RESIN, PHOTORESIST COMPOSITION AND PHOTORESIST PATTERN PRODUCTION PROCESS

专利摘要:
It is an object of the present invention to provide a resin capable of producing a resist pattern with satisfactory CD uniformity (CDU) and a resist composition comprising the resin. Disclosed is a resin and a resist composition incorporating it, said resin comprising a structural unit represented by formula (I) and a structural unit represented by formula (a2-A) as defined in claim 1, wherein , in these formulas, R1 represents a hydrogen atom or a methyl group; L1 and L2 each independently represent -O- or -S-; s1 represents an integer of 1 to 3; s2 represents an integer of 0 to 3; Ra50 represents a hydrogen atom, a halogen atom or an alkyl group optionally having a halogen atom; Ra51 represents a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylcarbonyl group or the like; Aa50 represents a single bond or * -Xa51- (Aa52-Xa52) nb-; Aa52 represents an alkanediyl group; xa51 and xa52 each independently represent -O-, -CO-O- or -O-CO-, nb represents 0 or 1, and mb represents an integer of 0 to 4.
公开号:BE1026584B1
申请号:E20205029
申请日:2020-01-16
公开日:2020-12-21
发明作者:Mutsuko Higo；Shingo Fujita；Koji Ichikawa
申请人:Sumitomo Chemical Co；
IPC主号:

专利说明:

[0001] The present invention relates to a resin, a resist composition and a method for producing a resist pattern using the resist composition and the like. BACKGROUND OF THE INVENTION
[0002] [0002] Patent document 1 mentions a resist composition comprising a resin including the following structural units.
[0003] [0003] Patent document 1: JP HO8-101507 A Patent document 2: JP 2014-041327 A Description of the invention Problems to be solved by the invention
[0004] An object of the present invention is to provide a resin which forms a resist pattern having a CD (CDU) uniformity better than that of a resist pattern formed from a resist composition comprising the mentioned resin. above.
[0005] [0005] The present invention includes the following inventions.
[1] [1] A resin comprising a structural unit represented by formula (I) and a structural unit represented by formula (a2-A): 1 Hz R VS
[2] [2] The resin according to [1], further comprising 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 formula (a1-2):
[3] [3] A resist composition comprising the resin according to [1] or [2] and an acid generator.
[4] [4] The composition of resist according to [3], where the acid generator includes a salt represented by the formula (B1): a zZ 0381 AT (Bt) Se ye 8507 a ’ where, in formula (B1),
[5] [5] A resist composition according to [3] or [4], further comprising an acid generating salt having an acidity lower than that of an acid generated by the acid generator.
[6] [6] A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to any one of [3] to [5] 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 heated composition layer. Effects of the invention
[0006] By using a resist composition comprising a resin of the present invention, it is possible to produce a resist pattern with satisfactory CD uniformity (CDU). Mode for implementing the invention
[0007] [0007] As used herein, the term "(meth) acrylate" means "at least one selected from the group consisting of acrylate and methacrylate"
[0008] [0008] [Resin] The resin of the present invention is a resin (hereinafter sometimes referred to as "resin (A)") comprising a structural unit represented by formula (I) (hereinafter sometimes referred to as structural unit (I) ) and a structural unit represented by the formula (a2-A) (hereinafter sometimes called structural unit (a2-A)).
[0009] [0009] <Structural unit (I)> In formula (I), R * is preferably a methyl group. Lt is preferably -O-. L is preferably -S-. s1 is preferably an integer of 1 to 2, and preferably 1. s2 is preferably an integer of 0 to 2, and preferably 1.
[0010] [0010] Examples of the structural unit (I) include the structural units mentioned below.
[0011] It is possible to cite as an example structural units in which a methyl group corresponding to R! is substituted with a hydrogen atom in structural units represented by formula (I-1) with formula (I-8) as specific examples of structural unit (I). Among them, the structural units represented by the formula (I-1) to the formula (I-4) are preferable, the structural units represented by the formula (I-1) to the formula (I-3) are more preferable, and a structural unit represented by formula (I-1) is even more preferable.
[0012] The content of the structural unit (I) in the resin (A) is preferably 3 to 80 mol%, more preferably 5 to 70 mol%, more preferably 7 to 70 mol%, and more preferably from 7 to 65 mol%, based on all structural units.
[0013] [0013] <Structural unit (a2-A)> A structural unit (a2-A) is represented by the following formula: Hz R3a50 He A250 (a2-A)
[0014] [0014] Examples of the halogen atom in R °°° include a fluorine atom, a chlorine atom and a bromine atom.
[0015] [0015] Examples of structural unit (a2-A) include structural units derived from the monomers mentioned in JP 2010-204634 A and JP 2012-12577 A.
[0016] The content of the structural unit (a2-A) in the resin (A) is preferably 5 to 85 mol%, more preferably 10 to 85 mol%, more preferably 15 to 80 mol%, and more preferably 20 to 75 mol%, based on all structural units.
[0017] The resin of the present invention (A) can be a polymer including one or more structural units other than the structural unit (I) and the structural unit (a2-A). Examples of structural unit other than structural unit (I) and structural unit (a2-A) include a structural unit having an acid labile group other than structural unit (I) (hereinafter sometimes called "structural unit (ai)"), a structural unit which is a structural unit other than the structural unit having an acid labile group and has a halogen atom (hereinafter sometimes called "structural unit (a4) "), A structural unit having no labile group in an acidic medium other than the structural unit (a2-A) (hereinafter sometimes called" structural unit unit (s) "), a structural unit having a hydrocarbon group non-starting (hereinafter sometimes called “structural unit (a5)”), and the like. The "acid labile group" means a group having a leaving group which is removed by contact with an acid, thereby forming a hydrophilic group (eg, a hydroxy group or a carboxy group). In particular, the resin (A) preferably includes, in addition to the structural unit (I) and the structural unit (a2-A), a structural unit having an acid labile group, and preferably includes in least one structural unit selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2).
[0018] [0018] <Structural Unit (a1)> The structural unit (a1) is derived from a monomer comprising a labile group in an acidic medium (hereinafter sometimes called "monomer (a1)").
[0019] [0019] Examples of the alkyl group for R ° *, R ° 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 analogues.
[0020] [0020] Examples of the hydrocarbon group in R °, R ° and R® 'include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and groups obtained by combining these groups. Examples of the alkyl group and the alicyclic hydrocarbon group include those which are the same as those mentioned in Ra *, R22 and R. Examples of the aromatic hydrocarbon group include an aryl group, such as a phenyl group, a naphthyl group, a group anthryl, a biphenyl group, and a phenanthryl group.
[0021] [0021] Examples of group (1) include the following groups.
[0022] [0022] Specific examples of group (2) include the following groups. * represents a binding position.
[0023] 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.
[0024] The structural unit derived from a (meth) acrylic monomer having a group (1) is preferably a structural unit represented by the formula (a1-0) (hereinafter sometimes referred to as structural unit (a1- 0) ), a structural unit represented by 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 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. .
[0025] [0025] R # 01 R ° * and R °° are preferably a methyl group.
[0026] [0026] Examples of the structural unit (a1-0) include a structural unit represented by any one of the formula (a1-0-1) in the formula (a1-0-12) and a structural unit in wherein a methyl group corresponding to R * ° in structural unit (a1-0) is substituted with a hydrogen atom and a structural unit represented by any one of the formula (a1-0-1) in the formula (a1-0-10) is preferred.
[0027] [0027] The structural unit (a1-1) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646A. Among these structural units, a structural unit represented by any one of the formula (a1-1-1) to the formula (a1-1-4) and a structural unit in which a methyl group corresponding to R ° * in l 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) with formula (a1-1-4) is favorite again.
[0028] [0028] Examples of structural unit (a1-2) include a structural unit represented by any one of formula (a1-2-1) to formula (a1-2-6) and a structural unit in which a methyl group corresponding to R3 in the structural unit (a1-2) is substituted with a hydrogen atom, and the structural units represented by the formula (a1-2-2), the formula (a1-2-5) and formula (a1-2-6) are preferred.
[0029] [0029] Examples of the structural unit having a group (2) in the structural unit (a1) include a structural unit represented by the formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1-4 ) "): Ra32 Lo DS (a1-4) ras} 34 | FO Ra36 Ra35 where, in formula (a1-4), R52 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms optionally having 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 group alkylcarbonyl having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group,
[0030] [0030] Examples of the alkyl group in R ° and R233 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.
[0031] In the formula (al-4), R °°° is preferably a hydrogen atom, R53 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, R35 * is preferably a hydrogen atom, and R3 ° 5 is preferably an alkyl group having 1 to 12 carbon atoms. carbon or an alicyclic hydrocarbon group, and more preferably a methyl group or an ethyl group.
[0032] [0032] 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 constituent unit (a1-4) is substituted with a methyl group, and more preferably them structural units represented by the formula (a1-4-1) to the formula (a1-4-5) and the formula (a1-4-10). Piter edt PET Pit OO OO O0 O0 O0. O0 vo Y ro TD (a1-4-1) (a1-4-2) (a1-4-3) ne mag 9 (a1-4-6) ore 5 LEE Pat Lu PET Tel © OL CHs OCHs f CH £ “Pers
[0033] The structural unit (a1) also comprises, for example, a structural unit represented by the formula (a1-OX) (hereinafter sometimes called structural unit (a1-0X)): Rx "out‚ p = ( a1-0X) RX RX3 x where in the formula (a1-0X), RX! represents a hydrogen atom or a methyl group, R ** and R ** each independently represent a group - saturated hydrocarbon having 1 to 6 atoms carbons, and Ar represents an aromatic hydrocarbon group having 6 to 36 carbon atoms
[0034] Examples of the saturated hydrocarbon group for R * and R °, include an alkyl group, an alicyclic hydrocarbon group and a group formed by combination thereof.
[0035] [0035] Examples of the structural unit (a1-OX) include the following structural units and a structural unit in which a methyl group corresponding to R * in the structural unit (a1-0X) is - substituted by a d atom 'hydrogen. The structural unit (a1-OX) preferably comprises one structural unit (a1-0X-1) to one structural unit (a1-OX-3).
[0036] [0036] Examples of the structural unit (a1) also include the following structural units. = = = 0 = 0 C = O = 0 = O x% H5 9 D Jo to (a1-3-1) (a1-3-2) (a1-3-3) (a1-3-4) (a1 -3-5) (a1-3-6) (a1-3-7) When the resin (A) comprises the aforementioned structural unit, the content is preferably 5 to 60 mol%, preferably 5 to 50 mol% and more preferably 10 to 40 mol%, based on all the structural units of the resin (A).
[0037] [0037] <Structural Unit (s)> It is possible to use, as the monomer from which the structural unit (s) are derived, a monomer having no labile group in an acid medium known in the field of resistance.
[0038] [0038] <Structural Unit (a2)> Examples of the hydroxy group belonging to the structural unit (a2) include an alcoholic hydroxy group, and examples of the structural unit (a2) include the unit mentioned later. The structural unit (a2) can be included alone, or two or more structural units can be included.
