[0040] The monomer (a1) is preferably a monomer having a labile group in an acidic medium and an unsaturated ethylenic bond, and more preferably a (meth) acrylic monomer having a labile group in an acidic medium.
[0041] Among the (meth) acrylic monomers having a labile group in an acid medium, 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.
[0042] The structural unit derived from a (meth) acrylic monomer having a group (1) is a structural unit represented by the formula (a1-0) (hereinafter sometimes called structural unit (a1-0)), a structural unit represented by formula (a1-1) (hereinafter sometimes called structural unit (a1-1)) or a structural unit represented by formula (a1-2) (hereinafter sometimes called 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 can be used in combination.
[0043] [0043] R20! R ° * and R °° are preferably a methyl group.
[0044] The structural unit (a1-0) includes, for example, a structural unit represented by any one of the formula (a1-0-1) to the formula (a1-0-12) and a structural unit wherein a methyl group corresponding to R °% * in the structural unit (a1-0) is substituted with 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).
[0045] The structural unit (a1-1) includes, for example, the 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) of the formula (a1-1-4) and a structural unit in which a methyl group corresponding to R ° * in the structural unit (a1-1) is substituted with 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. Lon> Lon,> Lon Lon
[0046] Examples of structural unit (a1-2) include a structural unit represented by any one of the formula (a1-2-1) to the formula (a1-2-6) and a structural unit in which a methyl group corresponding to R °° in the structural unit (a1-2) is substituted with a hydrogen atom, and a structural unit represented by any one of the formula (a1-2-2), the formula (a1-2-5) and the formula (a1-2-5) is preferred.
[0047] When the resin (A) includes a structural unit (a1-0), its content is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 40 mol%, on the basis of all the structural units of the resin (A).
[0048] In structural unit (a1), examples of structural unit having a group (2) include a structural unit represented by formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1-4) ) "): Ras Aaa To DD (a1-4) (R er pass where in the formula (a1-4), R222 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may optionally have a halogen atom, R ° 53 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, a 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, la represents an integer of 0 to 4, and when la is 2 or more, a plurality of R233 may be the same or different from each other, and R ° 5 * and R °° each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R836 represents a hydrocarbon group having 1 to 20 carbon atoms, or R33 and R °° are bonded with each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with -C- O- to which R33 and R ° * ° are attached, and -CH> - included in the hydrocarbon group and the divalent hydrocarbon group may be replaced by - O- or -S-.
[0049] Examples of the alkyl group in R °°° and R®3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and more preferably a methyl group.
[0050] In formula (a1-4), R °° is preferably a hydrogen atom, R233 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group and an ethoxy group, and more preferably a methoxy group, 1a is preferably 0 or 1, and more preferably 0, R ° 3 * is preferably a hydrogen atom, and R ° 3 ° is preferably an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group, and more preferably a methyl group or an ethyl group.
[0051] [0051] -OC (R2 *) (R235) -0-R3 ° 6 in structural unit (a1-4) is removed by contacting with an acid (eg p-toluenesulfonic acid) to form a hydroxy group.
[0052] The structural unit (a1-4) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646 A. The structural unit preferably includes the structural units represented by the formula (a1-4- 1) with the formula (a1-4-12) and a structural unit in which a hydrogen atom corresponding to R ° in the structural unit (a1-4) is substituted with a methyl group, and more preferably the units structures represented by the formula (a1-4-1) to the formula (a1-4-5) and the formula (a1-4-10).
[0053] When the resin (A) includes the structural unit (a1-4), the content is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, more preferably 20 to 85 mol%, of more preferably 20 to 70 mol%, and more preferably 20 to 60 mol%, based on the total of all structural units of the resin (A).
[0054] The structural unit derived from a (meth) acrylic monomer having a group (2) also includes a structural unit represented by the formula (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5) ").
[0055] The halogen atom includes a fluorine atom and a chlorine atom and is preferably a fluorine atom. Examples of an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a group. octyl, a fluoromethyl group and a trifluoromethyl group.
[0056] The structural unit (a1-5) includes, for example, the structural units derived from the monomers mentioned in JP 2010-61117 A. Among these structural units, the structural units represented by the formula (a1-5-1) to formula (a1-5-4) are preferred, and structural units represented by formula (a1-5-1) or formula (a1-5-2) are more preferred.
[0057] When the resin (A) includes the structural unit (a1-5), the content is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, more preferably 5 to 40 mol%, and more preferably 5 to 30 mol%, based on all the structural units of the resin (A).
[0058] The structural unit (a1) also includes the following structural units. that tan te ta a ter k 0H) DD on KM (a1-3-1) (a1-3-2) (a1-3-3) (a1-3-4) (a1-3-5) @ 198 ( a1-3-7)
[0059] When the resin (A) includes the structural units mentioned above as (a1-3-1) to (a1-3-7), the content is preferably 10 to 95 mol%, more preferably 15 to 90 mole%, more preferably 20 to 85 mole%, more preferably 20 to 70 mole%, and more preferably 20 to 60 mole%, based on all the structural units of the resin (A).
[0060] [0060] <Structural unit (s)> The structural unit (s) is derived from a monomer having no labile group in an acid medium (hereinafter sometimes called "monomer (s)"). It is possible to use, as the monomer from which the structural unit (s) is derived, a monomer having no acid labile group known in the field of resists.
[0061] [0061] <Structural unit (a2)> The hydroxy group belonging to the structural unit (a2) can be an alcoholic hydroxy group or a phenolic hydroxy group. When a resist pattern is produced from the resist composition of the present invention, in the case where high energy rays such as a KrF (248nm) excimer laser are used as the exposure source, an electron beam or extreme ultraviolet light (UVE), a structural unit (a2) having a phenolic hydroxy group is preferably used as a structural unit (a2), and a structural unit (a2-A) mentioned below is more preferably used. When using an ArF (193nm) excimer laser or the like, a structural unit (a2) having an alcoholic hydroxy group is preferably used as the structural unit (a2), and more preferably a structural unit (a2- 1) mentioned later. The structural unit (a2) can be included alone, or two or more structural units can be included.
