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 (a1-5) and a structural unit represented by formula (I) as represented in claim 1, wherein Ra8 represents an alkyl group optionally having a halogen atom, a hydrogen atom or a halogen atom; Za1 represents a single bond or * - (CH2) h3-CO-L54-; h3 represents an integer of 1 to 4; L51, L51, L52, L53 and L54 each independently represent -O- or -S-, s1 represents an integer of 1 to 3, and s1 'represents an integer of 0 to 3; R1 represents a hydrogen atom or a methyl group; A1 represents a single bond or * -CO-O-; R2 represents a halogen atom, a hydroxy group, a haloalkyl group or an alkyl group; mi represents an integer of 1 to 3; and ni represents an integer from 0 to 4, where mi + ni ≤ 5.
公开号:BE1026621B1
申请号:E20205030
申请日:2020-01-16
公开日:2021-02-10
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 Patent Document 3: JP 2002-214788 A Patent Document 4: JP 2013-205811 A Description of the Invention Problems to solve by 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 resin comprising the resins mentioned above.
[0005] [0005] The present invention includes the following inventions.
[1] [1] A resin comprising a structural unit represented by formula (a1-5) and a structural unit represented by formula (I): a8 Hs 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): The R ++ RS C St CE
[3] [3] The resin according to [1] or [2], further comprising a structural unit represented by the formula (a2-A): +, Rats map Lan | | A {aA}
[4] [4] The resin according to [1] to [3], where A represents a single bond.
[5] [5] A resist composition comprising the resin according to [1] to [4] and an acid generator.
[6] [6] The composition of resist according to [5], where the acid generator includes a salt represented by the formula (B1):
[7] [7] A resist composition according to [5] or [6], further comprising an acid generating salt having an acidity lower than that of an acid generated by the acid generator.
[8] [8] A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to any one of [5] to [7] on a substrate,
[0006] By using a resist composition of the present invention, it is possible to produce a resist pattern with satisfactory CD uniformity (CDU).
[0007] [0007] As used herein, the term "(meth) acrylate" means "at least one selected from the group consisting of acrylate and methacrylate" unless otherwise indicated. Terms such as "(meth) acrylic acid" and "(meth) acryloyl" also have the same meaning. When a structural unit having "CHz = C (CH3) -CO-" or "" CHz = CH-CO- "is cited as an example, a structural unit having both groups should similarly be cited as an example. Example. In the groups mentioned in the present description, those capable of having both linear and branched structures may have a linear or branched structure. "Combined group" means a group obtained by linking two or more groups mentioned by title. example, and a valence of the group may suitably vary depending on the binding state.
[0008] [0008] [Resin] The resin of the present invention is a resin (hereinafter sometimes called "resin (A)") comprising a structural unit represented by formula (a1-5) (hereinafter sometimes called structural unit ( a1-5)) and a structural unit represented by formula (I) (hereinafter sometimes called structural unit (I)).
[0009] [0009] <Structural unit (a1-5)> Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable .
[0010] Examples of the structural unit (a1-5) include 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 (a1-5-6) are preferable, and a structural unit represented by formula (a1-5-1) or formula (a1-5-2) is more preferable. 0 | 0 | Ge | 9; Y 2 x; i 6 To os, d $] ‘A S 1 - © is ar“ we To a {at-5-1} {at-5-2) (at-5-33 {a1-5-4}
[0011] [0011] <Structural unit (I)> In the formula (I), R * is preferably a hydrogen atom.
[0012] [0012] Examples of the structural unit (I) include the structural units mentioned below. It is possible to cite, by way of example, structural units in which a hydrogen atom corresponding to R * is substituted by a methyl group in structural units represented by the formula (I-1) in the formula (I-8 ) and structural units in which a methyl group corresponding to R * is substituted by a hydrogen atom in the structural units represented by formula (I-9) through formula (I-16) as specific examples of the unit structural (I). Among them, the structural units represented by the formula (I-1) to the formula (I-8) are preferable, the structural units represented by the formula (I-1) to the formula (I-4) are more preferable, and a structural unit represented by formula (I-1) is more preferable.
[0013] [0013] | DM, | Ch | 2h, Les Hs in Ki md]} CH, vrg 2H. co | Gi Sa: 5 = D JS Le fe © AA À Ar ca î Of eo Ê to er, se hd 1 2: sers x ë + “vez Bet GM DM br BC MH OE ers DH {1-83 Ln û- + 1 ) (6423; He + ON + SM | Cut | pende N CH, wle | © 5 = = LU = GC 7 €} ie M is Ô 5 OO O nm COM Ra ”vai Ee NN m a Feen peet, Kitt oee,
[0014] The resin of the present invention (A) can be a polymer including one or more structural units other than the structural unit (a1-5) and the structural unit (I). Examples of structural unit other than structural unit (a1-5) and structural unit (I) include a structural unit having an acid labile group other than structural unit (a1-5) (in suite sometimes called "structural unit (a1)"), a structural unit which is a structural unit other than the structural unit having an acid labile in an acid medium and has a halogen atom (in the following sometimes called "structural unit ( a4) "), a structural unit having no labile group in an acid medium other than the structural unit (I) (hereinafter sometimes called" structural unit unit (s) "), a structural unit having a hydrocarbon group non-starting (hereinafter sometimes referred to as "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 (a1-5), a structural unit having an acid labile group, and preferably includes at least one structural unit selected from the group consisting of into a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2). The resin (A) preferably comprises, in addition to the structural unit (I), a structural unit having no labile group in an acidic medium, and more preferably still comprises a structural unit represented by the formula (a2-A )
[0015] <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)).
