CARBOXYLATE, DEACTIVATING AGENT, RESIST COMPOSITION AND METHOD FOR PRODUCING RESIST PATTERN

专利摘要:
A carboxylate represented by formula (I), a deactivating agent and a composition comprising the same, wherein, in formula (I), R1, R2 and R3 each independently represent a halogen atom, an alkyl fluoride group or a hydrocarbon group which may have a substituent, and -CH2- included in the hydrocarbon group may be replaced by -O-, -CO-, -S- or -SO2-, m1 represents an integer from 0 to 5, and when m1 is 2 or more, a plurality of R1 may be the same or different from each other, m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R2 may be the same or different from each other, m3 represents an integer of 0 to 3, and when m3 is 2 or more, a plurality of R3 may be the same or different from each other, and X1 represents a bond, -CH2-, -O-, -S-, - CO-, -SO- or -SO2-.
公开号:BE1028240B1
申请号:E20215391
申请日:2021-05-14
公开日:2022-03-04
发明作者:Katsuhiro Komuro；Koji Ichikawa
申请人:Sumitomo Chemical Co；
IPC主号:

专利说明:

[0001] The present invention relates to a carboxylate, a "Quencher" deactivating agent including a carboxylate and a resist composition, as well as a method for producing a resist pattern using the resist composition. BACKGROUND OF THE INVENTION
[0002] JP 2017-202993 A mentions a resist composition including a carboxylate having the following structural formula. Where
[0003] It is an object of the present invention to provide a salt capable of producing a resist pattern having CD uniformity (CDU) better than that of a resist pattern formed from a resist composition including the aforementioned carboxylates. . SUMMARY OF THE INVENTION
[0004] The present invention includes the following inventions.
[1] [1] A carboxylate represented by the formula (I):
[2] [2] The carboxylate according to [1], in which m1 represents an integer from 1 to
[3] [3] The carboxylate according to [2], wherein at least one R! is bound at the para position relative to the S* binding site.
[4] [4] The carboxylate according to [2] or [3], in which at least one R' represents: either an alkyl group having 1 to 3 carbon atoms which may have an iodine atom and/or a fluorine atom, and wherein a -CH>- included in this group may be replaced by -O- or -CO- or a branched alkyl group having 3 or 4 carbon atoms.
[5] [5] The carboxylate according to [4], wherein at least one Rt represents an alkyl group having 1 to 3 carbon atoms in which one -CH:- included in this group is replaced by -O- bonded to a benzene ring.
[6] [6] The carboxylate according to [4], wherein said alkyl group having 1 to 3 carbon atoms further has one or more fluorine atoms.
[7] [7] The carboxylate according to any one of [2] to [6], wherein at least one R* represents a branched alkyl group having 3 or 4 carbon atoms.
[8] [8] The carboxylate according to any one of [2] to [7], wherein m1 represents 2 or 3 and at least one R* represents an iodine atom or a methyl group.
[9] [9] A deactivating agent comprising the carboxylate according to any one of [1] to [8].
[10] [10] A resist composition comprising the deactivating agent according to
[9] [9], a resin including a structural unit having an acid labile group and an acid generator.
[11] [11] The resist composition according to [10] wherein the resin including a structural unit having an acid-labile group includes at least one structural unit selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by the formula (a1-2): rs gas HS +5 =OD LE / Lez „| Foe Re jj af Int (a1-1) (a1-2) where, in formula (a1-1) and formula (a1-2), L°* and L°* each independently represent -O- or *- O- (CH2)k1-CO-O-, k1 represents an integer from 1 to 7, and * represents a bonding site at -CO-, R°* and R® each independently represent a hydrogen atom, a halogen or an alkyl group having 1 to 6 carbon atoms and which may have a halogen atom,
[12] [12] The resist composition according to [10] or [11], wherein the resin including a structural unit having an acid labile group includes a structural unit represented by the formula (a2-A): R350
[13] [13] The resist composition according to any one of [10] to [12], wherein the acid generator includes a salt represented by the formula (B1):
[14] [14] The resist composition according to any one of [10] to [13], further comprising an acid-generating salt having an acidity lower than that of an acid generated by the acid generator.