[0062] In structural unit (a2), examples of 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) ”): H, Ra” Let aso 9 (a2-A) '(RS) ab where, in the formula (a2-A),
[0063] Examples of the halogen atom in R ° ® include a fluorine atom, a chlorine atom and a bromine atom.
[0064] [0064] Examples of * -X °° 1- (A252-X252) pp ”include * -O-, * -CO-O-, * - O-CO-, * -CO-0-A252-CO- 0-, * -0-CO-A352-0-, * -OA ° -CO-O-, * -CO-0-A% - O-CO- and * -0-CO-A% ° 2 -0-CO-. Of these, * -CO-O-, * -CO-0-A332-CO-0- or * -0-A-52-CO-0- are preferred.
[0065] Examples of alkanediyl group include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane group -1,5-diyl, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group , a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
[0066] [0066] A is preferably a single bond, * -CO-O- or * -CO-O- A252-CO-O-, more preferably a single bond, * -CO-O- or * -CO-O- CH2-CO -O-, and more preferably a single bond or * -CO-O-.
[0067] [0067] mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.
[0068] Examples of structural unit (a2-A) include structural units derived from the monomers mentioned in JP 2010-204634 A and JP 2012-12577 A.
[0069] When the structural unit (a2-A) is included in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 10 to 70 mol. %, more preferably 15 to 65 mol%, and more preferably 20 to 65 mol%, based on all structural units.
[0070] [0070] Examples of a 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)" ).
[0071] In formula (a2-1), L ° * is preferably -O- or -O- (CH ”) j- CO-O- (fl represents an integer from 1 to 4), and more preferably -GOLD ! is preferably a methyl group, R3! 5 is preferably a hydrogen atom, RS is preferably a hydrogen atom or a hydroxy group, and ol is preferably an integer of 0 to 3, and more preferably 0 or 1.
[0072] The structural unit (a2-1) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646
[0073] When the resin (A) includes the structural unit (a2-1), the content is usually 1 to 45 mol%, preferably 1 to 40 mol%, more preferably 1 to 35 mol%, and preferably further 1 to 20 mol%, and more preferably 1 to 10 mol%, based on all the structural units of the resin (A).
[0074] <Structural unit (a3)> The lactone ring carried by the structural unit (a3) can be a monocyclic ring such as a B-propiolactone ring, a y-butyrolactone ring or an α-valerolactone ring, or a condensed ring a 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.
[0075] 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 can be included alone, or two or more structural units can be included:
[0076] Examples of the aliphatic hydrocarbon group in R ° *, R322 R ° 23 and R22 include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and a tert-butyl group.
[0077] In formula (a3-1) to formula (a3-3), L %, L® °, and L3 are each independently preferably -O- or a group in which k3 is an integer from 1 to 4 in * -O- (CH2) ç3-CO-O-, more preferably -O- and * -O-CH> -CO-O-, and more preferably an oxygen atom, RAS R319 R220 and RI are each independently preferably methyl, 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 of 0 to 2, and more preferably 0 or 1.
[0078] In 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, R22 is preferably a carboxy group, a cyano group or a methyl group, L ”is preferably -O- or * -OL ° 8-CO-O -, and more preferably -O-, -0-CH2-CO-0- or -0-C: H4-CO-0-, and wl is preferably an integer from 0 to 2, and more preferably 0 or 1. In particular, the formula (a3-4) is preferably the formula (a3-4) ': Ra24 ted + C = O Jar (a3-4)'
[0079] Examples of structural unit (a3) include structural units derived from the monomers mentioned in JP 2010-204646 A, from the monomers mentioned in JP 2000-122294 A and from the monomers mentioned in JP 2012-41274 A. The unit structural (a3) is preferably a structural unit represented by any one of the formula (a3-1-1), the formula (a3-1-2), the formula (a3-2-1), the 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 in which the methyl groups corresponding to R2! 3, RP, R220 and R ° 2 * in the formula (a3-1) in the formula (a3-4) are substituted with hydrogen atoms in the structural units below above.
[0080] Hs H3 CHs CH3 Hs Hz Hz Hz PE PP D te © 55} Oo © di, & 4, ® 4, = (a3-1-1) TS (a3-2-1) O (a3-2x- 1) A (a3-3-1) Z (e3-1-2) (032-2) (e3-2x2) 03.22 Na CH 2 CH He CH 12 CH; © CH © Hs Cs ce C fear LT Her tes Ter TETE TA We N © ze 7 2 t ° 0 Q 9 X Ö 0 a8-4- (a3-4-1) 3.49 343 (a3-44) 4 (345 ( a3-4-6) Hs HH Hs Hz Ho 2 CHs c CHa 82 CH c £ Hs c _CH3 LI
[0081] When the resin (A) includes the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, and more preferably 10 to 60 mol%, based on of all the structural units of the resin (A). Each content of structural unit (a3-1), structural unit (a3-2), structural unit (a3-3) or structural unit (a3-4) is preferably 5 to 60 mol% , more preferably 5 to 50 mol%, and more preferably 10 to 50 mol%, based on all the structural units of the resin (A).
[0082] <Structural unit (a4)> Examples of structural unit (a4) include the following structural units: H, RA + O (a4) 0 Nu where, in formula (a4), R * represents an atom d hydrogen or a methyl group, and R * 2 represents a saturated hydrocarbon group having 1 to 24 carbon atoms which has a fluorine atom, and -CH2- included in the saturated hydrocarbon group may be replaced by -O- or -CO -.
[0083] Examples of the chain hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group , a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; and saturated polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* represents a binding site).
[0084] 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): R52 ton + (a4-0) O
[0085] Examples of the divalent aliphatic saturated hydrocarbon 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 group 2- - methylpropan-1,2-diyl.
[0086] [0086] L “is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
[0087] Examples of 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) in the following structural units is substituted with a hydrogen atom: tf glass The ze (a4-0-1) (a4-0-2) (a4-0-3) (a4-0-4) PEP ret re Pet Fa 2Fs Fac Fc pad Ce F3 Fx 8F17 (a4-0-7) (e4-0-8) (24-09) ro 0) (a4-0-11) (24-0-12)
[0088] [0088]
[0089] [0089] 41
[0090] Examples of the saturated hydrocarbon group in R * include a chain saturated hydrocarbon group and a monocyclic or polycyclic saturated alicyclic hydrocarbon group, and groups formed by combining these groups.
[0091] Examples of a substituent carried by 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 the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred:% - xa43_ Aa45 (ag 3) where in the formula (a-g3), X represents an oxygen atom, a carbonyl group, * -O- CO- or * -CO-0-, A: represents a saturated hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, and * represents a binding site at R °.
[0092] Examples of aliphatic hydrocarbon group in A2 *% include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group; monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* represents a binding site): Examples of a 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, an alicyclic hydrocarbon group-alkyl group, an alkanediyl group-alicyclic hydrocarbon group-alkyl group and the like.