[0016] [0016] 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 analogues.
[0017] [0017] Examples of the hydrocarbon group in R °, R2 and R °° 'include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and groups obtained by combining these groups.
[0018] [0018] Examples of group (1) include the following groups. A group where, in formula (1), R °, R22 and R °° are alkyl groups, Ma = 0 and na = 1. The group is preferably a tert-butoxycarbonyl group.
[0019] [0019] Specific examples of group (2) include the following groups. * represents a binding position.
[0020] 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.
[0021] 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.
[0022] [0022] R20! R ° * and R are preferably a methyl group.
[0023] [0023] 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 formula (a1-0-10) is preferred.
[0024] [0024] The structural unit (al-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) to 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.
[0025] [0025] Examples of structural unit (a1l-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 the structural units represented by the formula (a1-2-2), the formula (a1-2-5 ) and formula (a1-2-6) are preferred.
[0026] 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).
[0027] [0027] 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 ass} 5 a34 91) | Lee Rass where, in formula (a1-4), R222 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, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 atoms of carbon, 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 R334 and R °°° represent each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R356 represents a hydrocarbon group having 1 to 20 carbon atoms, or R2 and R °° are bonded with each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with -C- O- in which R °°° and R °° are linked, and -CHz- included in the hydrocarbon group and the divalent hydrocarbon group can be replaced by - O- or -S-.
[0028] [0028] Examples of the alkyl group in R222 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. Examples of the halogen atom in R ** and R °° * include a fluorine atom, a chlorine atom and a bromine atom. Examples of an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a group 1, 1,2,2-tetrafluoroethyl, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3 group, 3,4,4-octafluorobutyl, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, a perfluorohexyl group and analogues. Examples of an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Among these groups, an alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group are more preferred, and a methoxy group is more preferred. Examples of an alkylcarbonyl group include an acetyl group, a propionyl group and a butyryl group. Examples of an alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like. Examples of a hydrocarbon group in R2 °%, R °°° and R2% include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and groups obtained by combining these groups.
[0029] In formula (a1-4), R °° is preferably a hydrogen atom,
[0030] [0030] 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 the units structures represented by the formula (a1-4-1) to the formula (a1-4-5) and the formula (a1-4-10).
[0031] The structural unit (a1) also comprises, for example, a structural unit represented by the formula (a1-OX) (hereinafter sometimes called structural unit (a1-OX)): Rx! Loud] CH ”= O (a1-0X) fr Ar“! where in the formula (a1-0X), RX! represents a hydrogen atom or a methyl group, RZ and R * each independently represent a saturated hydrocarbon group having 1 to 6 carbon atoms, and Ar “represents an aromatic hydrocarbon group having 6 to 36 carbon atoms.
[0032] 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.
[0033] [0033] 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).
[0034] [0034] Examples of the structural unit (a1) also include the following structural units. ddd% CC Do D MD FO HK) (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 structural units of the resin (A).
[0035] [0035] - <Structural Unit (s)> The structural unit (s) derive from a monomer having no labile group in an acidic medium (hereinafter sometimes called "monomer (s)"). It is possible to use, as the monomer from which the structural unit (s) are derived, a monomer which does not have an acid labile group known in the field of resist. The structural unit (s) preferably has a hydroxy group or a lactone ring. When a resin comprising a structural unit having a hydroxy group and not having an acid labile group
[0036] <Structural Unit (a2)> The hydroxy group belonging to the structural unit (a2) can be either an alcoholic hydroxy group or a phenolic hydroxy group.
[0037] In structural unit (a2), examples of structural unit having a phenolic hydroxy group include a structural unit represented by formula (a2-A) (hereinafter sometimes referred to as "structural unit (a2-A) "): Ho RaS0
[0038] [0038] Examples of the halogen atom in R ° “include a fluorine atom, a chlorine atom and a bromine atom.
[0039] [0039] Examples of * -X °°! - (A °° 2-X252) p- include * -O-, * -CO-O-, * - O-CO-, * -CO-0-A 52-CO-0-, * -O-CO-A "** - 0-, * -OA ° 2-CO-0-, * -CO-OA °° - O-CO- and * -0 -CO-A7 ° 2-0-CO-. Of these, * -CO-O-, * -CO-0-A7 ° 2-CO-0- or * -OA® -CO-O- is prefer.
[0040] [0040] mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.
[0041] Examples of structural unit (a2-A) include structural units derived from the monomers mentioned in JP 2010-204634 A and JP 2012-12577 A.
[0042] [0042] 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)" ). Ra14 Tst
[0043] In formula (a2-1), L ° * is preferably -O- or -O- (CHz);: -… CO-O- (fl represents an integer from 1 to 4), and preferably further -O-, R3! $ is preferably a methyl group, R3! 5 is preferably a hydrogen atom,
[0044] [0044] 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
[0045] <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.
[0046] Examples of the aliphatic hydrocarbon group in R ° *, R ° 22, R ° 2 ° and R °°° include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a group butyl, a sec-butyl group and a tert-butyl group.
[0047] In formula (a3-1) with 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- (CH2): 3-CO-O-, more preferably -O- and * -O- CH-CO-O-, and more preferably an oxygen atom, R318 to R22! are 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.