[15] [15] A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to any one of [10] to [14] onto a substrate, (2) a step 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
[0005] It is possible to produce a resist pattern with satisfactory CD (CDU) uniformity by using a resist composition including a carboxylate of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0006] In the present specification, “(meth)acrylic monomer” means at least one selected from the group consisting of a monomer having a structure of “CH2=CH-CO-” and a “CH; =C(CH3)-CO-". Similarly, “(meth)acrylate” and “(meth)acrylic acid” each mean “at least one selected from the group consisting of acrylate and methacrylate” and “at least one selected from the group consisting of acrylic acid and methacrylic acid”. When a structural unit having “CH2=C(CH3)-CO-” or “CH2=CH-CO-” is exemplified, a structural unit having both groups shall be considered to be similarly exemplified. In the groups mentioned in the present description, the groups capable of having a linear structure and a branched structure, may have the linear structure or the branched structure. When -CH2- included in a hydrocarbon group or the like is replaced by -O-, -S-, -CO-, or -S(O0)2-, an example of replacement applies to all possible replacements. “Combined group” means a group in which two or more exemplified groups are bonded, and the valences of these groups can be changed appropriately depending on a form of bonding. "Derivative" means that a C=C polymerizable bond included in the molecule becomes a -C-C- group upon polymerization. Where stereoisomers exist, all stereoisomers are included.
[0007] In the present description, the term "solid component of resist composition" means the total amount of components, excluding the solvent (E) mentioned below from the total amount of the resist composition.
[0008] The present invention relates to a carboxylate represented by formula (I) (hereinafter sometimes called “carboxylate (T)” or “salt (I)”):
[0009] In formula (I), examples of the halogen atom in R}, R and R* include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl fluoride group having 1 to 6 carbon atoms in R*, R and R° include alkyl fluoride groups such as trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, perfluoropropyl group , a 2,2,3,3,3-pentafluoropropyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a perfluoropentyl group, a 2,2,3 group ,3,4,4,5,5,5-nonafluoropentyl and a perfluorohexyl group. The number of carbon atoms of the alkyl fluoride group is preferably 1 to 4, more preferably 1 to 3. Examples of the hydrocarbon group having 1 to 18 carbon atoms in R*, R2 and R3 include a chain hydrocarbon group such as an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a group obtained by combining these groups. Examples of the alkyl group include alkyl groups such as methyl group, ethyl group, propyl group, -isopropyl group, butyl group, isobutyl group, tert-butyl group,
[0010] [0010]
[0011] [0011] 4″9
[0012] <Process for synthesizing the carboxylate (I)> The carboxylate (I) can be obtained by reacting a salt represented by the formula (Ia) in the presence of a basic catalyst in a solvent, then subjecting the reaction medium to treatment with an aqueous solution of oxalic acid. It is also possible to obtain this carboxylate by reacting a salt represented by formula (Ia) in the presence of a basic catalyst in a solvent, then by passing the reaction medium over an ion exchange resin (d ions), by subjecting the product obtained to a treatment with a base, then by subjecting the reaction medium to a treatment with an aqueous solution of oxalic acid: (RD ma (Rm O+S—CF , Le ei O $ SO SK (RS) ma SK (R$) ms (RÈ) m2 (R2)m2 (Ia) (I) where all symbols are as previously defined Examples of the base include hydroxide sodium chloride, potassium hydroxide, triethylamine and the like Examples of the solvent include chloroform, ion-exchanged water and the like The reaction is generally carried out at a temperature in a range of 0 to 80 °C for 0.5 to 24 hours.
[0013] [0013]
[0014] The compound of formula (I-b) can be obtained by reacting a compound represented by formula (I-d) in the presence of hydrogen peroxide in a solvent
[0015] <Quenching agent, "Quencher"> The quencher of the present invention includes a carboxylate (I). When the carboxylate (I) is used as a quencher, the latter may contain one or two or more carboxylates (I).