[0093] 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).
[0094] When R * is a saturated hydrocarbon group having the group represented by the formula (a-g3), R ° * is more preferably a group represented by the formula (a-g2): + —A246 - Xa44_ Aa47 (ag 2) where, in the formula (a-g2), A ° * ° represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom,
[0095] The number of carbon atoms of the saturated hydrocarbon group for A ° * ° is preferably 1 to 6, and more preferably 1 to 3.
[0096] The preferred structure of the group represented by the formula (a-g2) is the following structure (* is a binding site to a carbonyl group).
[0097] 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 group and hexane-1 group, 6-diyl; 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.
[0098] Examples of a divalent saturated hydrocarbon group represented by A *, A and A ** in the group represented by formula (a-g1) include a linear or branched alkanediyl group and a monocyclic divalent alicyclic saturated hydrocarbon group, and divalent saturated hydrocarbon groups formed by combining an alkanediyl group and an alicyclic saturated hydrocarbon group divalent. Specific examples thereof 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 1- group. methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like.
[0099] In a 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 ** is a -O-CO-R2 * 2 binding site.
[0100] [0100] Examples of structural unit represented by formula (a4-1) include the following structural units, and structural units in which a methyl group corresponding to A® * in the structural unit represented by formula (a4- 1) in the following structural units is substituted with a hydrogen atom. Hs Hs Hs Hs Hs Ha CH CH »CH» CH »ets
[0101] [0101] Hs Hs CH CH CH CH CHs 1 + I ° = {er 5 vr Tet O $
[0102] [0102] Examples of structural unit represented by formula (a4-1) include a structural unit represented by formula (a4-2): H2 R® TT
[0103] [0103] Examples of the alkanediyl group having 1 to 6 carbon atoms of L ** include the same groups as those mentioned for the alkanediyl group A *. Examples of the saturated hydrocarbon group of R include the same groups as those mentioned for R ° 2.
[0104] 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 R in the structural unit (a4-2) is substituted with a hydrogen atom is also exemplified as the structural unit represented by the formula (a4-2).
[0105] [0105] Examples of the structural unit (a4) include a structural unit represented by the formula (a4-3):
[0106] [0106] Examples of the alkanediyl group in L ° include those which are the same as mentioned in the alkanediyl group in A ° **. The divalent saturated hydrocarbon group optionally having a fluorine atom in A is preferably an aliphatic saturated hydrocarbon group. divalent optionally having a fluorine atom and a divalent alicyclic saturated hydrocarbon group optionally having a fluorine atom, and more preferably a perfluoroalkanediyl group.
[0107] [0107] In formula (a4-3), L ° is preferably an ethylene group.
[0108] The structural unit represented by the formula (a4-3) 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 R ”in the structural unit (a4-3) is substituted with a hydrogen atom is also exemplified as the structural unit represented by the formula (a4-3).
[0109] It is also possible to cite by way of example, as structural unit (a4), a structural unit represented by the formula (a4-4):
[0110] [0110] Examples of the saturated hydrocarbon group for R * include those which are the same as the saturated hydrocarbon group represented by R2 * 2. R ° 22 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 carbon atoms having a fluorine atom.
[0111] [0111] In the formula (a4-4), A! is preferably - (CHz); 1-, more preferably an ethylene group or a methylene group, and more preferably a methylene group.
[0112] [0112] 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
[0113] [0113] When the resin (A) includes the structural unit (a4), the content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and more preferably 3 to 10 mol%, on the basis of basis of all the structural units of the resin (A).
[0114] [0114] <Structural unit (a5)> Examples of a non-leaving hydrocarbon group carried by 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 Hz 55 4 R52 where in the formula (a5-1), R “! represents a hydrogen atom or a methyl group,
[0115] The alicyclic hydrocarbon group in R ° 2 can be monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon group includes, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. The polycyclic alicyclic hydrocarbon group includes, for example, an adamantyl group and a norbornyl group.
[0116] 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) in the formula (L1-4). In the following formulas, * and ** each represent a binding site, and * represents an oxygen atom binding site. ST LS a LS 4 a er ”i B (L1-1) (L1-2) (L1-3) (L1-4) In the formula (L1-1), X represents * -O-CO- or * - CO-O- (* represents a binding site to L *), Lt 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 L1 is 16 or less. In formula (L1-2), LS represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms, L ** represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms, and the number total carbon atoms of L3 and DL is 17 or less. In formula (L1-3), L $ represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms, L * and L each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms , and the total number of carbon atoms of L * °, L $ and LV is 15 or less. In the formula (L1-4),
[0117] L is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
[0118] [0118] The group represented by the formula (L1-1) includes, for example, the following divalent groups. N Os Are Ar Onee D ag Ayo O Ô O
[0119] The group represented by the formula (L1-2) includes, for example, the following divalent groups. OON Hr OY Hs Hs 3 Do ”Aho” Aho ”Ao Aho”
[0120] [0120] The group represented by the formula (L1-3) includes, for example, the following divalent groups.
[0121] [0121] The group represented by the formula (L1-4) includes, for example, the following divalent groups. O kk NGA> AT A AG x * Q xx. DD hd DA 2 Io
[0122] [0122] L ° ”is preferably a single bond or a group represented by the formula (L1-1).
[0123] [0123] Examples of structural unit (a5-1) include the following structural units and structural units in which a methyl group corresponding to R ° in the structural unit (a5-1) in the following structural units is substituted with a hydrogen atom.
[0124] [0124] <Structural unit (IT)> The resin (A) can further include a structural unit which is broken down by exposure to radiation to generate an acid (hereinafter sometimes referred to as "structural unit (IT)"). 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.
[0125] [0125] The structural unit having a sulfonate group or a carboxylate group in a side chain is preferably a structural unit represented by the formula (II-2-A "):