[0039] In formula (a2-1), L ° * is preferably -O- or -O- (CH2); - CO-O- (fl represents an integer from 1 to 4), and more preferably - O-, R3! $ Is preferably a methyl group, R3! 5 is preferably a hydrogen atom,
[0040] [0040] The structural unit (a2-1) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646 A. A structural unit represented by any one of the formula (a2-1-1) to formula (a2-1-6) is preferred, a structural unit represented by any one of formula (a2-1-1) to formula (a2- 1-4) is more preferred, and a structural unit represented by formula (a2-1-1) or formula (a2-1-3) is more preferred. Hz CH3 H2 H Hz CH; Ho H Hz H3C Ha H Li ES HESS EE It oO Oo Don Don Dos Des> 9> 9
[0041] <Structural unit (a3)> The lactone ring belonging to the structural unit (a3) can be a monocyclic ring such as a B-propiolactone ring, a y-butyrolactone ring or a ö-valerolactone ring, or a condensed ring a monocyclic lactone ring and the other ring. Preferably, an 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.
[0042] Examples of the aliphatic hydrocarbon group in R ° **, R222, R ° and R225 include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec- group. butyl and a tert-butyl group.
[0043] In the formula (a3-1) to the formula (a3-3), preferably, L ** to L® are each independently -O- or a group in which k3 is an integer of 1 to 4 in * -O- (CHz): 3-CO-O-, more preferably -O- and * -O- CHz-CO-O-, and more preferably an oxygen atom,
[0044] [0044] 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 of the formula (a3-1-1), the formula (a3-1-2), the formula (a3-2-1), the formula ( a3- 2-2), formula (a3-3-1), formula (a3-3-2) and formula (a3-4-1) to formula (a3-4-12), and the units in which the methyl groups corresponding to R213, Ra! °, R220 and R22 * in the formula (a3-1) to the formula (a3-4) are substituted with hydrogen atoms in the above structural units.
[0045] [0045] CH3 Ha CH3 CH3 CH3 Hs CH3 CH3 ct = Let 5 eh, 5 Joh, 5 on> Jor © ett © Ten © Oo O: O 0 (a3-1-1) (a3-2-1) & z ( 23-2x-1) & (a3-3-1) (a3-1-2) (8322) (a3-2x-2) 3.32) Me SR HH 4% * + Y (a3-4-1) (a3 - 3 3 x (es-> (a3-4-6) Hz HH Hz Ha Hz Ht He HE + Eu HH> ee 5% A (a3-4-7) (a3-4-B) A re (a3-4 -9) (83-4-10 (a3-4-11) (a3-4-12) When resin (A) includes structural unit (a3), the total content is usually 2 to 70 mol%, preferably 3 to 60 mol%, and more preferably 5 to 50 mol%, based on all the structural units of the resin (A). Each content of the structural unit (a3-1), of the the structural unit (a3-2), of the structural unit (a3-3) or of the structural unit (a3-4) is preferably from 1 to 60 mol%, more preferably from 1 to 50 mol%, and more preferably from 1 to 40 mol%, based on all the structural units of the resin (A).
[0046] [0046] <Structural unit (a4)> Examples of structural unit (a4) include the following structural units: FE}
[0047] Examples of a chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group. , a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group.
[0048] [0048] 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 by the formula (a4-4):
[0049] [0049] Examples of the divalent aliphatic 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 - methylpropane-1,2-diyl.
[0050] [0050] L * is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
[0051] [0051] 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) is substituted with an atom of hydrogen in the following structural units:
[0052] [0052] a41 HR ——
[0053] Examples of a saturated hydrocarbon group in R ° # include a chain saturated hydrocarbon group and a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and groups formed by combining these groups.
[0054] Examples of the substituent optionally belonging to R ** include at least one selected from the group consisting of a halogen atom and a group represented by the formula (a-g3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred: x ——_ Xa43__ 4245 (a-g3) where, in the formula (a-g3), X represents an oxygen atom, a carbonyl group, * -O- CO- or * -CO-O-, A: represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, and * represents a binding site.
[0055] Examples of the aliphatic hydrocarbon group in A * ® include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an 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 a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* represents a bond): Examples of a group formed by combination include a group obtained by combining one or more alkyl groups or one or more several 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.
[0056] [0056] R3 * is preferably a saturated hydrocarbon group optionally having a halogen atom, and more preferably an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula (a-g3).
[0057] [0057] When R ** is an aliphatic hydrocarbon group having the group represented by the formula (a-g3), R ** is more preferably a group represented by the formula (a-g2): pe - Aa46__ya44__ A247 (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, X represents ** - O-CO- or ** - CO-O- (** represents a binding site to A ° *), A represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, the total number of carbon atoms of Aë “°, A and X ° ** is 18 or less, and at least one of A * ® and A7 has at least one halogen atom, and * represents a carbonyl group binding site.
[0058] [0058] The number of carbon atoms of the aliphatic hydrocarbon group for A ° * ° is preferably 1 to 6, and more preferably 1 to
[0059] The preferred structure of the group represented by the formula (a-g2) is the following structure (* is a binding site to a carbonyl group).
[0060] [0060] 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- group. 1,5-diyl and a hexane-1,6-diyl group; and branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
[0061] [0061] Examples of a divalent saturated hydrocarbon group represented by A °°°, A and A in the group represented by the formula (a-g1) include a linear or branched alkanediyl group and a monocyclic divalent alicyclic saturated hydrocarbon group, and groups formed by combining an alkanediyl group and a divalent alicyclic hydrocarbon group. 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.
[0062] In a group represented by the formula (a-g1), examples of the group in which Xx 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-R ° ** binding site,
[0063] Examples of structural unit represented by formula (a4-1) include the following structural units, and structural units in which a methyl group corresponding to R ** in the structural unit represented by formula (a4- 1) in the following structural units is substituted with a hydrogen atom.
[0064] CHs Ha CH CH H Hs CHa Pd PR et erf Leu 1 4 4 8 Oo OÖ X F "a 0 o = <X X + Fa CF" F2 / 2 CF, FC O
[0065] The structural unit represented by the formula (a4-1) is preferably a structural unit represented by the formula (a4-2): Ha RS + ”NT (a4-2) A“ pe where, in the formula (a4-2), RF represents a hydrogen atom or a methyl group, L ** represents an alkanediyl group having 1 to 6 carbon atoms, and -CH; - included in the alkanediyl group can be replaced by -O- or -CO-, RF represents a saturated hydrocarbon group having 1 to 20 carbon atoms having a fluorine atom, and the upper limit of the total number of carbon atoms of L ** and R® is 21.
[0066] [0066] Examples of the alkanediyl group having 1 to 6 carbon atoms for L ** include the same groups as those mentioned for the alkanediyl group in A **,
[0067] 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).
[0068] [0068] Examples of the structural unit (a4) include a structural unit represented by the formula (a4-3): Ho Rf + o
[0069] [0069] Examples of the alkanediyl group in L ° include those which are the same as those mentioned in the alkanediyl group of A ° **. The divalent saturated hydrocarbon group optionally having a fluorine atom in Af is preferably a divalent chain saturated hydrocarbon group optionally having a fluorine atom and a divalent alicyclic saturated hydrocarbon group optionally having a fluorine atom, and more preferably a perfluoroalkanediyl group.
[0070] In formula (a4-3), L ° is preferably an ethylene group.
[0071] 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 R7 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).
[0072] The structural unit (a4) also includes a structural unit represented by the formula (a4-4):
[0073] Examples of the saturated hydrocarbon group for R2 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 atoms of carbon having a fluorine atom.
[0074] 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 Rf ! in the structural unit (a4-4) is substituted with a hydrogen atom in the structural units represented by the following formulas.
[0075] [0075] <Structural unit (a5)> Examples of a non-leaving hydrocarbon group belonging to the structural unit (a5) include groups having a linear, branched or cyclic hydrocarbon group. Of these, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. The structural unit (a5) includes, for example, a structural unit represented by the formula (a5-1): Hz 51 C a5-1 + ° (a5-1) 55 4 R52 where in the formula (a5- 1), R ° represents a hydrogen atom or a methyl group, R ° 2 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom included in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and L °° represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH> - included in the saturated hydrocarbon group may be replaced by -O- or -CO-.
[0076] The alicyclic hydrocarbon group in R ° 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.
[0077] The group in which -CH2- included in the divalent saturated hydrocarbon group represented by L ° 5 is replaced by -O- or - CO- includes, for example, the groups represented by the formula (L1-1) at formula (L1-4). In the following formulas, * and ** each represent a binding site, and * represents a binding site to an oxygen atom. er LS Wi LS gr AR] SO a ”RMS OS (L1-1) (L1-2) as (L1-4) ° In the formula (L1-1), X *! represents * -O-CO- or * -CO-O- (* represents a binding site to L **), [** represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms, L ** represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms, and the total number of carbon atoms of L * and L is 16 or less. In formula (L1-2), L ** 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 total number of carbon atoms of L and L ““ is 17 or less. In formula (L1-3), L * represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms,
[0078] [0078] Dl is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
[0079] The group represented by the formula (L1-1) includes, for example, the following divalent groups. From Aa Ae To Aa Aaron
[0080] [0080]
[0081] [0081] The group represented by the formula (L1-2) includes, for example, the following divalent groups.
[0082] [0082] The group represented by the formula (L1-3) includes, for example, the following divalent groups.
[0083] [0083] The group represented by the formula (L1-4) includes, for example, the following divalent groups. X A Ae DONATIONS SO x xx Q kk * Q ** DIT 047 A
[0084] [0084] L ”is preferably a single bond or a group represented by the formula (L1-1).