[0016] <Resist composition> The resist composition includes a deactivating agent including the carboxylate (T) of the present invention, an acid generator (hereinafter sometimes referred to as "acid generator (B)") and a resin comprising a structural unit having an acid-labile group (hereinafter sometimes referred to as "resin (A)"). 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).
[0017] [0017] <Acid Generator (B)> A non-ionic or ionic acid generator can be used as the acid generator (B). Examples of nonionic acid generator include sulfonate esters (eg, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (eg, disulfone, ketosulfone, sulfonyldiazomethane) and the like. Typical examples of the ionic acid generator include onium salts containing an onium cation (eg, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the onium salt anion include sulfonic acid anion, sulfonylimide anion, sulfonylmethide anion and the like.
[0018] [0018] Specific examples of acid generator (B) include compounds which generate acid upon exposure to radiation mentioned in JP 63-26653 A, JP 55-164824 A, JP 62-69263 A, JP 63-146038 A , JP 63-163452 A, JP 62-153853 A, JP 63-146029 A, US patent
[0019] The acid generator (B) is preferably an acid generator containing fluorine, and more preferably a salt represented by the formula (B1) (hereinafter sometimes called "acid generator (B1) ”, excluding salt (1)): Qh + -0.S [61 zit Os Ÿ X, (81) a where, in formula (B1), QPt and Q° each independently represent a fluorine atom or a group perfluoroalkyl having 1 to 6 carbon atoms, LP represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CHz- included in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom included in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CH>- included in the hydrocarbon group alicyclic can be replaced by -O-, -S(O)2- or -CO-, and Z1* represents an organic cation.
[0020] [0020] Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by QP! and QP* 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.
[0021] [0021] Examples of divalent saturated hydrocarbon group in LP! include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, or the divalent saturated hydrocarbon group may be a group formed by combining two or more of these groups.
[0022] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by LP is replaced by -O- or -CO- includes, for example, a group represented by any one of formula (b1-1) to formula (b1-3). In the groups represented by formula (b1-1) to formula (b1-3) and the groups represented by formula (b1-4) to formula (b1-11) which are specific examples, * and ** represent a binding site, and * represents a -Y binding site.
[0023] [0023] p b3 wa 0. 185 + 0 * No So , DS, b4 1 DS, be” 077
[0024] In the groups represented by the formula (b1-1) to the formula (b1-3), when -CHz- included in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of atoms of carbon before replacement is taken as the number of carbon atoms of the saturated hydrocarbon group.
[0025] [0025] LP is preferably a single bond.
[0026] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by LP! is replaced by -O- or -CO- is preferably a group represented by formula (b1-1) or formula (b1-3).
[0027] [0027] Examples of the group represented by the formula (b1-1) include the groups represented by the formula (b1-4) to the formula (b1-8).
[0028] [0028] LPS is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. LP is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. [P19 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
[0029] [0029] Examples of the group represented by the formula (b1-3) include the groups represented by the formula (b1-9) to the formula (b1-11).
[0030] [0030] In the groups represented by formula (b1-9) to formula (b1-11), when a hydrogen atom included in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before substitution is taken as the number of carbon atoms of the saturated hydrocarbon group.
[0031] Examples of alkylcarbonyloxy group include acetyloxy group, propionyloxy group, butyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group and the like.
[0032] [0032] Examples of the group represented by the formula (b1-4) include the following:
[0033] [0033] Examples of the group represented by the formula (b1-5) include the following: 0 O O O O A Fortis. ee Ao Ao. O O oO CH O , O , gn Aer Ae Age 0 TH to CH Oo Hs N , PH N AH HALS u AS AD
[0034] [0034] Examples of the group represented by the formula (b1-6) include the following: x OT xx PSE x ek PE ge ONT / f OY | LA to O GO; x “Actor Ae Ate Arg AT
[0035] [0035] Examples of the group represented by the formula (b1-7) include the following:
[0036] [0036] Examples of the group represented by the formula (b1-8) include the following:
[0037] [0037] Examples of the group represented by the formula (b1-2) include the following: A, He He u A, Hot, 3 3
[0038] [0038] Examples of the group represented by the formula (b1-9) include the following:
[0039] [0039] Examples of the group represented by the formula (b1-10) include the following: Hs Hs Hz AO > De DH oi COA ne nf PA Ao: FFFFF Fa # E Fa F Fo fl F3 Of F3 F F3 N AFP do from [e! in H
[0040] [0040] Examples of the group represented by the formula (b1-11) include the following:
[0041] [0041] Examples of the alicyclic hydrocarbon group represented by Y include groups represented by formula (Y1) to formula (Y11) and formula (Y36) to formula (Y38).