[0126] [0126] Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0127] [0127] X represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms.
[0128] [0128] Examples of the organic cation of ZA * include an organic onium cation, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation and an organic phosphonium cation. Among these organic cations, 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. the formula).
[0129] [0129] (RP qe pbs (RE ) N2 res o © (RES) (RES), © b5-e + R Te OP eu so {s D RP y: a Le (RP fo 2 (b2-1) (b2 -2) (b2-3) (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, an 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 carbon atoms, 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, an aliphatic hydrocarbon group 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 s the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms,
[0130] [0130] The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.
[0131] [0131] Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-methyladamantan-2-yl group, a 2-ethyladamantan-2- group. yl, 2-isopropyladamantan-2-yl group, methylnorbornyl group, isobornyl group and the like. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.
[0132] [0132] Examples of an aromatic hydrocarbon group include aryl groups such as phenyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group and examples of the aromatic hydrocarbon group having a chain hydrocarbon group include a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a p- group. ethylphenyl, a p-tert-butylphenyl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, and the like and examples of the aromatic hydrocarbon group having an alicyclic hydrocarbon group include a p-cyclohexylphenyl group, a p-adamantylphenyl group and the like.
[0133] [0133] Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.
[0134] The ring formed by bonding R ° * and RP with each other, with the sulfur atoms to which R® * and R ”are linked, can be a monocyclic, polycyclic, aromatic, non-aromatic ring, saturated or - unsaturated. This ring includes a ring having 3 to 18 carbon atoms and is preferably a ring having 4 to 18 carbon atoms. The sulfur-containing ring includes a 3- to 12-membered ring and is preferably a 3- to 7-membered ring and includes, for example, the following rings and the like. * represents a binding site. | & L & £ ù Se 5 59000440
[0135] [0135] The cycle formed by combining RP and RP! together can be a monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated ring. This ring includes a 3 to 12 membered ring and is preferably a 3 to 7 membered ring. The ring includes, for example, a thiolan-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, a 1,4-oxathian-4-ium ring and the like.
[0136] Among the cation (b2-1) to the cation (b2-4), a cation (b2-1) is preferred.
[0137] [0137] (b2-c-21) (b2-c-22) (b2-c-23) (b2-c-24) (b2-c-25) $ aan Se lS] IS © 75 {b2-c -473 {b2-c-48} jh> -0-481
[0138] [0138] Examples of cation (b2-2) include the following cations and the like. (b2-c-28) (b2-c-29) (b2-c-30)
[0139] [0139] Examples of cation (b2-3) include the following cations and the like.
[0140] [0140] Examples of cation (b2-4) include the following cations and the like. Hs © © © 7 TOO ZOO ZOO 3050 @ (2 (b2-c-35) (b2-c-36) (b2-c-37) (b2-c-38) Ha Hs Ha Ha 2 2 2 2 3970 JOO 3900 500 ”(b2-c-39) U (b2-c-40) Hac (b2-c-41) Ha (b2-c-42) t-CaHo t-CaH9 t-CaHo t-CaHo & © © 3900 00m 300 ZOO ©) (b2-c-44) (y S (b2-c-46) (b2-c-43) teak (b2-c-45) od
[0141] [0141] The structural unit represented by the formula (II-2-A ") is preferably a structural unit represented by the formula (II-2-A): RIIS
[0142] [0142] The structural unit represented by the formula (II-2-A) is preferably a structural unit represented by the formula (II-2-A-1): R! LI3
[0143] [0143] The structural unit represented by the formula (II-2-A-1) is preferably a structural unit represented by the formula (II-2-A-2): RIIS
[0144] [0144] The structural unit represented by the formula (II-2-A ") includes, for example, the following structural units, structural units in which a group corresponding to a methyl group of RS 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 optionally have a halogen atom (for example, a trifluoromethyl group, etc.) and the like and the like structural units mentioned in WO 2012/050015 A. ZA ”represents an organic cation.
[0145] [0145] The structural unit having a sulfonio group and an organic anion in a side chain is preferably a structural unit represented by the formula (II-1-1): R'l4 ef RIS (Il-1-1) or ,
[0146] [0146] Examples of a structural unit including a cation in the formula (II-1-1) include the following structural units and structural units in which a group corresponding to R! * Is substituted by a hydrogen atom, a fluorine atom, trifluoromethyl group or the like.
[0147] [0147] Examples of the organic anion represented by A include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion and a carboxylic acid anion. The organic anion represented by A is preferably a sulfonic acid anion, and the sulfonic acid anion is preferably an anion included in the subsequently mentioned salt represented by the formula (B1).
[0148] [0148] Examples of the sulfonylimide anion represented by A include the following. Ff: £ Fs F, C-CF, E _ _—, _— / 2 020 CF3 020 CF »020 CF» O2 CF EN | |. LL 47 O2S-CF3 OS O2S-CF2 O2S — CF2 O, S — CF, F3 FÈ-CF, CF,
[0149] [0149] Examples of the sulfonylmethide anion include the following. £ F3 F2 -CF3 O, S CF; O, S-CF, bone, ©, | F2 0, | - F4C, Fo O2 | F, C-S 5 FsC-C-S = FXX-C-S “O, S-CF3 O2S-GF2 O25-CFs CF F, C-CF;
[0150] [0150] Examples of the carboxylic acid anion include the following. O 0 0 D _ Ho HC A HEA een Oe
[0151] [0151] Examples of structural unit represented by formula (II-1-1) include structural units represented by the following formulas. Hs Hz Hz ES Jos CO RE BF SE He 03 LL. © Os Ton Hz A Jon, Hz N iron. Hz)
[0152] [0152] When the structural unit (IT) is included in the resin (A), the content of the structural unit (IT) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and more preferably 3 to 10 mol%, based on all the structural units of the resin (A).
[0153] [0153] The resin (A) can include structural units other than the structural units mentioned above, and examples of such structural units include structural units well known in the art.
[0154] The resin (A) is preferably a resin composed of a structural unit (a1) and a structural unit (s), that is to say a copolymer of a monomer (a1) and a monomer (s).