[0048] Examples of structural unit (a3) include structural units derived from monomers mentioned in JP 2010-204646 A, monomers mentioned in JP 2000-122294 A and monomers mentioned in JP 2012-41274 A. 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), 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 R # 8, R21 °, R220 and R ° 2 * in the formula (a3-1) in the formula (a3-4) are substituted with hydrogen atoms in the structural units ci -above.
[0049] [0049] CH Hz H CH3 ch 7 tou} Tos = Lu 9 to p D + Oo XK U 2 (a3-1-1) (a3-1-2) (83-21) (a322) © H CH CHs CH3 er te ter: © Test
[0050] [0050] <Structural unit (a4)> Examples of structural unit (a4) include the following structural units:
[0051] 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. Examples of a monocyclic or polycyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* represents a binding site).
[0052] 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):
[0053] [0053] 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.
[0054] [0054] L “is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
[0055] [0055] 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 a hydrogen atom in the following structural units: Hs Hs Hs Hs Hs Ha teit bf Ft Pt F2 Fe Fg F F3 F2 F2 Fz HF, FH F3 F2H (a4-0-5) (a4-0-6) (a4-0-1) (a4-0-2) (a4-0-3) (a4-0-4) mother ee ET F, Fs 5 F2 FE F2 FE, CF3 F3 F2 gF17 (a4-0-7) (a4-0-8 ) F3 (a4-0-9) (a4-0-10) (a4-0-11) (a4-0-12) Hs Hz Hz Hz tested Le F3 CaF5 RF C2F5 C2F5 F Fra 7 PN (a4-0 -13) (a4-0-14) (a 40-1 5) (a4-0-16)
[0056] [0056] a41 Ho A ——
[0057] Examples of a saturated hydrocarbon group in Re ° # include a chain saturated hydrocarbon group and a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and groups formed by combining these groups.
[0058] Examples of a 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: + - Xa43 - a 845 (a-g3) where , in the formula (a-g3), X represents an oxygen atom, a carbonyl group, * -O- CO- or * -CO-0-, A represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, and * represents a binding site at R ° **,
[0059] [0059] Examples of the aliphatic hydrocarbon group in A include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group; monocyclic alicyclic hydrocarbon groups such as 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 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.
[0060] [0060] 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).
[0061] [0061] When R ** is an aliphatic hydrocarbon group having the group represented by the formula (a-g3), R °° is more preferably a group represented by formula (a-g2): + ——A2416— xa44__ Aa47 (a-g2) where in formula (a-g2), A2% represents a divalent saturated hydrocarbon group having 1 with 17 carbon atoms optionally having a halogen atom, x2 %% represents ** - O-CO- or ** - CO-O- (** represents a binding site to A2), A27 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, the total number of carbon atoms of A **, A °° 7 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.
[0062] The number of carbon atoms of the aliphatic hydrocarbon group for A ** ° is preferably 1 to 6, and more preferably 1 to
[0063] [0063] The preferred structure of the group represented by the formula (a-g2) is the following structure (* is a site for binding to a carbonyl group).
[0064] 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.
[0065] 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 divalent alicyclic saturated hydrocarbon group monocyclic, 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.
[0066] [0066] 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-RE binding site **, N * EN * Ek * ek * sk os on on AA SOSE a * B * B * UT * VV * N "Ar _ ST Aa A
[0067] 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.
[0068] [0068] CH3 Hs Hz H3 CH3 CH3 vr vp "a TE PF PF O O O O Oo O O O = O pe pr br E F2 E Fa pe
[0069] The structural unit represented by the formula (a4-1) is preferably a structural unit represented by the formula (a4-2): Ha RS
[0070] [0070] Examples of the alkanediyl group having 1 to 6 carbon atoms per L *% include the same groups as those mentioned for the alkanediyl group in A ° **, Examples of the saturated hydrocarbon group of R include the same groups as those mentioned for R ° *, The alkanediyl group having 1 to 6 carbon atoms in L # is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.
[0071] 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) .
[0072] [0072] Examples of the structural unit (a4) include a structural unit represented by the formula (a4-3): Ha Rf + " O
[0073] Examples of the alkanediyl group in L5 include those which are the same as those mentioned in the alkanediyl group of A ° **,
[0074] [0074] In formula (a4-3), L5 is preferably an ethylene group. The saturated hydrocarbon group for A ** is preferably a group including a chain hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a chain hydrocarbon group. having 2 to 3 carbon atoms.
[0075] 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).
[0076] The structural unit (a4) also includes a structural unit represented by the formula (a4-4):
[0077] Examples of the saturated hydrocarbon group for R2 include those which are the same as the saturated hydrocarbon group represented by Rê #, R ′ 22 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or a fluorine atom. 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. carbon having a fluorine atom.
[0078] In the formula (a4-4), Af ! is preferably - (CHz); 1-, more preferably an ethylene group or a methylene group, and more preferably a methylene group.
[0079] 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
[0080] [0080] <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):
[0081] 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.
[0082] The group in which -CH2- 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 a binding site to an oxygen atom.
[0083] [0083] [* is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
[0084] [0084] The group represented by the formula (L1-1) includes, for example, the following divalent groups. Oe „Os A A„ Ay AO
[0085] CH4 H3 Des O CH; O ax ++ VTT 0 T 2e DM CH; CH3
[0086] The group represented by the formula (L1-2) includes, for example, the following divalent groups.