[0042] The alicyclic hydrocarbon group represented by Y is preferably a group represented by any one of formula (Y1) to formula (Y20), formula (Y26), formula (Y27), formula (Y30 ), formula (Y31) and formula (Y39) to formula (Y43), more preferably a group represented by formula (Y11), formula (Y15), formula (Y16), formula (Y20) , formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43), and more preferably a group represented by formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43).
[0043] [0043] Examples of the methyl group substituent represented by Y include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an glycidyloxy, a -(CHz ); a -CO-O-RE* or a group -(CH: ); a -O-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 a group obtained by combining these groups, -CHz - included in the alkyl group or the alicyclic hydrocarbon group can be replaced by -O-, -S(0)2- or -CO-, a hydrogen atom included in the alkyl group, the alicyclic hydrocarbon group or the hydrocarbon group aromatic may be substituted with a hydroxy group or a fluorine atom), and j represents an integer of 0 to 4, Examples of the substituent of the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms which may be substituted by a hydroxy group, (-CH:- included in the alkyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms , an aromatic hydrocarbon group having 6 to 1 8 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, a glycidyloxy group, a -(CHz ) group; a -CO-O-RE* or a group -(CH: ); a -O-CO-RP! (where RP represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group obtained by combining these groups, - CHz- included in the alkyl group and the alicyclic hydrocarbon group can be replaced by -O-, -SO-- or -CO-, and a hydrogen atom included in the alkyl group, the alicyclic hydrocarbon group or the aromatic hydrocarbon group may be substituted by a hydroxy group or a fluorine atom, and ja represents an integer of 0 to 4).
[0044] [0044] Examples of halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.
[0045] [0045] Examples of Y include the following. . J * 0 ee A Ap 7 3 À a 706 (0) (101) { ; Y104° * (Y102) (Y103) ( ) > (105) (1106)
[0046] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group substituted by a hydroxy group, and more preferably an adamantyl group which may have a substituent, and -CHz- included in the alicyclic hydrocarbon group or the group adamantyl can be replaced by -CO-, -S(O)>- or -CO-. Specifically, Y! is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or groups represented by the formula (Y42) and the formula (Y100) to the formula (Y114), and more preferably a hydroxyadamantyl group, an oxoadamantyl group, a group including these groups, or groups represented by formula (Y42), formula (Y100) to formula (Y114).
[0047] [0047] The anion in the salt represented by the formula (B1) is preferably an anion represented by the formula (B1-A-1) to the formula (B1-A-59) [hereinafter sometimes called "anion (B1-A-1) > according to the number of the formula], and more preferably an anion represented by any one of the formula (B1-A-1) to the formula (B1-A-4), the formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40) and formula (B1-A-47) to formula (B1-A-59).
[0048] [0048] OH Oo aM Q»2 OH b1 b2 QE! a2 - or A4 _ Q Q Oo 7 OS On A4 O3S L 038 LA 3 O O 0 (B1-A-1) (B1-A-2) (B1-A-3) an! eo“ ob! a“ R2 ob to os DL “os YT SLA os
[0049] [0049] 0 OH Qs! „a2 QE! do 0 7 0:57 SO ï 072 al! ab Lo F F O - bone O. (B1-A-13) (B1-A-14) FF Ô o (B1-A-15) OH 9 X OH b1 2 a a2 - SONO 0 vO On Ok on 035 ESF or „or O3S ESF O oo A O (B1-A-16) EOF O (B1-A-18) (B1-A-17) OH OH
[0050] [0050] QE Qb2 O CH; Q a“ 9 CHs - €, A4 _ os © os L ° O > 0 ò
[0051] [0051] 0 Mpis bl 2 R7 oh on - : N = LA4 - fr LA4 Oss LA4 O,S 0 GS © O Qb2 F QP2 F (B1-A-39) (B1-A-34) (B1-A- 35) F F
[0052] [0052] O. O © O > © © o F Oo QP” ab Oy bi b2 b1 b2 a" Q o aM ao _ Ox os “T LE eN eN (B1-A-47) 9 (Bl-A-48) 0 (B1-a-49) O. O Oo O Oo OH or Mr Dr X oO A O O O
[0053] [0053] Preferred anions in the salt represented by formula (B1) include anions represented by formula (B1a-1) to formula (B1a-38).