[0085] 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) is substituted with a hydrogen atom in the following structural units.
[0086] [0086] <Structural unit (II)> The resin (A) can further include a structural unit which is decomposed by exposure to radiation to generate an acid (hereinafter sometimes referred to as "structural unit (II)"). Specific examples of the structural unit (II) 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.
[0087] 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 "):
[0088] [0088] Examples of the halogen atom represented by RS include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0089] X * represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X * represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X ° represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X ° represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 'represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms. x8 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.
[0090] Examples of the organic cation represented by ZA * in the formula (II-2-A ") include those which are the same as the Z * cation in the salt represented by the formula (B1).
[0091] The structural unit represented by the formula (II-2-A ") is preferably a structural unit represented by the formula (II-2-A): RIIS
[0092] The structural unit represented by the formula (II-2-A) is preferably a structural unit represented by the formula (II-2-A-1):
[0093] 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
[0094] 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 the methyl group for RI 2 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 optionally having a halogen atom (for example, a trifluoromethyl group, etc.) and the mentioned structural units in WO 2012/050015 A. ZA ”represents an organic cation.
[0095] The structural unit having a cation having a sulfonio group and an organic anion in a side chain is preferably a structural unit represented by the formula (II-1-1): R114 ef ais (II-1-1) O OAN RK 4 "A where in formula (II-1-1), All represents a single bond or a divalent linking group, RI! Represents an aromatic divalent hydrocarbon group having 6 to 18 carbon atoms, RZ and RI each independently represent a hydrocarbon group having 1 to 18 carbon atoms, and R1 and R “* may be bonded to each other to form a ring with the sulfur atoms to which R and RIE are attached, RI! represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, and A "represents an organic anion.
[0096] Examples of structural unit including a cation in formula (II-1-1) include the following structural units and structural units in which a group corresponding to the methyl group for R !! * is substituted by a d atom. hydrogen, fluorine atom, trifluoromethyl group and the like.
[0097] [0097] 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 aforementioned salt represented by formula (B1).
[0098] Examples of sulfonylimide anion represented by A "include the following. CFs SF3 F2C-CF2 E - _— _— 2 025 CF3 025 CF, Oes CF, 023 Fa eN lees od EL 028 CFa 028-GF2 O2S- CF2 O2S — CF, 028 —CFz CF3 F2C-CF2 CF3 (lb-1) (lb-2) (Ib-3) (lb-4) (lb-5)
[0099] Examples of sulfonylmethide anion include the following. £ F3 F2C-CF3 O25-CF3 O; S-CF O2S-CF O2 ‘| F, 02 7 77 RG 20 F3C-S ai F3C-C -S ai F, C-C Ss ai O »S-CF3 O2S-CF» O2S-CF2 CF3 F, C-CF3
[0100] [0100] Examples of carboxylic acid anion include the following. 0 Oo 0 O
[0101] [0101] Examples of structural unit represented by formula (II-1-1) include structural units represented by the following.
[0102] [0102] When the structural unit (IT) is included in the resin (A), the content of the structural unit (II) 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).
[0103] [0103] 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.
[0104] [0104] The resin (A) is preferably a resin composed of a structural unit (I), and of a structural unit (a2-A), a resin composed of a structural unit (I), of a structural unit (a2-A), one structural unit (a1-1) and one structural unit (a1-2), a resin composed of one structural unit (I), one structural unit (a2- A), and a structural unit (a1-1), a resin composed of a unit structure (I), a structural unit (a2-A) and a structural unit (a1-2), a resin composed of a structural unit (I), a structural unit (a2-A), a structural unit (a1-1), a structural unit (a1-2) and a structural unit ( s), a resin composed of a structural unit (I), a structural unit (a2-A), a structural unit (a1-1) and a structural unit (s), a resin composed of 'a structural unit (I), a structural unit (a2-A), a structural unit (a1-2) and a structural unit (s), a resin c composed of a structural unit (I), a structural unit (a2-A) and a structural unit (s), a resin composed of a structural unit (I), a structural unit (a2- A), a structural unit (a1-1), a structural unit (a1-2), a structural unit (s), a structural unit (a4) and / or a structural unit (a5), or a resin composed of a structural unit (I), a structural unit (a2-A), a structural unit (a1-1), a structural unit (a1-2) and a unit structural unit (a4), and more preferably a resin composed of a structural unit (I) and a structural unit (a2-A), a resin composed of a structural unit (I), of a structural unit ( a2-A), one structural unit (al-1) and one structural unit (a1-2), a resin composed of one structural unit (I), one structural unit (a2-A) and a structural unit (a1-1), a resin composed of a structural unit (I), a structural unit (a2-A) and a structural unit (a1-2), a resin composed of structural unit (I), one structural unit (a2-A), one structural unit (a1-1), one structural unit (al-2 ), and a structural unit (s), a resin composed of a structural unit (I), a structural unit (a2-A), a structural unit (a1-1) and a unit structural unit (s), a resin composed of a structural unit (I), a structural unit (a2-A), a structural unit (a1-2), and a structural unit (s), or a resin composed of a structural unit (I), a structural unit (a2-A) and a structural unit (s).
[0105] [0105] The structural unit (s) is preferably at least one unit selected from the group consisting of a structural unit (a2) and a structural unit (a3). The structural unit (a2) is preferably a structural unit (a2-1). The structural unit (a3) is preferably at least one unit selected from the group consisting of a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2) and a structural unit represented by the formula (a3- 4).
[0106] [0106] The respective structural units constituting the resin (A) 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 these structural units by a known polymerization process (eg, a radical polymerization process). The content of respective structural units included in the resin (A) can be adjusted depending on the amount of monomer used in the polymerization.
[0107] [0107] [Resist Composition] The resist composition of the present invention preferably includes a resin (A) and an acid generator (hereinafter sometimes referred to as "acid generator (B)").
[0108] [0108] <Resin other than resin (A)> In the resist composition of the present invention, a resin other than resin (A) can be used in combination therewith. The resin other than the resin (A) can be a resin which does not include a structural unit (I) or a structural unit (a2-A). Examples of the resin include a resin in which the structural unit (T) is removed from the resin (A) (hereinafter sometimes referred to as "resin (AY)"), a resin in which the structural unit (a2-A ) is removed from the resin (A) (hereinafter sometimes called "resin (AZ)"), a resin composed only of one structural unit (a4) and one structural unit (a5) (hereinafter sometimes called resin (X)) and the like.
[0109] [0109] In particular, the resin (X) is preferably a resin including a structural unit (a4).
[0110] [0110] The respective structural units 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 these structural units 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.
[0111] [0111] 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% to 99% by mass, on the basis of 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 from 90% to 99% by weight, 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.
[0112] [0112] <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.
[0113] It is possible to use as acid generator (B) compounds which generate an acid by exposure to radiation mentioned in JP 63-26653 A, JP 55-164824 A, JP 62-69263 A, JP 63- 146038 A, JP 63-163452 A, JP 62-153853 A, JP 63-146029 A, U.S. Patent No.
[0114] [0114] 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) "): QP! + -O, S LD1 Z O3 NL Ny (B1) ee where, in formula (B1), Q ° and Q” each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 atoms of carbon, LP! represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CH> - 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 18 carbon atoms which may have a substituent, and -CHz- inclusive in the alicyclic hydrocarbon group may be replaced by -O-, -S (O) z- or -CO-, and Z * represents a cat organic ion.
[0115] [0115] Examples of the perfluoroalkyl group represented by Q ° and Q ° * 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.
[0116] [0116] 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 using two or more of these groups in combination.
[0117] [0117] 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 formula (b1-1) through formula (b1-3). In the groups represented by the formula (b1-1) with the formula (b1-3) and the groups represented by the formula (b1-4) with the formula (b1-11) which are specific examples thereof, * and ** represent a binding site, and * represents an α -Y bond.
[0118] [0118] x 9 03 xx O_ 155 ++ O + No A x mb T _ DIE 677 (b1-1) (b1-2) (b1-3) In the formula (b1-1), LP represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom, LP3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CHz- included in the saturated hydrocarbon group may be replaced by -O- or -CO-, and the total number of carbon atoms in LP and LP is 22 or less.
[0119] In the groups represented by formula (b1-1) to 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.
[0120] [0120] LP is preferably a single bond.
[0121] [0121] The group in which -CH2- included in the divalent saturated hydrocarbon group represented by L! is replaced by -O- or - CO- is preferably a group represented by formula (b1-1) or formula (b1-3).
[0122] [0122] Examples of the group represented by formula (b1-3) include groups represented by formula (b1-9) to formula (b1-11).
[0123] [0123] 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.
[0124] [0124] Examples of the group represented by the formula (b1-4) include the following:
[0125] [0125] Examples of the group represented by the formula (b1-5) include the following: O Oo O Ay Ao, eN Ao, Frequently
[0126] [0126] Examples of the group represented by the formula (b1-6) include the following:
[0127] [0127] Examples of the group represented by the formula (b1-7) include the following:
[0128] [0128] Examples of the group represented by the formula (b1-8) include the following:
[0129] [0129] Examples of the group represented by the formula (b1-2) include the following: ++ X + Ar 0 PA 0 AA O NE, x ae Ho> - Hos 9 FF to Ho “Ho,“ hot, A dt 3