[0087] [0087] The group represented by the formula (L1-3) includes, for example, the following divalent groups.
[0088] The group represented by the formula (L1-4) includes, for example, the following divalent groups. 0 To Gold
[0089] L ° is preferably a single bond or a group represented by the formula (L1-1).
[0090] 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.
[0091] [0091] <Structural unit (II)> The resin (A) may further include a structural unit which is decomposed by exposure to radiation to generate an acid (hereinafter sometimes referred to as "structural unit (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.
[0092] [0092] 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 "): RI !!! 3 AND (II-2-A ") Aion ZA * where, in the formula (II-2-A"), xl represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, -CH> - included in the saturated hydrocarbon group can be replaced by -O -, -S- or -CO-, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, or a hydroxy group, A “! represents an alkanediyl group having 1 to 8 carbon atoms, and a hydrogen atom included in the alkanediyl group may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms , RA ”represents a sulfonate group or a carboxylate group, RS represents a hydrogen atom, a halogen atom or a group alkyl having 1 to 6 carbon atoms optionally having a halogen atom, and ZA * represents an organic cation.
[0093] [0093] Examples of the halogen atom represented by RS include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0094] 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. x6 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms.
[0095] 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).
[0096] [0096] The structural unit represented by the formula (II-2-A ") is preferably a structural unit represented by the formula (II-2-A): RI !! 3
[0097] The structural unit represented by the formula (II-2-A) is preferably a structural unit represented by the formula (II-2-A-1): RIN! 3
[0098] The structural unit represented by the formula (II-2-A-1) is preferably a structural unit represented by the formula (II-2-A-2):
[0099] 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 RS is substituted by a hydrogen atom , a halogen atom (eg, a fluorine atom) or an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom (eg a trifluoromethyl group, etc.) and the structural units mentioned in WO 2012/050015 A. ZA ”represents an organic cation.
[0100] [0100] 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): R114 “es, RIS (II-1-1) OO —A "1-R! 14S7 R! 12" A where in formula (II-1-1), Af represents a single bond or a divalent linking group, R 'represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, RI and RB each independently represent a hydrocarbon group having 1 to 18 carbon atoms, and RI et and R ! may be bonded to each other to form a ring with the sulfur atoms to which RI2 and RTS are bonded, RI1 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.
[0101] [0101] 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 hydrogen atom. , a fluorine atom, a trifluoromethyl group and the like.
[0102] [0102] 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 the formula (B1).
[0103] [0103] Examples of sulfonylimide anion represented by A "include the following. CFs CF3 F2C-CF2 E 029 CFa 028 CF, 028 CF2 O28-CF2 0; 8C | Len ol 7 025 CFa 0257GF2 _ O2S-CF2 O; S —CF2 025 —CF2 CF3 F2C-CF2 CF3 (Ib-1) (b-2) (Ib-3) (Ib-4) (Ib-5)
[0104] [0104] Examples of the sulfonylmethide anion include the following. £ F3 F2C-CF3 O23-CF3 O; S-CF O, S-CF O2 | F202 2 2 FaG F, 0, 71 2 F3C-S a F3C-C -S Bi F, C-C -S $ O; S-CF3 O2S-CF2 O25-CF2 CF3 F, C-CF3
[0105] [0105] Examples of the carboxylic acid anion include the following. 9 oO Q O
[0106] [0106] Examples of structural unit represented by formula (II-1-1) include structural units represented by the following. Hs Ha
[0107] [0107] 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).
[0108] [0108] 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.
[0109] [0109] The resin (A) is preferably a resin composed of a structural unit (I) and of a structural unit (a1-5), a resin composed of a structural unit (I), of a unit structural unit (a1-5), one structural unit (a1-1) and one structural unit (a1-2), a resin composed of one structural unit (I), one structural unit (a1-5 ) and a structural unit (a1-1), a resin composed of a unit structure (I), a structural unit (a1-5) and a structural unit (a1-2), a composite resin a structural unit (I), a structural unit (al- 5), 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 (a1-5), a structural unit (a1-1) and a structural unit (s), a resin composed of a structural unit (I), a structural unit (a1-5), a structural unit (a1-2) and a structural unit (s), a resin com posed of a structural unit (I), a structural unit (a1-5) and a structural unit (s), a resin composed of a structural unit (I), a structural unit (a1- 5), a structural unit (a1-1), a structural unit (a1-2), a structural unit (s), a structural unit (a4) and / or a structural unit (85), or a resin composed only of a structural unit (I), a structural unit (a1- 5), a structural unit (a1-1), a structural unit (a1-2) and a structural unit (a4), and more preferably a resin composed of a structural unit (I) and a structural unit (a1-5), a resin composed of a structural unit (I), a structural unit (a1-5), a structural unit (al-1) and a structural unit (a1-2), a resin composed of a structural unit (I), a structural unit (a1-5) and a structural unit (a1-1), a resin composed of a structural unit (I), a structural unit (a1-5) and a structural unit (ai-2), a resin composed of a structural unit (I), a structural unit (a1-5), a structural unit (a1-1), a unit structural unit (a1-2) and one structural unit (s), a resin composed of one structural unit (I), one structural unit (a1- 5), one structural unit (a1-1) and a structural unit (s), a resin composed of a structural unit (I), a structural unit (al- 5), a structural unit (a1-2) and a structural unit (s) , or a resin composed of a structural unit (I), a structural unit (a1-5) and a structural unit (s).