[0054] [0054] O
[0055] Of these, an anion represented by any one of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-19) and formula (B1a-22) to formula (B1a-38) is preferred.
[0056] [0056] Examples of organic cation as for Z1* include organic onium cation, organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation and organic phosphonium cation. Of these, an organic sulfonium cation and an organic iodonium cation are preferred, and an arylsulfonium cation is more preferred. Specific examples thereof include a cation represented by any one of formula (b2-1) to formula (b2-4) (hereinafter sometimes referred to as "(b2-1)cation" depending on the number of the formula).
[0057] 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. © CoH5 6 a CeH43 CeaH417 of 7578 0; "to C6 where of (b2-c-1) (b2-c-2) (b2-c-3) (b2-c-4) (b2-c5) (b2-c6) (b2-c-7) (b2-c-8) H3 H3 H3 -C4He -C4Hg © © Ge O © 2 Os RC 9 CHA OE + (Vp H 6 tC,H, (b2-c-14) (b2-c-9) (b2 -c-10) (b2-c-11) (b2-c-12) (62-013)
[0058] [0058] H Ss | XQQ © DO 0 © {<= p HOL sb O+ a Ö ' + + Le SZ 5 Od 75 © (b2-c-15) (b2-c-16) 621) (02018) (2019) F (b2-c -21) (b2-c-22) Ç (b2-c-20) +) 8 +) 4) CC oO oO © | © C Cs] HIST] AND ® (2 U) (62-0-23) (b2024) (02025) 2.426) (6227) (02047) (b2-c-48) (b2-c-49) F3 R ( 4 (9 (4 CF3 F FF (b2-c-51) (b2-c-52) (b2-c-53)
[0059] [0059] Examples of cation (b2-2) include the following cations. + + + + CX) — IX )— > IX > L FA (b2-c-28) (b2-c-29) (b2-c-30) (b2-c-50)
[0060] [0060] Examples of cation (b2-3) include the following cations. DO Lo AE oP 607 0” (b2-c-31) (b2-c-32) (b2-c-33) (b2-c-34)
[0061] [0061] Examples of cation (b2-4) include the following cations and the like. ; 30-0 oo Oe Zoo D 5 v (D (b2-c-35) (b2-c-36) (b2-c-37) (b2-c-38) Hs Ha Hs Hs 2 2 Q 2 STO: Bo 0 30-0 7 Kp Cen (b2-c-39) U (b2-c-40) Hs (b2-c-41) $ (b2-c-42) ve t-C4Hs tC4Hg t-CaHo 30-0 30 -0 30-0 ZOO D (7 (b2-c-44) (9 ©) (b2-c-46) (b2-c-43) tok, (2045) 0.4, (4
[0062] [0062] The acid generator (B) is a combination of the aforementioned anion and the aforementioned organic cation, and these may be optionally combined. The acid generator (B) preferably includes a combination of an anion represented by any one of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula (B1a-19) and from formula (B1a-22) to formula (B1a-38) with a cation (b2-1), a cation (b2-3), a cation (b2-4).