[0130] [0130] Examples of the group represented by the formula (b1-9) include the following:
[0131] [0131] Examples of the group represented by the formula (b1-10) include the following: AAA & ne O ** Ö O 9 3 * a * 5 + B + + H + LN AM rer de Anr Ah: FFF Tr 20 ° F3 Hs OH
[0132] [0132] Examples of the group represented by the formula (b1-11) include the following: Hs o o O O 9 LS otho moto. otho oto. oto F F 9 F F 9 der Art dre Ar F F H30 F F3 © F Fa Ar A. ALA APA OH
[0133] [0133] Examples of the alicyclic hydrocarbon group represented by Y include the groups represented by formula (Y1) to formula (Y11) and by formula (Y36) to formula (Y38).
[0134] [0134] 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 - (CH2); a-CO-O-RP * or a group - (CH2);: - 0-CO-RP! (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, ja represents an integer from 0 to 4 and -CH; - included in an alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -S (O) - or -CO-, a hydrogen atom included in the group alkyl, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a hydroxy group or a fluorine atom and the like.
[0135] [0135] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0136] [0136] Examples of Y include the following. CH CH3 H3C4, CH3 A oA 49 ab De OH
[0137] [0137]
[0138] [0138] Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, 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 (O) 2- or -CO-. Y is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, or groups represented by the following formulas.
[0139] [0139] The anion in the salt represented by formula (B1) is preferably an anion represented by formula (B1-A-1) to formula (B1-A-55) [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-55).
[0140] [0140] OH 9 gold! "at X bt Ob2 Q ol! The Where QY Q _ O - We have - Oo. O3S SLAM 087 L IT LA41 3 al (B1-A-1) (B1-A-2) (B1-A-3) el Qb2 a! Qr2 rice ar Q ° 2 ee] BC BD RO
[0141] [0141]
[0142] [0142]
[0143] [0143] O0 0 is; Know eo ”, | at! as, À Laer RE% R “087 SLA os TT 07 O 0 a’! a (B1-A-31) "087 UM (B1-A-30) Oo (B1-A-32) O OO ° ° al!‚ ar R ar 0 VE a 9 = A41 - 70387 Sp sum U o ass o 0 a2 É Q ” F (B1-A-33) (B1-A-34) (B1-A-35)
[0144] [0144] Fr N
[0145] [0145] N 0 o De Ke De O, L_ 9 4 5 4 + 07} a ‚or X ab ab The o ”ar O oss bone bone
[0146] [0146] Examples of the anion in the salt represented by formula (B1) are preferably anions represented by formula (Bla-1) to formula (Bla-34).
[0147] [0147]
[0148] [0148] The
[0149] [0149] Among these, the anion is preferably an anion represented by any one of the formula (Bla-1) to the formula (Bla-3) and of the formula (B1a-7) to the formula (B1a-16), formula (Bla-18), formula (B1a-19) and formula (B1a-22) to formula (B1a-34).
[0150] [0150] Examples of the organic cation of Z * 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).
[0151] [0151] 16 Ee (REP) 2 (RPB) 2 Rb9 9 RS Or) —2s * -CH-C — RP12 Rb6 To WW, rb70 011 (b2-1) (b2-2) (b2-3) ( RES) 2 (RPT) L eus s + (b2-4)
[0152] [0152] Among the cation (b2-1) to the cation (b2-4), a cation (b2-1) is preferred.
[0153] [0153]
[0154] [0154] Examples of cation (b2-2) include the following cations. (b2-c-28) (b2-c-29) (b2-c-30)
[0155] [0155] Examples of cation (b2-3) include the following cations.
[0156] [0156] Examples of cation (b2-4) include the following cations.
[0157] [0157] The acid generator (B) is a combination of the above-mentioned anions and the above-mentioned organic cations, and these can optionally be combined. Examples of the acid generator (B) are preferably combinations of anions represented by any one of formula (Bla-1) to formula (B1a-3) and of formula (B1a-7) to formula (Bla-16), formula (Bla 18), formula (Bla-19) and from formula (B1a-22) to formula (B1a-34) with a cation (b2-1) or a cation (b2-3).
[0158] [0158] Examples of the acid generator (B) are preferably those represented by the formula (B1-1) to the formula (B1-48). Among these,
[0159] [0159] Hz at t-CaH9 <F F € KF „LH ON X 08 X
[0160] [0160] ® (81-13) (B1-14) (B1-15) OAQ (N F OH 0, | À 117) (B1-18) (B1-16) + FH Dae Ds GATE À ”Ô ° O (B1-21) (B1-19) (B1-20)
[0161] [0161] Por - "03 ® G> <O (81-22) OH 0.8 y + O3 © (B1-23) © (B1-24)
[0162] [0162] To © A S + 7035 OQ. +. O CF F Ô ’" AL Les oi XX PET (B1-28) (B1-29) x L (B1-30) Fr O LF F () TK © Fo oF [5 ZN °
[0163] [0163]
[0164] In the resist composition of the present invention, the acid generator content is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and of 40 parts by mass or less based on 100 parts by mass of the resin (A).
[0165] [0165] <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.
[0166] [0166] <Quencher quencher (C)> Examples of quencher (C) include an organic compound containing basic nitrogen and an acid-generating salt having an acidity lower than that of an acid. generated from an acid generator (B). The content of the deactivating agent (C) is preferably about 0.01 to 5% by mass, and more preferably from 0.01 to 3% by mass based on the amount of the solid component of the resist composition. .
[0167] [0167] The acidity in an acid generating salt having an acidity lower than that of an acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). Regarding the acid generating salt having lower acidity than an acid generated from the acid generator (B), the acid dissociation constant of an acid generated from the salt usually responds to the inequality next :
[0168] [0168] Examples of the weak acid internal salt (D) include the following salts.
[0169] [0169] <Other components> The resist composition of the present invention may also include components other than the components mentioned above (hereinafter sometimes referred to as "other components (F)"). The other components (F) do not are not particularly limited and it is possible to use various additives known in the resist field, for example sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes and the like.
[0170] [0170] <Preparation of resist composition> The resist composition of the present invention can be prepared by mixing a resin (A) and an acid generator (B) according to the present invention, and if necessary, a resin other than resin (A) (a resin (AY), a resin (AZ), a resin (X) etc.), a deactivating agent (C) such as an acid generating salt having an acidity lower than that of an acid generated from the acid generator, a solvent (E), and other components (F). The order of mixing these components is any order and is not particularly limited.
[0171] [0171] <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. Before 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 evaporating the solvent by means of a heating device such as a hotplate (called "precooking") 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.
[0172] [0172] <Applications> The resist composition of the present invention is suitable as a resist composition for exposure to a KIF excimer laser, a resist composition for exposure to an ArF excimer laser, a resist composition for exposure to an ArF excimer laser. electron beam (FE) or a resist composition for exposure to extreme ultraviolet (UVE), and more suitable as a resist composition for exposure to an electron beam (EB) or as a resist composition for exposure to EUV and the Resist composition is useful for fine processing of semiconductors.
[0173] [0173] 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.
[0174] Resin Synthesis The compounds (monomers) used in the synthesis of resins are shown below.
[0175] [0175] Example 1 [Synthesis of resin A1] A monomer (a1-4-2), a monomer (a1-1-3) and a monomer (I-1) were used as monomers. These monomers were mixed in a molar ratio of 38:24:38 [monomer (a1-4-2): monomer (a1-1-3): monomer (I-1)]. This mixture of monomers was then mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added, which was followed by stirring for 6 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A1 resin (copolymer) having a weight average molecular weight of about 5.8 x 10 ° with a yield of 66%. This A1 resin includes the following structural units.
[0176] [0176] Example 2 [Synthesis of resin A2] Acetoxystyrene, a monomer (al-1-3) and a monomer (I-1) were used as monomers. These monomers were mixed in a molar ratio of 38:24:38 [acetoxystyrene: monomer (a1-1- 3): monomer (I-1)]. This mixture of monomers was then mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. Then, 25% aqueous tetramethylammonium hydroxide solution was added to the polymerization solution, which was followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A2 resin (copolymer) having a weight average molecular weight of about 5.7 x 10 ° with a yield of 78%. This A2 resin includes the following structural units: CH3 Hs Lc + CHz ° 4 + CHz 5 € A2 OH Ss
[0177] [0177] Example 3 [Synthesis of resin A3] A monomer (a1-4-2), a monomer (a3-2-1) and a monomer (I-1) were used as monomers. These monomers were mixed in a molar ratio of 30:10:60 [monomer (a1-4-2): monomer
[0178] [0178] Example 4 [Synthesis of the resin A4] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a3-2-1) and a monomer (I-) were used. 1) as monomers. These monomers were mixed in a molar ratio of 36: 26: 12: 30 [monomer (a1-4-2): monomer (a1-1-3): monomer (a3-2-1), monomer (I-1 )]. This mixture of monomers was then mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by heating at 73 ° C for about 5 hours.
[0179] Example 5 [Synthesis of resin A5] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a2-1-3), a monomer (a3-) were used. 2-1) and a monomer (I-1) as monomers. These monomers were mixed in a molar ratio of 32: 23: 3: 12: 30: 10 [monomer (a1-4-2): monomer (a1-1-3): monomer (a2-1-3): monomer (a3-2-1): monomer (I-1)]. This mixture of monomers was then mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in the respective amounts of 2.1% by moles and 6.3% by moles on the basis of. basis of the total number in moles of all monomers, followed by heating at 73 ° C for about 5 hours. Then, the solution of the polymerization reaction was cooled to 23 ° C and an aqueous solution of p-toluenesulfonic acid was added, which was followed by stirring for 3 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A5 resin (copolymer) having a weight average molecular weight of about 5.7 x 10 ° with a yield of 62%. This A5 resin includes the following structural units. “3 ea 7 4 E, A5 OH Ss H OH
[0180] [0180] Example 6 [Synthesis of the resin A6] A monomer (a1-4-2) and a monomer (I-1) were used as monomers. These monomers were mixed in a molar ratio of 38:62 [monomer (a1-4-2): monomer (I-1)]. This mixture of monomers was then mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in the respective amounts of 2.1% by moles and 6.3% by moles on the basis of. basis of the total number in moles of all monomers, which was followed by polymerization by heating at 73 ° C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added, which was followed by stirring for 6 hours and further isolation by separation. The recovered organic layer was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A6 resin (copolymer) having a weight average molecular weight of about 5. , 7 x 103 with a yield of 64%. This A6 resin includes the following structural units.