[0155] [0155] <Resin other than resin (A)> In the resist composition of the present invention, resins other than resin (A) can be used in combination. The resin other than the resin (A) includes, for example, a resin including a structural unit (a4) or a structural unit (a5) (hereinafter sometimes called resin (X)). The resin (X) is preferably a resin including a structural unit (a4), in particular. In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, and more preferably 45 mol% or more, based on the total of all the structural units of the resin (X). Examples of a structural unit, which may be further included in the resin (X), include a structural unit (a1), a structural unit (a2), a structural unit (a3), and structural units derived from other monomers. known. In particular, the resin (X) is preferably a resin composed only of one structural unit (a4) and / or one structural unit (a5). The respective structural unit constituting the resin (X) can be used alone, or two or more structural units can be used in combination. By using a monomer from which these structural units are derived, it is possible to produce a resin by a known polymerization process (eg, radical polymerization process). The content of the respective structural units included in the resin (X) can be adjusted according to the amount of the monomer used in the polymerization.
[0156] [0156] When the resist composition includes the resin (X), the content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, more preferably 1 to 40 parts by mass, more preferably 1 to 30 parts by mass, and more preferably 1 to 8 parts by mass, based on 100 parts by mass of the resin (A).
[0157] [0157] 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 wt% or more and 99 wt% 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.
[0158] [0158] <Acid Generator (B)> A nonionic or ionic acid generator can be used as an acid generator (B). Examples of the 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 anion of the onium salt include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion and the like.
[0159] The acid generator (B) is preferably an acid generator containing fluorine, and more preferably a salt represented by formula (B1) (hereinafter sometimes called “acid generator (B1) "): QP1 Z * O3S Le! SU, (BIJ) Lo Where in formula (B1), QPt and QP Each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, 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 divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CH> - included in the hydrocarbon group alicyclic can be replaced by -O-, -S (O) 2- or -CO-, and Z * represents a cation o organic.
[0160] [0160] Examples of the perfluoroalkyl group represented by Q ”and QP2 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group. and a perfluorohexyl group.
[0161] [0161] 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.
[0182] [0182] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by L ”is replaced by -O- or - CO- includes, for example, a group represented by any one of the formula (b1- 1) to the formula (b1-3). In the groups represented by the formula (b1-1) in the formula (b1-3) and in the groups represented by the formula (b1-4) in the formula (b1-11) which are specific examples thereof, * and ** represent a binding site, and * represents a -Y binding site.
[0163] [0163] + Lx + OS 0 + oro, DS, ba ”1> See Sp a7 7
[0164] In the groups represented by the formula (b1-1) in 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.
[0165] [0165] Examples of the group represented by the formula (b1-1) include the groups represented by the formula (b1-4) to the formula (b1-8).
[0166] [0166] Examples of the group represented by the formula (b1-3) include the groups represented by the formula (b1-9) to the formula (b1-11). AA AE AA SC
[0167] [0167] In the groups represented by the formula (b1-9) in the 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.
[0168] [0168] Examples of an alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.
[0169] [0169] Examples of the group represented by the formula (b1-4) include the following: O0 O O O CH3
[0170] [0170] Examples of the group represented by the formula (b1-5) include the following: ANA Ah ES Aa At Ad Sa ANSE À va As AON CH3 CH3 No. 2 3 CHs 3 x ASS sn AA DM ere Ae D Ö Ç yy ï +
[0171] [0171] Examples of the group represented by the formula (b1-6) include the following: 0 Aetos Ado Atos ZA A0
[0172] [0172] Examples of the group represented by the formula (b1-7) include the following: CHs Ee Aak. Ag Ae AN A Ag Q x Q Ede x AD AAST LAS op Je Ad T CS AA
[0173] [0173] Examples of the group represented by the formula (b1-8) include the following: sek Lx, x Vo Dt OL Le
[0174] [0174] Examples of the group represented by the formula (b1-2) include the following: | Q $ * AY Q X GAS As un, HA, 3 CH3 + Hs Hot AA AA AA A a ak A Ar iel
[0175] [0175] Examples of the group represented by the formula (b1-9) include the following:
[0176] [0176] Examples of the group represented by the formula (b1-10) include the following: Ha Ha Hz A AN A „DOW>„ oA „oA step Oe„ of DA 3 CHs No. ak FFF Fr F F3 Arde PP Arde : dre 4th CHs} 2 | 5 dede dote) endow H O
[0177] [0177] Examples of the group represented by the formula (b1-11) include the following: CHs 0 Aho Ao FF X F X F F CH3 F F3 F F3 dg AA JT AR
[0178] [0178] Examples of the alicyclic hydrocarbon group represented by Y include the groups represented by formula (Y1) to formula (Y11) and formula (Y36) to formula (Y38).
[0179] [0179] 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, a group glycidyloxy, a group - (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 groups obtained by combining these groups,, -CHz- included in an alkyl group and the alicyclic hydrocarbon group can 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 with a hydroxy group or a fluorine atom and ja represents an integer of 0 to 4) and the like.
[0180] [0180] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0181] [0181] Examples of Y include the following =. KA SX de) / -CF2 © CF, Ó d Ur Das ae rde TA 3 * 9 oO Oy 0 7 A (Y100) * *. Oy 0 101) (Y102) (Y103) (Y104) * x ©. Oo © (Y105) (v106) dr A UV A O CH oO CHs 0 CH,
[0182] [0182] 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, and more preferably an adamantyl group which may have a substituent, and -CHz- constituting the alicyclic hydrocarbon group or the adamantyl group may be replaced by -CO-, -S (0)> - or -CO-. More specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, or groups represented by the formula (Y42), and the formula (Y100) to the formula (Y114).
[0183] [0183] The anion in the salt represented by formula (B1) is preferably an anion represented by formula (B1-A-1) to formula (B1-A-59) [hereinafter sometimes referred to as "anion (B1-A-1) "according to the number of the formula], and more preferably an anion represented by any one of the formula (B1-A-1) to the formula (B1-A-4), the formula (B1- A-9), formula (B1-A- 10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40) and formula (B1-A-47) to formula (B1-A-59).
[0184] [0184] OH OH 5 om (KX om! „Or Q Bt Se or (B1-A-1) O (B1-A-2) (B1-A-3) b1 b2 b1 b2 i2 b1 b2 7,077 ° „A T os Where R os AO ° (B1-A-4) ° (B1-A-5) ° (B1-A-6)
[0185] [0185] RS b1 b2 - b1 b2 Q Q abi Lab À _ QUO Or 4 O “os On A4“ os N 058 L 5 3 I L 5 Ô 0 b (B1-A-7) (B1-A-8) (B1-A-9) 9
[0186] [0186] OH
[0187] [0187] 0 OOR i i7 af! Lab RIS ab! To À at RIS Ri 70:87 Sp SuM 7038 O. O7 el on Ô O os SLAM
[0188] [0188] Ri3 ar! "To se se a 70.8 O. oo O + S f Ô Ô 9 (B1-A-42) (B1-A-43) (B1-A-44) a9 ab2 De. 0:57 703 x 9 1-0 O © (B1-A-45) (B1-A-46)
[0189] [0189] O Oo 0 O O D. + D Oo Q "Q52 ION a a 0 ap! Q ° 2 O - Os Ad - XS A4 OST L - 0: 8 Sp si OS L
[0190] [0190]