[0110] [0110] 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 represented by the formula (a2-A) or a structural unit represented by the formula (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).
[0111] [0111] 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.
[0112] [0112] [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)").
[0113] [0113] <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 (a1-5). Examples of the resin include a resin in which the structural unit (I) is removed from the resin (A) (hereinafter sometimes referred to as "resin (AY)"), a resin in which the structural unit (a1-5 ) 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.
[0114] [0114] In particular, the resin (X) is preferably a resin including a structural unit (a4).
[0115] [0115] 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. Each weight average molecular weight of resin (AY), resin (AZ), and resin (X) is preferably 6000 or more (more preferably 7000 or more), and 80,000 or less (more preferably 60,000 or more). less). The way of measuring the weight average molecular mass of resin (AY), resin (AZ) and resin (X) is the same as in the case of resin (A).
[0116] [0116] 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, based on 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% 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.
[0117] [0117] <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.
[0118] It is possible to use as an 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.
[0119] 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) ”): Q” + '048 LD zZ 038 | ALA (B1) Wherein in formula (B1), QPt 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 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- included in the alicyclic hydrocarbon group can be replaced by -O-, -S (O) 2- or -CO-, and Z * represents an organic cation.
[0120] [0120] Examples of the perfluoroalkyl group represented by QP! 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.
[0121] [0121] Examples of divalent saturated hydrocarbon group in L °! 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.
[0122] [0122] The group in which -CH2- included in the divalent saturated hydrocarbon group represented by LP! is replaced by -O- or - CO- includes, for example, a group represented by any one of formula (b1-1) to formula (b1-3). In the groups represented by 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 a binding to -Y.
[0123] [0123] ‘x N b3 ++ OE + O + No SOS, DS b4 T Eb L7 (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 of L ”and LP is 22 or less.
[0124] 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.
[0125] [0125] LP is preferably a single bond.
[0126] [0126] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by L * is replaced by -O- or - CO- is preferably a group represented by formula (b1-1) or formula (b1 -3).
[0127] [0127] Examples of the group represented by formula (b1-3) include groups represented by formula (b1-9) to formula (b1-11).
[0128] [0128] In the groups represented by the formula (b1-9) to 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.
[0129] [0129] Examples of the group represented by the formula (b1-4) include the following: O O O, O O 7407 AD to> ON CH3
[0130] [0130] Examples of the group represented by the formula (b1-5) include the following:
[0131] [0131] Examples of the group represented by the formula (b1-6) include the following:
[0132] [0132] Examples of the group represented by the formula (b1-7) include the following: O H3 O 9 O ANA TT Ages O Hs O oO oO OQ oO O Q * 9 Q Q X ANDI Ay y OE
[0133] [0133] Examples of the group represented by the formula (b1-8) include the following:
[0134] [0134] Examples of the group represented by the formula (b1-2) include the following:
[0135] [0135] Examples of the group represented by the formula (b1-9) include the following:
[0136] [0136] Examples of the group represented by the formula (b1-10) include the following: H3 H3 H3 ANA AAA NS che A As he Ô xk O x O ** Ö Ô
[0137] [0137] Examples of the group represented by the formula (b1-11) include the following:
[0138] [0138] 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).
[0139] [0139] 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 (0) 2- or -CO-, a hydrogen atom included in the alkyl group, alicyclic hydrocarbon group and aromatic hydrocarbon group may be substituted with hydroxy group or fluorine atom and the like.
[0140] [0140] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0141] [0141] Examples of Y include the following.
[0142] [0142]
[0143] [0143] 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.
[0144] [0144] 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), 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).
[0145] [0145] OH ° gold! "at OG b1 Ob2 Q ol! The Where a »a - o - On, aai - oO. O4S SAN YT | y is ST (B1-A-1) (B1-A-2) (B1-A-3) el Qb2 a! Qr2 rice ar Q ° 2 ee] BC BD RO
[0146] [0146]
[0147] [0147]
[0148] [0148] | O2 00 a! The" R® ab! mL Laa rie * R ° 7 bones On A 7 bones 9 07 O 0 a ’! Qb 70487 Sp Siam (B1-A-30) (B1-A-31) q (B1-A-32) 0 On ie ° ° i7 b1 b1 le ae © 1 A41 0 - 1 HL © 70387 Sp sum as o as voro O What F Q F (B1-A-33) (B1-A-34) (B1-A-35)
[0149] [0149] Fr N
[0150] [0150] 0 o | VD p A 10% X or ° Deo ©, L. 9, 0-16 a ‚or where ab ab 2 Os ar Lo 7 on - Sr Os, Aai - 0, LA (B1-A-47) 0 (B1-A-48) © (B1-A-49) 0 0 Me A le X À A 9 D 9 5 9 Ò 0 o Qb ”Q2 Oo a 'Q” O a! Qb2 oO SEN „SEX SEN
[0151] [0151] Examples of the anion in the salt represented by formula (B1) are preferably anions represented by formula (Bia-1) to formula (B1a-34).
[0152] [0152]
[0153] [0153] F
[0154] [0154] Among these, 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 (Bla-34).
[0155] [0155] 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).