[0181] [0181] Example 7 [Synthesis of the resin A7] A monomer (a1-4-2) and a monomer (I-1) were used as monomers. These monomers were mixed in a molar ratio of 70:30 [monomer (a1-4-2): monomer (I-1)]. This mixture of monomers was then mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in the respective amounts of 2.1% by moles and 6.3% by moles on the basis of. basis of the total number in moles of all monomers, which was followed by polymerization by heating at 73 ° C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added, which was followed by stirring for 6 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A7 resin (copolymer) having a weight average molecular weight of about 5.8 x 103 with a yield of 58%. This A7 resin includes the following structural units. CHs Leck os 5 8 A7 OH ©
[0182] [0182] Example 8 [Synthesis of resin A8] Acetoxystyrene, monomer (a1i-1-3), monomer (I-2) were used as monomers. These monomers were mixed in a molar ratio of 38:24:38 [acetoxystyrene: monomer (a1-1-3): monomer (I-2)]. This mixture of monomers was then mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in the respective amounts of 2.1% by moles and 6.3% by moles on the basis of basis of the total mol number of all monomers, and polymerization was carried out by heating at 73 ° C for about 5 hours. Then, 25% aqueous tetramethylammonium hydroxide solution was added to the polymerization solution, which was followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A8 resin (copolymer) having a weight average molecular weight of about 5.9 x 10 ° with a yield of 69%. This A7 resin includes the following structural units. Hs CHs {Lc + cH, + cH, 5> € A8 OH
[0183] [0183] Example 9 [Synthesis of resin A9] Acetoxystyrene, a monomer (al-1-3) and a monomer (I-3) were used as monomers. These monomers were mixed in a molar ratio of 38:24:38 [acetoxystyrene: monomer (a1-1- 3): monomer (I-3)]. This mixture of monomers was then mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as guinitiators were added in amounts of 2.1% by moles and 6.3% by moles based on the molar number. total of all monomers, which was followed by polymerization by heating to 73 ° C for about 5 hours. Then, 25% aqueous tetramethylammonium hydroxide solution was added to the polymerization solution, which was followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A9 resin (copolymer) having a weight average molecular weight of about 5.5 x 103 with a yield of 61%. This A9 resin includes the following structural units.
[0184] [0184] Example 10 [Synthesis of the resin A10] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a2-1-3), a monomer (a3-) were used. 2-1) and a monomer (I-2) as monomers. These monomers were mixed in a molar ratio of 32: 23: 3: 12: 30 [monomer (a1-4-2): monomer (a1-1-3): monomer (a2-1-3): monomer (a3 -2-1): monomer (I-2)]. This mixture of monomers was then mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in amounts of 2.1% by moles and 6.3% by moles on the basis of total molar number of all monomers, which was followed by heating at 73 ° C for about 5 hours. Then, the solution of the polymerization reaction was cooled to 23 ° C and an aqueous solution of p-toluenesulfonic acid was added, which was followed by stirring for 3 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A10 resin (copolymer) having a weight average molecular weight of about 6.1 x 10 ° with a yield of 58%. This A10 resin includes the following structural units.
[0185] Example 11 [Synthesis of the resin A11] A monomer (al-4-2), a monomer (al1-1-3), a monomer (a2-1-3), a monomer (a3-) were used. 2-1), and a monomer (I-3) as monomers. These monomers were mixed in a molar ratio of 32: 23: 3: 12: 30 [monomer (a1-4-2): monomer (a1-1-3): monomer (a2-1-3): monomer (a3 -2-1): monomer (I-3)]. This mixture of monomers was then mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in the respective amounts of 2.1% by moles and 6.3% by moles on the basis of. basis of the total number in moles of all monomers, followed by heating at 73 ° C for about 5 hours. Then, the solution of the polymerization reaction was cooled to 23 ° C and an aqueous solution of p-toluenesulfonic acid was added, which was followed by stirring for 3 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an All resin (copolymer) having a weight average molecular weight of about 5.5 x 10 ° with an efficiency of 55%. This A11 resin includes the following structural units. CH3 CH3 Hs CHs Len + CH, HE tc tc
[0186] [0186] Example 12 [Synthesis of the resin A12] A monomer (a2-2-1), a monomer (a1-1-3) and a monomer (I-1) were used as monomers. These monomers were mixed in a molar ratio of 38:24:38 [monomer (a2-2-1): monomer (a1-1-3): monomer (I-3)]. This mixture of monomers was then mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in the respective amounts of 2.1% by moles and 6.3% by moles on the basis of basis of the total number of moles of all monomers, and polymerization was then carried out by heating at 73 ° C for about 5 hours. Then, the solution of the polymerization reaction was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A12 resin (copolymer) having an average molecular weight in weight of about 5.8 x 10 ° with a yield of 75%. This A12 resin includes the following structural units. Ha Hs Ha + CHz + CcH, ° 6, © A12 OH
[0187] [0187] Synthesis Example 1 [Synthesis of AX1 resin] Acetoxystyrene and a monomer (IX-1) were used. These monomers were mixed in a 70:30 molar ratio [acetoxystyrene: monomer (IX-1)]. This mixture of monomers was then mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. Then, 25% aqueous tetramethylammonium hydroxide solution was added to the polymerization solution, which was followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an AX1 resin (copolymer) having a weight average molecular weight of about 5.8 x 10 ° with a yield of 75%. This AX1 resin includes the following structural units. {ch + CH,; > AX1 ie D 5
[0188] [0188] Synthesis Example 2 [Synthesis of the AX2 resin] A monomer (a1-4-2), a monomer (a3-2-1) and a monomer (IX-2) were used as monomers. These monomers were mixed in a molar ratio of 30:10:60 [monomer (a1-4-2): monomer (a3-2-1): monomer (IX-2)]. This mixture of monomers was then mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by heating at 73 ° C for about 5 hours. Then, the solution of the polymerization reaction was cooled to 23 ° C and an aqueous solution of p-toluenesulfonic acid was added, which was followed by stirring for 3 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an AX2 resin (copolymer) having a weight average molecular weight of about 5.7 x 103 with a yield of 60%. This AX2 resin includes the following structural units. 5 Lon Ha {CH CHs
[0189] [0189] <Preparation of resist compositions> A mixture obtained by mixing and dissolving the respective components shown in Table 1 was filtered through a fluorine resin filter having a pore diameter of 0.2 µm to prepare resist compositions. [Table 1] Composition GE ERE PB / PEB deactivation agent Composition 1 | Al = B1-43 = D1 = 130 ° C / 120 ° C parts | 3.4 parts 0.7 parts Composition 2 | A2 = B1-43 = 130 ° C / 120 ° C 10 parts | 3.4 parts 0.7 parts Composition 3 | A3 = B1-43 = Dl = 130 ° C / 120 ° C 10 parts | 3.4 parts 0.7 parts Composition 4 | A4 = B1-43 = D1 = 130 ° C / 120 ° C 10 parts | 3.4 parts 0.7 parts Composition 5 | A5 = B1-43 = D1 = 130 ° C / 120 ° C 10 parts | 3.4 parts 0.7 parts Composition 6 | A6 = B1-43 = D1 = 130 ° C / 120 ° C 10 parts | 3.4 parts 0.7 parts Composition 7 | A7 = B1-43 = 130 ° C / 120 ° C 10 parts | 3.4 parts 0.7 parts Composition 8 | A8 = B1-43 = D1 = 130 ° C / 120 ° C 10 parts | 3.4 parts 0.7 part Composition 9 B1-43 = 130 ° C / 120 ° C 10 parts | 3.4 parts 0.7 parts Composition A10 = B1-43 = D1 = 130 ° C / 120 ° C 10 10 parts | 3.4 parts 0.7 parts Composition | A11 = B1-43 = 130 ° C / 120 ° C 11 10 parts | 3.4 parts 0.7 part 12 10 parts | 3.4 parts 0.7 part Composition B1-43 = 130 ° C / 120 ° C Comparative 1 | 10 games | 3.4 parts 0.7 reference part 2 | 10 games | 3.4 parts 0.7 part 10
[0190] [0190] <Resin> Al to A12, AX1, AX2: Al resin to A12 resin, AX1 resin, AX2 resin. <Acid generator> B1-43: salt represented by the formula (B1-43), (synthesized according to the examples of JP 2016-47815A).
[0191] [0191] <Evaluation of the exposure of the resist composition with an electron beam: Development in an alkaline medium> Each silicon wafer 6 inches in diameter was treated with hexamethyldisilazane and then baked on a direct heating plate at 90 ° C for 60 seconds. A resist composition was applied by centrifugal application (“spin coating”) to the silicon wafer so that the thickness of the composition is then 0.04 μm. The coated silicon wafer was precooked on the direct hot plate at the temperature shown in the "PB" column of Table 1 for 60 seconds to form a composition layer. Using a direct electron beam writing system (“ELS-F125 125 keV”, manufactured by ELIONIX INC.), Contact hole patterns (40 nm hole spacing / 17 mm hole diameter nm) were written directly onto the composition layer formed on the wafer while the exposure dose was changed in stages.
[0192] [0192] <Evaluation of CD Uniformity (CDU)> In the effective sensitivity, the hole diameter of 17 nm was determined by measuring 24 times a same hole and the mean of the measured values was taken as the mean diameter. the hole. The standard deviation was determined under the conditions where the average diameter of 400 holes around the patterns formed using the mask having a hole diameter of 17 nm in the same wafer was considered a population.
[0193] [0193] (Evaluation of the exposure of the resist composition with an electron beam: Development using butyl acetate) Each 6 inch diameter silicon wafer was treated with hexamethyldisilazane on a plate. direct heating at 90 ° C for 60 seconds. A resist composition was applied by centrifugal application (“spin coating”) to the silicon wafer so that the thickness of the composition is then 0.04 μm. The coated silicon wafer was precooked on the direct hot plate at the temperature shown in the "PB" column of Table 1 for 60 seconds to form a composition layer. By means of a direct writing system by electron beam (“ELS-F125 125 keV”, manufactured by ELIONIX INC.), Contact hole patterns (50 nm hole spacing / 23 mm hole diameter nm) were written directly onto the composition layer formed on the wafer while the exposure dose was changed in stages.
[0194] [0194] <Evaluation of CD Uniformity (CDU)> In the effective sensitivity, the hole diameter of 23 nm was determined by measuring 24 times a same hole and the average of the measured values was taken as the average diameter. the hole. The standard deviation was determined under the conditions where the average diameter of 400 holes around the patterns formed using the mask having a 23 nm hole dimeter in the same wafer was considered a population.
[0195] [0195] A resin of the present invention and a resist composition including the resin are suitable for fine processing of semiconductors due to obtaining a resist pattern with satisfactory CD uniformity (CDU), and therefore are very useful from an industrial point of view.