[0191] [0191] R to RU each independently represent, for example, an alkyl group having 1 to 4 carbon atoms, and preferably a methyl group or an ethyl group. R® is, for example, a chain 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 groups formed in 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.
[0192] Preferred anions in the salt represented by formula (B1) are anions represented by formula (B1a-1) to formula (B1a-38). HO
[0193] [0193]
[0194] [0194]
[0195] [0195] A = "O3S
[0196] [0196] Among these, anion represented by any one of formula (B1a-1) to formula (B1a-3) and from formula (B1a-7) to formula (B1a-16), the formula (B1a-18), the formula (B1a-19) and the formula (B1a-22) to the formula (B1a-38) are preferable.
[0197] [0197] Examples of the organic cation of Z * include an organic cation onium, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation and an organic phosphonium cation, and include those identical to the organic cation ZA '. in the structural unit represented by the formula (II-2-A "). Among them, an organic sulfonium cation and an organic iodonium cation are preferable, and an arylsulfonium cation is more preferable.
[0198] [0198] The acid generator (B) is a combination of the aforementioned anions and the aforementioned organic cations, and these can optionally be combined. Examples of the acid generator (B) are preferably combinations of an anion represented by any one of formula (B1a-1) with formula (B1a-3), of formula (B1a-7) to the formula (B1a-16), the formula (Bla 18), the formula
[0199] Examples of the acid generator (B) are preferably those represented by formula (B1-1) to formula (B1-56). Of these, 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 preferable. <© 5;
[0200] [0200] y KF 9 KF OA; OER SETRS ord (B1-13) (B1-14) (B1-15) 7 © a sea Ron - xd * "0.8 cer F (+ * 0.8 Tets VS pos |
[0201] [0201]] REF OC OD ST G… O (81-22) LI 0:58 3-5 05 © (B1-23) OO (B1-24) won Shan Lahn 05 ca 24 ca t OE gf) (B1- 25) (B1-26) (B1-27) ox LÀ + 033 + FF SSL AA Oo (B1-28) (B1-29) (B1-30)
[0202] [0202] 0 LF G F O () f 9 SE A ho F (B1-37) (B1-38) (B1-39) o Le aL aL Ot SE 3 © d
[0203] [0203] Oo
[0204] [0204] In the resist composition of the present invention, the content of acid generator is preferably 1 part by mass or more and
[0205] [0205] <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 known analytical means such as liquid chromatography or gas chromatography.
[0206] [0206] <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)"), if necessary.
[0207] [0207] <Preparation of resist composition> The resist composition of the present invention can be prepared by mixing a salt (I), a resin (A), an acid generator (B), and if necessary, resins other than resin (A), a solvent (E), a deactivating agent (C) and other components (F). The order of mixing these components is any order and is not particularly limited. It is possible to choose, as the temperature during mixing, an appropriate temperature of 10 to 40 ° C, depending on the type of the resin, the solvent solubility (E) of the resin and the like. It is possible to choose, as the mixing time, an appropriate duration 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 stirring. After mixing the respective components, the mixture is preferably filtered through a filter having a pore diameter of about 0.003 to 0.2 µm.
[0208] [0208] (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 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 development of the heated composition layer. The resist composition can usually be applied to a substrate by means of an apparatus used conventionally, such as a centrifugal applicator ("spin coater"). Examples of the substrate include inorganic substrates such as a silicon wafer. Prior to application of the resist composition, the substrate can be washed, and an organic anti-reflective film can be formed on the substrate. The solvent is removed by drying the applied composition to form a composition layer. The drying is carried out by evaporation of the solvent by means of a heating device such as a hot plate (called a "pre-cook") or a decompression device. The heating temperature is preferably 50 to 200 ° C and the heating time is preferably 10 to 180 seconds. The pressure during drying under reduced pressure is preferably about 1 to 1.0 x 10 ° Pa.
[0209] [0209] (Applications) The resist composition of the present invention is suitable as a resist composition for exposure to a KrF excimer laser, a resist composition for exposure to an ArF excimer laser, a resist composition for exposure to a KrF excimer laser. electron beam (FE) or a resist composition for exposure to extreme ultraviolet (UVE), and more suitable as a resist composition for ArF excimer laser exposure, a resist composition for exposure of an electron beam an electron beam (FE) (or EB for electon beam) or as a resist composition for exposure to UVE and the resist composition is useful for fine processing of semiconductors.
[0210] [0210] The present invention will be described more specifically by way of examples. The percentages and the parts expressing the contents or the amounts used in the examples are by weight unless otherwise indicated.
[0211] [0211] Example 1: Synthesis of the salt represented by the formula (I-1) HO. te EF wi CoH Pa A FN / TL SA 97/7 C00Me to MeO .__ COOMe Ee = SP WHERE 7 id nn ji ie —— Dee EN meu TT A; PSE ÔMe (1-1-b) {-te) (; (1-1-a} {1-1-d) parts of a compound represented by formula (I-1-a) and 40 5 parts of chloroform were mixed and, after stirring at 23 ° C for 30 minutes, 7.51 parts of a compound represented by formula (I-1-b) were added and the temperature was raised to 50 ° C, followed by stirring at 50 ° C for 2 hours To the mixture thus obtained, 8.74 parts of a compound represented by formula (I-1-c) was added, followed by stirring at 50 ° C for 3 The mixture thus obtained was cooled to 23 ° C followed by 40 parts of ion-exchanged water and, after stirring at 23 ° C for 30 minutes, the organic layer was isolated by separation. organic layer thus obtained, 40 parts of a 5% aqueous solution of oxalic acid was added and, after stirring at 23 ° C for 30 minutes, the organic layer was isolated by separation. The organic layer thus obtained was concentrated. to obtain 15.65 parts of a co mpositive represented by formula (I-1-d). FD = Or Men, AUOMe VA A © VE Le
[0212] [0212] Example 2: Synthesis of the salt represented by the formula (I-8) N Î ol a.
[0213] [0213] Example 3: synthesis of the salt represented by formula (I-2)
[0214] [0214] 1.00 part of a salt represented by formula (I-1) and 20 parts of 1,2-dichloroethane were mixed and, after stirring at 23 ° C for 30 minutes, 0.58 part of a compound represented by the formula (I-2-a) and 0.03 part of p-toluenesulfonic acid were added, which was followed by stirring under reflux at 100 ° C for 3 hours. The reaction product thus obtained was cooled to 23 ° C, then 50 parts of chloroform and 25 parts of a 5% aqueous sodium hydrogencarbonate solution were added, which was followed by stirring at 23 °. C for 30 minutes. After stirring and standing, isolation by separation was performed. To the organic layer thus recovered, 25 parts of ion-exchanged water was added and, after stirring at 23 ° C for 30 minutes, the organic layer was recovered by isolation by separation. This water washing operation was carried out five times. The organic layer thus obtained was concentrated and then 20 parts of tert-butylmethyl ether was added to the concentrate thus obtained, which was followed by stirring at 23 ° C for 1 hour and further by filtration to obtain 0.58 part. of a salt represented by formula (I-2). MASS (ESI spectrum (+)): 701.2 [M + H] *