[0156] [0156] 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) Ÿ (R ”" a2 s + (b2-4)
[0157] [0157] Among the cation (b2-1) to the cation (b2-4), a cation (b2-1) is preferred. Examples of cation (b2-1) include the following cations. 6 CaH5 6 t-CaHg CeH43 CaH 47 of 3 of "5 of oË of (b2-c-1) (b2-c-2) (b2-c-3) (b2-c-4) (b2-c- 5) (b2-c-6) (b2-c-7) (b2-c-8) 6 6 5 t-C4Hg -C4Hg + + + CH3 QV
[0158] [0158]
[0159] [0159] Examples of cation (b2-2) include the following cations. (b2-c-28) (b2-c-29) (b2-c-30)
[0160] [0160] Examples of cation (b2-3) include cations. OS OA CO ” of (b2-c-31) (b2-c-32) (b2-c-33) (b2-c-34)
[0161] [0161] Examples of cation (b2-4) include cations. 0-0 O-Oe ee (b2-c-35) (b2-c-36) (b2-c-37) H3G H3 H3 0-0 JOO A} tc (b2-c-38) (b2-c- 39) (b2-c-40) Hs Ha t-C4Hg 3 ds) 30-0. 30: 0 Ha (b2-c-41) Ha (b2-c-42) (b2-c-43)
[0162] [0162] 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 anions represented by any one of formula (Bla-1) to formula (Bla-3) and of formula (Bla-7) to formula (B1a-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).
[0163] [0163] Examples of the acid generator (B) are preferably those represented by formula (B1-1) to formula (B1-48). 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 ( B1-48) are particularly preferable. Q eG ed KF LR co LÀ CC (B1-1) (B1-2) (B1-3) t-C, Hg CH3
[0164] [0164]
[0165] [0165] 4 Qs 948 - +. F (B1-13) (B1-14) ° (B1-15) 0 5 (81-17) (7 (B1-18) (B1-16)
[0166] [0166] CO) nr "03 Q. F f _ F (B1-22) OS 038 HS 98 N = (B1-23) (B1-24) © FF E oO OA Gi of Kase y (B1-25) ( B1-26) I (84:27)
[0167] [0167]
[0168] [0168]
[0169] [0169] <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.
[0170] [0170] <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 weight, and more preferably 0.01 to 3% by weight based on the amount of the solid component of the resist composition. .
[0171] [0171] 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 following: -3 <pKa, preferably -1 <pKa <7, and more preferably 0 <pKa <
[0172] [0172] Examples of the weak acid internal salt (D) include the following salts.
[0173] [0173] <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.
[0174] [0174] <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. 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 a suitable duration of 0.5 to 24 hours as the mixing time depending on the mixing temperature. The mixing means is not particularly limited and it is possible to use mixing with stirring.
[0175] [0175] <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.
[0176] [0176] <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 (FE) or as a resist composition for exposure to EUV and the Resist composition is useful for fine processing of semiconductors.
[0177] [0177] 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.
[0178] Resin synthesis The compounds (monomers) used in the synthesis of the resins are indicated below.
[0179] Example 1 [Synthesis of the resin A1] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-5-1) and a monomer (I-) were used. 1) as monomers. These monomers were mixed in a molar ratio of 32: 26: 30: 12 [monomer (al-4-2): monomer (al-1-3): monomer (al-5-1): 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 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 Al resin (copolymer) having a weight average molecular weight of about 5.7 x 10 ° with a yield of 62%. This A1 resin includes the following structural units.
[0180] [0180] Example 2 [Synthesis of resin A2] Acetoxystyrene, a monomer (a1-1-3), a monomer (a1-5-1) and a monomer (I-1) were used as monomers. These monomers were mixed in a molar ratio of 32: 26: 30: 12 [acetoxystyrene: monomer (a1-1-3): monomer (a1-5-1): 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 polymerization of the mixture by heating at 73 ° C for about 5 hours. Then, a 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 5.9 x 103 with a yield of 73%. This A2 resin includes the following structural units:
[0181] [0181] Example 3 [Synthesis of resin A3] A monomer (a1-4-2), a monomer (a3-2-1), a monomer (a1-5-1) and a monomer (I -1) as monomers. These monomers were mixed in a molar ratio of 30: 10: 50: 10 [monomer (a1-4-2): monomer (a3-2-1): monomer (a1-5-1): 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 polymerization of the mixture 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 A3 resin (copolymer) having a weight average molecular weight of about 5.5 x 10 ° with a yield of 58%. This A3 resin includes the following structural units.
[0182] Example 4 [Synthesis of the resin A4] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a3-2-1), a monomer (a1-) were used. 5-1) and a monomer (I-1) as monomers. These monomers were mixed in a molar ratio of 30: 20: 10: 30: 10 [monomer (a1-4-2): monomer (a1-1-3): monomer (a3-2-1), monomer (al -5-1): 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 polymerization of the mixture 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 A4 resin (copolymer) having a weight average molecular weight of about 5.7 x 10 ° with an efficiency of 60%. This A4 resin includes the following structural units. Hz Hs Hs Long {Hz ° toy, + CHz> {ch 27 A4 OH s FC CF, = OH
[0183] [0183] 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), a monomer (a1-5-1) and a monomer (I-1) as monomers. These monomers were mixed in a molar ratio of 30: 20: 3: 7: 30: 10 [monomer (a1-4- 2): monomer (a1-1-3): monomer (a2-1-3): monomer (a3-2-1):
[0184] [0184] Example 6 [Synthesis of the resin A6] A monomer (a1-5-1) and a monomer (1-1) were used as monomers. These monomers were mixed in a molar ratio of 38:62 [monomer (a1-5-1): 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 polymerization reaction solution was cooled to 23 ° C and then 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)
[0185] [0185] Example 7 [Synthesis of the resin A7] A monomer (a1-5-1) and a monomer (1-1) were used as monomers. These monomers were mixed in a molar ratio of 70:30 [monomer (a1-5-1): 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 polymerization reaction solution was cooled to 23 ° C and then 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 5.5 x 10 ° with a yield of 55%. This A7 resin includes the following structural units.