权利要求:
Claims (8)
[1]
1. A resin comprising a structural unit represented by formula (I) and a structural unit represented by formula (a2-A): 1 Hs R
VS
O O |
NP C “yd s2 where, in formula (I), R * represents a hydrogen atom or a methyl group, L * and L * each independently represent -O- or -S-, s1 represents an integer from 1 to 3, and S2 represents an integer from 0 to 3: and Ho RS - Aas0 (a2-A)
OH a51 (R31) where in the formula (a2-A), R ° represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, R2 ! represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group,
A2 ° 0 represents a single bond or * -X2 ** - (A252-X252) p-, and * represents a binding site to carbon atoms to which -R °° is attached, A represents an alkanediyl group having 1 to 6 carbon atoms, x °° 1 and X each independently represent -O-, -CO-O- or -O-CO-, nb represents 0 or 1, and mb represents an integer of 0 to 4, and when mb is an integer of 2 or more, a plurality of R ° * can be the same or different from each other.
[2]
2. The resin according to claim 1, further comprising 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 formula (a1-2):
DAD
CC
O O La ’La2 Mo el nt! (a1-1) (a1-2) where in formula (a1-1) and formula (a1-2), Lt and L each independently represent -O- or * -O- (CH>) y1-CO -O-, k1 represents an integer of 1 to 7, and * represents a bond to -CO-, 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 from 0 to 14, nl represents an integer from 0 to 10, and nl 'represents an integer from 0 to 3.
[3]
3. The resin according to claim 1, further comprising a structural unit represented by the formula (a2-1): H, Ra14
TST 15 (a2-1) fe
H Ra16 where in the formula (a2-1), L ° * represents -O- or * -0- (CH2) i2-CO-0-, k2 represents an integer from 1 to 7, and * represents a site of bond to -CO-, R2! * represents a hydrogen atom or a methyl group, R ° 15 and RS each independently represent a hydrogen atom, a methyl group or a hydroxy group, and 01 represents an integer from 0 to 10.
[4]
4. The resin according to claim 1, further comprising at least one structural unit selected from the group consisting of a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2), a structural unit represented by formula (a3-2), a. structural unit represented by formula (a3-3) and a structural unit represented by formula (a3- 4): where in formula (a3-1), formula (a3-2), formula (a3-3 ) and formula (a3-4), L ° *, L® and L ° each independently represent -O- or a group represented by * -O- (CHz) (3-CO-O- (k3 represents an integer of 1 to 7), L ° ”represents -O-, * -OL ° 8-0-, * -OL ° 8-CO-O-, * -OL °° -CO-O- L29-CO-0- or * -0-L3-0-CO-L ° -0-,
L® and L °° each independently represent an alkanediyl group having 1 to 6 carbon atoms, * represents a bonding site to a carbonyl group, RAS R ° 19 and R220 each independently represent a hydrogen atom or a methyl group, R22 * represents an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, a hydrogen atom or a halogen atom, X ° * represents -CHz- or an oxygen atom, R321 represents a aliphatic hydrocarbon group having 1 to 4 carbon atoms, R322 R223 and R °°° each independently represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, p1 represents an integer of 0 to 5, q1 represents an integer from 0 to 3, r1 represents an integer from 0 to 3, w1 represents an integer from 0 to 8, and when p1, q1, r1 and / or wl is / are 2 or more, a plurality of R ° !, R222 R223 and / or R °°° may be identical or different from each other.
[5]
5. A resist composition comprising the resin of claim 1 and an acid generator.
[6]
6. The resist composition of claim 5, wherein the acid generator includes a salt represented by the formula (B1): Q »* 0.8 LE: 208 LN, (BI) due where in the formula (B1 ), Q "* and Q ° 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 saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom included in the 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 18 carbon atoms which may have a substituent, and -CH> - included in the alicyclic hydrocarbon group may be replaced by -O-, -S (O) 2- or -CO-, and Z * represents an organic cation.
[7]
7. The resist composition of claim 5 further comprising an acid generating salt having an acidity lower than that of an acid generated by the acid generator.
[8]
A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition of claim 5 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.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BE1025620B1|2019-05-06|PHOTORESIST COMPOSITION AND METHOD FOR PRODUCING PHOTORESIST PATTERN