[0215] [0215] Example 4: Synthesis of a salt represented by the formula (I-39) | nc Eh A an De - SP> j 7 ON 50th F ’ue (8) (28) (1-39)
[0216] [0216]
[0217] [0217] Example 5: Synthesis of a salt represented by the formula (I-38) ry HO in Sa | TO y COOME MeD__eN_ COOMe
[0218] [0218] Example 6: Synthesis of a salt represented by the formula (I-40) A | + TD. Meo @ oo + Ho> 2 20, Me oo T ° OMe ° OMe (-38) (2-2 (1-40)
[0219] [0219] 1.03 part of a salt represented by formula (I-38) and 20 parts of 1,2-dichloroethane were mixed and, after stirring at 23 ° C for 30 minutes, 0.58 part of a compound represented by the formula (I-2-a) and 0.03 part of p-toluenesulfonic acid were added, which was followed by stirring under reflux at 100 ° C for 3 hours. The reaction product thus obtained was cooled to 23 ° C, then 50 parts of chloroform and 25 parts of a 5% aqueous sodium hydrogencarbonate solution were added, which was followed by stirring at 23 °. C for 30 minutes. After stirring and standing, isolation by separation was performed. To the organic layer thus recovered, 25 parts of ion-exchanged water was charged, and after stirring at 23 ° C for 30 minutes, the organic layer was recovered after being isolated by separation. This water washing operation was carried out five times. The organic layer thus obtained was concentrated, then 20 parts of tert-butylmethyl ether was added to the concentrate thus obtained, followed by stirring at 23 ° C for 1 hour and further filtration to obtain 0.62 part of a salt shown. by the formula (I -40).
[0220] [0220] Example 7: Synthesis of a salt represented by the formula (I-35) 0 ”| Hol Meo, "COOMe MH SG 9 A COOMe o SI I" A TO T Me 4 eee 0 x {t-1-b} (11-0); (-35-a) {1-35-d) 9.38 parts of a compound represented by formula (I-35-a) and 40 parts of chloroform were mixed and, after stirring at 23 ° C for 30 minutes, 7.51 parts of a compound represented by formula (1-1-b) was added and the temperature was raised to 50 ° C, which was followed by stirring at 50 ° C for 2 hours . To the mixture thus obtained, 8.74 parts of a compound represented by the formula (I-1-c) was added, which was followed by stirring at 50 ° C for 3 hours. The thus obtained mixture was cooled to 23 ° C, then 40 parts of ion-exchanged water was added and, after stirring at 23 ° C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 40 parts of a 5% aqueous solution of oxalic acid was added and, after stirring at 23 ° C for 30 minutes, the organic layer was isolated by separation. The organic layer thus obtained was concentrated to obtain 16.11 parts of a compound represented by the formula (I-35-d).
[0221] [0221] Synthesis of Resin The compounds (monomers) used in the synthesis of the resin (A) are indicated below. Hereinafter, these compounds are called "monomer (a1-1-3)" depending on the number of the formula.
[0222] [0222] Synthesis Example 1: Synthesis of Resin A1 A monomer (a1-1-3), a monomer (a1-2-5), a monomer (a2-1-3) and a monomer (a3) were used. -4-2) as monomers, and these monomers were mixed in a ratio of 45: 14: 2.5: 38.5 [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-3): monomer (a3-4-2)] and propylene glycol monomethyl ether acetate was added to this mixture of monomers in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in the amounts of 1 mol% and 3 mol% based on the total molar number of all monomers, then the mixture was heated to 73 ° C for about 5 hours. The reaction mixture thus obtained was poured into a large amount of a methanol / water mixture solvent to precipitate a resin, and this resin was filtered. This was followed by a reprecipitation operation which consists in dissolving the resin thus obtained again in propylene glycol monomethyl ether acetate to obtain a solution, in pouring the solution into a methanol / water mixture solvent to precipitate the solution. resin, and filtering the resin twice to obtain an A1 resin having a weight average molecular weight of 7.6 x 103 in a yield of 68%. This A1 resin has the following structural units.
[0223] Synthesis Example 2: Synthesis of the X1 Resin A monomer (a5-1-1) and a monomer (a4-0-12) were used as monomers, these monomers were mixed in a molar ratio of 50: 50 [monomer (a5-1-1): monomer (a4-0 -12)], and methyl isobutyl ketone was added to this mixture of monomers in an amount of 1.2 times the mass of all monomers. To the mixture thus obtained, azobis (2,4-dimethylvaleronitrile) was added as an initiator in an amount of 3 mol% based on the total molar number of all monomers, and then the mixture was heated to 70 ° C for about 5 hours. The reaction mixture thus obtained was poured into a large amount of a methanol / water mixture solvent to precipitate a resin, and this resin was filtered to obtain a resin X1 having a weight average molecular weight of 1.0 x 10% with a 91% yield. This X1 resin has the following structural units. CH
[0224] [0224] <Preparation of Resist Compositions> As shown in Table 1, the following respective components were mixed and the mixtures thus obtained were filtered through a fluororesin filter having a pore diameter of 0.2 µm for preparing resist compositions.
[0225] [0225] <Resin> A1, X1: resin A1, resin X1 <Acid generator (B)> B1-21: salt represented by formula (B1-21) B1-22: salt represented by formula (B1- 22) O C J O
[0226] [0226] (Production of the resist pattern and its evaluation) A composition for an organic anti-reflective film (ARC-29, manufactured by Nissan Chemical Co. Ltd.) was applied to a silicon wafer and baked at 205 ° C for 60. seconds to form an organic anti-reflective film 78 nm thick on the silicon wafer. Then, the aforementioned resist composition was applied to the organic anti-reflection film by centrifugal application (spin coating) so that the thickness of the film after drying becomes 85 nm.
[0227] [0227] The effective sensitivity was represented as the exposure dose at which the diameter of the hole formed using the mask reached 45 nm in the resist pattern obtained after development.
[0228] [0228] <Evaluation of mask error factor (MEF)> Using masks each having a hole diameter (hole dimeter of the translucent part of the mask) of 57 nm, 56 nm, 55 nm, 54 nm and 53 nm (the hole pitch is 90 nm in all cases), resist patterns were produced at the effective sensitivity. When the mask hole diameters are plotted on the x-axis, while the hole diameters of the resist patterns formed (transferred) on the substrate by exposure are plotted on the y-axis, the slope of a line regression plotted was determined as the value of the MEF.
[0229] [0229] A resist salt and composition including the salt of the present invention provide a resist pattern with a satisfactory mask error factor (MEF) and therefore are extremely useful for fine processing semiconductors. .