[0186] [0186] Example 8 [Synthesis of resin A8] A monomer (a3-2-1), a monomer (a1-5-1) and a monomer (I-1) were used as monomers. These monomers were mixed in a molar ratio of 10:50:40 [monomer (a3-2-1): monomer (a1-5-1): 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 then 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 58%. This A7 resin includes the following structural units. to ch; 5 Len O c A8 & S F, C — CF3
[0187] [0187] Example 9 [Synthesis of resin A9] Acetoxystyrene, a monomer (a1-1-3), a monomer (a1-5-5) and a monomer (I-1) were used as monomers. These monomers were mixed in a molar ratio of 32: 26: 30: 12 [acetoxystyrene: monomer (a1-1-3): monomer (a1-5-5): 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, a 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 6.1 x 103 with a yield of 68%. This A9 resin includes the following structural units.
[0188] [0188] Example 10 [Synthesis of resin A10] Acetoxystyrene, a monomer (a1-1-3), a monomer (a1-5-3) and a monomer (I-1) were used as monomers. These monomers were mixed in a molar ratio of 32: 26: 30: 12 [acetoxystyrene: monomer (a1-1-3): monomer (a1-5-3): 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, a 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 A10 resin (copolymer) having a weight average molecular weight of about 5.6 x 103 with a yield of 61%. This A10 resin includes the following structural units. {cha os + -CH, {che © A10 OH VO J CF3 -} - CF3 5 OH
[0189] Example 11 [Synthesis of the resin A11] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a2-1-3), a monomer (a3-) were used. 2-1), a monomer (a1-5-5) and a monomer (I-1) as monomers. These monomers were mixed in a molar ratio of 30: 20: 3: 7: 30: 10 [monomer (a1-4- 2): monomer (a1-1-3): monomer (a2-1-3): monomer (a3-2-1): monomer (a1-5-5): 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 A11 resin (copolymer) having a weight average molecular weight of about 6.1 x 103 with a yield of 58%. This All resin includes the following structural units.
[0190] [0190] Example 12 [Synthesis of the resin A12] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a2-1-3), a monomer (a3 -2-1), a monomer (a1-5-3) and a monomer (I-1) as the monomers. These monomers were mixed in a molar ratio of 30: 20: 3: 7: 30: 10 [monomer (a1-4- 2): monomer (a1-1-3): monomer (a2-1-3): monomer (a3-2-1): monomer (a1-5-3): 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) 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 A12 resin (copolymer) having a weight average molecular weight of about 5.6 x 10 ° with a yield of 53%. This A12 resin includes the following structural units.
[0191] [0191] Synthesis Example 1 [Synthesis of the AX1 resin] Acetoxystyrene and a monomer (a1-5-X1) were used. These monomers were mixed in a 70:30 molar ratio
[0192] [0192] Synthesis Example 2 [Synthesis of the AX2 Resin] A monomer (a1-4-2), a monomer (a3-2-1) and a monomer (a1-5-X2) 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 (a1-5-X2)]. 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 mol% and 63 mol% based on molar number. total of all monomers, which was followed by polymerization of the mixture 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 10 ° with an efficiency of 60%. This AX2 resin includes the following structural units. at {ch Hs sc CHs
[0193] [0193] Synthesis Example 3 [Synthesis of the AX3 resin] A monomer (a1-1-1) and a monomer (I-1) were used as monomers. These monomers were mixed in a molar ratio of 31:69 [monomer (a1-1-1): 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 polymerization of the mixture 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 AX3 resin (copolymer) having an average molecular weight in weight of about 5.8 x 103 with a yield of 80%. This AX3 resin includes the following structural units.
[0194] [0194] Synthesis Example 4 [Synthesis of the AX4 resin] A monomer (a1-4-2), a monomer (a1i-1-2), a monomer (II-2-A1) and a monomer ( I-1) as monomers. These monomers were mixed in a molar ratio of 30: 35: 5: 30 [monomer (al-4-2): monomer (al-1-2): monomer (II-2-A1): 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 AX4 resin (copolymer) having a weight average molecular weight of about 5.6 x 10 ° with a yield of 61%. This AX4 resin includes the following structural units.
[0195] [0195] <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] ee in EP a of resist deactivation PEB parts | 3.4 parts 0.7 part 10 parts | 3.4 parts 0.7 part 10 parts | 3.4 parts 0.7 part 10 parts | 3.4 parts 0.7 part 10 parts | 3.4 parts 0.7 part 10 parts | 3.4 parts 0.7 part 10 parts | 3.4 parts 0.7 part 10 parts | 3.4 parts 0.7 part 10 parts | 3.4 parts 0.7 part 10 10 parts | 3.4 parts 0.7 part 11 10 parts | 3.4 parts 0.7 part 12 10 parts | 3.4 parts 0.7 Comparative part 1 | 10 games | 3.4 parts 0.7 reference part 2 | 10 games | 3.4 parts 0.7 reference part 3 | 10 games | 3.4 parts 0.7 reference part 4 | 10 games | 3.4 parts 0.7 parts
[0196] [0196] <Resin> Al to A12, AX1 to AX4: Al resin to A12 resin, AX1 resin to AX4 resin.