---

BE1026753B1|2020-10-12|SALT, DEACTIVATION AGENT, COMPOSITION OF RESIST AND PROCESS FOR PRODUCTION OF PHOTORESIST PATTERN

---

BE1026584B1|2020-12-21|RESIN, PHOTORESIST COMPOSITION AND PHOTORESIST PATTERN PRODUCTION PROCESS

---

BE1027310B1|2021-05-18|SALT, DEACTIVATION AGENT, COMPOSITION OF RESIST AND METHOD FOR PRODUCING A PATTERN OF RESIST

---

KR102206130B1|2021-01-22|Resin, photoresist composition, and method for producing photoresist pattern

---

BE1027246B1|2021-03-12|SALT, DEACTIVATION AGENT, RESIST COMPOSITION AND PHOTORESIST PATTERN PRODUCTION PROCESS

---

TW201527327A|2015-07-16|Resin, photoresist composition, and method for producing photoresist pattern

---

BE1026621B1|2021-02-10|RESIN, PHOTORESIST COMPOSITION AND PHOTORESIST PATTERN PRODUCTION PROCESS

---

BE1028077B1|2022-03-09|RESIST COMPOSITION AND RESIST PATTERN PRODUCTION METHOD

---

BE1027107B1|2021-02-15|COMPOUND, RESIN, PHOTORESIST COMPOSITION AND PROCESS FOR THE PRODUCTION OF PHOTORESIST PATTERNS

---

BE1027311B1|2021-05-18|SALT, DEACTIVATION AGENT, RESIST COMPOSITION AND METHOD FOR PRODUCING RESIST PATTERN, AND A METHOD FOR PRODUCING SALT

---

BE1026526B1|2020-04-29|RESIN, PHOTORESIST COMPOSITION AND PROCESS FOR PRODUCING PHOTORESIST PATTERN

---

BE1027509A9|2021-07-27|SALT, DEACTIVATION AGENT, COMPOSITION OF RESIST AND METHOD FOR PRODUCING A PATTERN OF RESIST

---

KR20190042460A|2019-04-24|Salt and photoresist composition containing the same

---

KR20190039650A|2019-04-15|Salt and photoresist composition containing the same

---

BE1028139B1|2022-02-18|RESIST COMPOSITION AND RESIST PATTERN PRODUCTION METHOD

---

BE1025883B1|2019-08-06|PHOTORESIST COMPOSITION AND METHOD FOR PRODUCING PHOTORESIST PATTERN

---

BE1028078B1|2022-02-11|RESIST COMPOSITION AND RESIST PATTERN PRODUCTION METHOD

---

BE1028240B1|2022-03-04|CARBOXYLATE, DEACTIVATING AGENT, RESIST COMPOSITION AND METHOD FOR PRODUCING RESIST PATTERN

---

BE1027510B1|2021-08-12|SALT, DEACTIVATION AGENT, COMPOSITION OF RESIST AND METHOD FOR PRODUCING A PATTERN OF RESIST

---

BE1028011B1|2022-01-26|CARBOXYLATE, CARBOXYLIC ACID GENERATOR, RESIST COMPOSITION AND METHOD FOR PRODUCING RESIST PATTERN

---

BE1028305A1|2021-12-09|COMPOUND, RESIN, RESIST COMPOSITION AND METHOD FOR PRODUCING RESIST PATTERN

---

BE1028306A1|2021-12-09|COMPOUND, RESIN, RESIST COMPOSITION AND METHOD FOR PRODUCING RESIST PATTERN

---

BE1025534B1|2019-04-08|COMPOUND, RESIN, PHOTORESIST COMPOSITION AND METHOD FOR PRODUCING PHOTORESIST PATTERN

---

BE1027801B1|2022-02-07|RESIN, PHOTORESIST COMPOSITION AND METHOD FOR PRODUCING PHOTORESIST PATTERN AND COMPOUND

同族专利:

---

公开号 | 公开日

---

KR20200090120A|2020-07-28|

---

TW202035475A|2020-10-01|

---

BE1026584A1|2020-03-25|

---

JP2020117693A|2020-08-06|

---

US20200233300A1|2020-07-23|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

JP2010191221A|2009-02-18|2010-09-02|Kuraray Co Ltd|Chemically amplified photoresist composition for exposure to extreme-ultraviolet ray|

---

JP2012153878A|2011-01-06|2012-08-16|Sumitomo Chemical Co Ltd|Resin, resist composition, and method of manufacturing resist pattern|

---

JP2014114438A|2012-11-19|2014-06-26|Sumitomo Chemical Co Ltd|Resin, resist composition and resist pattern production method|

---

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|

---

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

---

JPS63146029A|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|

---

JPH08101507A|1994-09-30|1996-04-16|Japan Synthetic Rubber Co Ltd|Radiation sensitive resin composition|

---

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

---

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|

---

JP5850873B2|2012-07-27|2016-02-03|富士フイルム株式会社|Actinic ray-sensitive or radiation-sensitive resin composition, resist film using the same, pattern formation method, and electronic device manufacturing method|

---

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

---

JP6450660B2|2014-08-25|2019-01-09|住友化学株式会社|Salt, acid generator, resist composition, and method for producing resist pattern|

---

JP6423681B2|2014-10-14|2018-11-14|住友化学株式会社|Resin, resist composition and method for producing resist pattern|US11262654B2|2019-12-27|2022-03-01|Intel Corporation|Chain scission resist compositions for EUV lithography applications|

法律状态:
2021-02-10| FG| Patent granted|Effective date: 20201221 |

优先权:

---

申请号 | 申请日 | 专利标题

---

JP2019007243|2019-01-18|

---