权利要求:
Claims (9)
[1]
1. A salt represented by formula (I): R4 (Rm x Te -0 + a (RE) m2 where, in formula (I), R * represents a halogen atom, an alkyl fluoride group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, and -CHz- included in the hydrocarbon group may be replaced by -O- or -CO-, R2 and R3 each independently represent a halogen atom , an alkyl fluoride group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, -CHz- included in the hydrocarbon group may be replaced by -O-, -CO-, or R2 and R3 can be linked to each other to form a single bond or an alkanediyl bridge having 1 to 6 carbon atoms with the carbon atoms to which R and R are attached, and -CH> - included in the alkanediyl bridge can be replaced by - O-, -S-, -CO-, -SO- or -SO2- m1 represents an integer of 0 to 3, and when m1 is 2 or more, a plurality of R * may be the same or different each other s, m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R2 may be the same or different from each other, m3 represents an integer of 0 to 4, and when m3 is 2 or more, a plurality of R * can be identical or different from each other,
R *, R ° and R ° each independently represent a hydrogen atom or -X ° -R7, wherein at least one of R *, R ° and R ° represents -X7-R7, X ”represents * - CO-O-, * -O-CO- or * -O-CO-O-, and * represents a benzene ring binding site, and R ”represents a hydrocarbon group including a cyclic hydrocarbon group having 3 to 18 carbon atoms. carbon (the cyclic hydrocarbon group may have a substituent), and -CH> - included in the hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-.
[2]
2. The salt of claim 1, where R * represents -X * -R ’,
[3]
3. A deactivating agent comprising a salt according to claim 1.
[4]
4. A resist composition comprising the deactivating agent of claim 3, a resin including a structural unit having an acid labile group, and an acid generator.
[5]
5. The resist composition of claim 4, wherein the resin comprising a structural unit including an acid labile group includes at least one structural unit selected from the group consisting of a structural unit represented by formula (a1-1). and a structural unit represented by the formula (a1-2): pad 38 Ha / Ha AR # 0. AO Sm A UP {OH art {Hs Ra UJ (CH RT> CH} En 7 Se {at-1} (ai-2} where, in formula (a1-1) and formula (a1-2), L # and L ° each independently represent -O- or * -O- (CH2) z1-CO-O-, k1 represents an integer from 1 to 7, and * represents a -CO- binding site,
R ° * and R® each independently represent a hydrogen atom or a methyl group, R °° and R each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 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 n1 'represents an integer from 0 to 3.
[6]
6. The resist composition of claim 4, wherein the acid generator includes a salt represented by formula (B1): + OS [61 Z O3 Se ”, (BT) where, in formula (B1), QP! and QP each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, 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 the hydrogen atom included in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CH> - included in the group Alicyclic hydrocarbon can be replaced by -O-, -S (O) 2- or -CO-, and Z * represents an organic cation.
[7]
7. The resist composition of claim 4 further comprising an acid generating salt having an acidity lower than that of an acid generated by the acid generator.
[8]
8. The resist composition of claim 4, further comprising a resin comprising a structural unit having a fluorine atom.
[9]
A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition of claim 4 to a substrate, (2) a step of drying the applied composition to form a layer. composition, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and (5) a step of developing the heated composition layer.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

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|

---

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|

---

JP5750242B2|2009-07-14|2015-07-15|住友化学株式会社|resist composition|

---

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|

---

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|

---

JP6583136B2|2016-05-11|2019-10-02|信越化学工業株式会社|Novel sulfonium compound and method for producing the same, resist composition, and pattern forming method|

---

US10042251B2|2016-09-30|2018-08-07|Rohm And Haas Electronic Materials Llc|Zwitterionic photo-destroyable quenchers|

---

KR20180066985A|2016-12-11|2018-06-20|연세대학교 산학협력단|Thienopyrimidine derivative and use thereof|

---

WO2019123895A1|2017-12-22|2019-06-27|富士フイルム株式会社|Active-light-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, method for manufacturing electronic device, and compound|

---

法律状态:
2021-08-18| FG| Patent granted|Effective date: 20210812 |

优先权:

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申请号 | 申请日 | 专利标题

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JP2019156973|2019-08-29|

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