[0197] [0197] <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.
[0198] [0198] <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 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 hole diameter of 17 nm in the same wafer was considered a population.
[0199] [0199] (Evaluation of the exposure of the resist composition with an electron beam: Development using butyl acetate) Each silicon wafer of 6 inches in diameter was treated with hexamethyldisilazane and then baked on a direct hot plate at 90 ° C for 60 seconds. A resist composition was applied by centrifugal application (“spin coating”) on the silicon wafer so that the thickness of the composition is then 0.04 μm.
[0200] [0200] <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 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 23 nm hole dimeter in the same wafer was considered a population. The results are shown in Table 3. The numerical value in the table represents the standard deviation (nm). [Table 3] | __ | Composition of resist ____ | ŒDU |
[0201] [0201] 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 (10)
[1]
1. A resin comprising a structural unit represented by formula (a1-5) and a structural unit represented by formula (I): a8 Hs R
VS
O LS (a1-5) Nat Ka = s1 'where, in formula (a1-5), R ° 8 represents an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom or a hydrogen atom or a halogen atom, Z °! represents a single bond or * - (CH ») n3-CO-L ° * -, h3 represents an integer from 1 to 4, and * represents a binding site at L ° *, Lt, L ° , L ° * and L ** each independently represent -O- or -S-, s1 represents an integer of 1 to 3, and s1 'represents an integer of 0 to 3: 3 | Mo 7 | Al A, @>, Pa ”OF (4) (eg OH) Ani 1 mi where, in the formula (T),
R * represents a hydrogen atom or a methyl group, A 'represents a single bond or * -CO-O-, * represents a bonding site to a carbon atom to which -R * is bonded, R2 represents a d atom halogen, a hydroxy group, a haloalkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and -CH2- included in the alkyl group may be replaced by -O- or -CO-, mi represents an integer of 1 to 3, and ni represents an integer of 0 to 4, and when ni is 2 or more, a plurality of R * may be the same or different from each other, and mi + ni <5.
[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): and THE]
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-A): Hs fase. Jaso # {a2-À} Je (RA) put where in the formula (a2-A), R250 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, R °°! 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 * -X °° 1- (a252-x252) 5; and * represents a binding site to carbon atoms to which -R2 ° is bonded, A2 ° 2 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 ° ** may be the same or different from each other.
[4]
4. The resin of claim 1, wherein A1 represents a single bond.
[5]
5. The resin according to claim 1, further comprising a structural unit represented by the formula (a2-1): H, Ra14
TST (3 (a2-1) fe
H Ra16 where, in formula (a2-1), L ° * represents -O- or * -O- (CH2) x2-CO-O-, k2 represents an integer from 1 to 7, and * represents a site of bond to -CO-, R2! * represents a hydrogen atom or a methyl group, R ° 15 and RS each independently represent a hydrogen atom, a methyl group or a hydroxy group, and 01 represents an integer from 0 to 10.
[6]
6. 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 unit structural unit represented by formula (a3-3) and a structural unit represented by formula (a3- 4): Ra18 ie ie ie | to TS tot Tl | 34 (RE), (the X (/ a6 L‘a7 i; He, Pe NE 9 9 O 9 O
O (a3-1) (a3-2) (a3-3) (a3-4) where in the formula (a3-1), the formula (a3-2), the formula (a3-3) and the formula (a3-4),
L ° *, L® and L3 each independently represent -O- or a group represented by * -O- (CHz2) e3-CO-O- (k3 represents an integer of 1 to 7), L represents -O-, * -OL ° 8-0-, * -0-L9% -CO-0-, * -OL °° -CO-O- L °° -CO-O- or * -OL ° 8 -0-CO-L °° -O-, L® and L °° each independently represent an alkanediyl group having 1 to 6 carbon atoms, * represents a binding site to a carbonyl group, RAS R ° 19 and R ° ° each independently represent a hydrogen atom or a methyl group, R ° 7 * 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, R22 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R322 R223 and RS 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 of 0 to 3, r1 represents an integer of 0 to 3, wl represents an integer of 0 to 8, and when p1, ql, r1 and / or wl is / are 2 or more, a plurality of R2! R222 R ° and / or R22 may be the same or different from each other.
[7]
7. A resist composition comprising the resin of claim 1 and an acid generator.
[8]
8. The resist composition of claim 7, wherein the acid generator includes a salt represented by formula (B1):
Qt 2 OS LAS, {B1) i where, in formula (B1), QP! 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, -CH> - 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 can be replaced by -O-, -S (O)> - or -CO-, and Z * represents an organic cation.
[9]
9. The resist composition of claim 7 further comprising an acid generating salt having an acidity lower than that of an acid generated by the acid generator.
[10]
10. A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition of claim 7 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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法律状态:
2021-04-19| FG| Patent granted|Effective date: 20210210 |

优先权:

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申请号 | 申请日 | 专利标题

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JP2019007244|2019-01-18|

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