[0063] [0063] The acid generator (B) preferably includes those represented by the formula (B1-1) to the formula (B1-56), and among these acid generators, those containing an arylsulfonium cation are preferred, and those represented by formula (B1-1) to formula (B1-3), formula (B1-5) to formula (B1-7), formula (B1-11) to formula (B1-14) , formula (B1-20) to formula (B1-26), formula (B1-29) and formula (B1-31) to formula (B1-56) are particularly preferred. H Hs H A od EF
[0064] [0064] O; X. F OF os F OS OR V6, 1 (B1-13) (B1-14) (B1-15); ee Ge Of oe OB ST a Ö À (B1-17) (2 (B1-18) (B1-16) À” À 0 (B1-19) ° (B1-20) (8137)
[0065] [0065]
[0066] [0066] > F
[0067] [0067]
[0068] When the resist composition of the present invention comprises an acid generator (B), the content of the acid generator (B) is preferably 1 mass part or more and 45 mass parts or less. , preferably 1 part by mass or more (more preferably 3 parts by mass or more) and preferably 50 parts by mass or less, (more preferably 45 parts by mass or less, and more preferably 40 parts by mass or less) based on 100 parts by mass of the resin (A).
[0069] [0069] <Resin (A)> The resin (A) includes a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). It is preferred that the resin (A) includes further a structural unit other than the structural unit (a1) Examples of a structural unit other than the structural unit (a1) include a structural unit having no acid-labile group (hereinafter sometimes referred to as “structural unit(s)"), a structural unit other than the structural unit(al) and the structural unit(s) (e.g. a structural unit having a halogen atom mentioned later (hereinafter sometimes referred to as “ structural unit (a4)"), a structural unit having a non-leaving hydrocarbon group mentioned later (hereinafter sometimes referred to as "structural unit (a5)")), and other structural units derived from monomers known in the art.
[0070] <Structural unit (a1)> The structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter sometimes referred to as "monomer (a1)".
[0071] [0071] Examples of the alkyl group for R2%, R22 and R°° include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group and analogues. Examples of alkenyl group in R*, R°2 and R° include ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octynyl group, isooctynyl group, nonenyl group and the like. The alicyclic hydrocarbon group in R°*, R°2 and R® can be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* represents a bond). The number of carbon atoms of the alicyclic hydrocarbon group of R°*, R2 and R® is preferably from 3 to 16.
[0072] [0072]
[0073] [0073] Examples of group (1) include the following groups.
[0074] [0074] Specific examples of group (2) include the following groups. * represents a binding position.
[0075] The monomer (al) is preferably a monomer having an acid-labile group and an ethylenically unsaturated bond, and more preferably a (meth)acrylic monomer having an acid-labile group.
[0076] Among the (meth)acrylic monomers having an acid-labile group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferably cited by way of example. When a resin (A) including a structural unit derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in a resist composition, it is possible to improve the resolution of a resist pattern.
[0077] [0077] The structural unit derived from a (meth)acrylic monomer having a group (1) is preferably a structural unit represented by the formula (a1-0) (hereinafter sometimes referred to as structural unit (a1-0) , a structural unit represented by the formula (a1-1) (hereinafter sometimes referred to as structural unit (a1-1)) or a structural unit represented by the formula (a1-2) (hereinafter sometimes referred to as structural unit (a1 -2) ).The structural unit is preferably at least one structural unit selected from the group consisting of a structural unit (a1-1) and a structural unit (a1-2).These structural units can be used alone, or two or more structural units can be used in combination.
[0078] [0078] RO R°* and R°° are preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
[0079] The structural unit (a1-0) includes, for example, a structural unit represented by any one of formula (a1-0-1) to formula (a1-0-18) and a structural unit wherein a methyl group corresponding to R*° in the structural unit (a1-0) is substituted by a hydrogen atom, a halogen atom, a haloalkyl group, or another alktyl group, and is preferably a structural unit represented by any one of formula (a1-0-1) to formula (a1-0-10), formula (a1-0-13) and formula (a1-0-14).
[0080] The structural unit (a1-1) includes, for example, structural units derived from the monomers mentioned in JP 2010-204646 A. Of these structural units, a structural unit represented by any of the formula (a1-1-1) to the formula (a1-1-7) and a structural unit in which a methyl group corresponding to R** in the structural unit (a1-1) is substituted by an atom of hydrogen, a halogen atom, a haloalkyl group, or another alktyl group, and a structural unit represented by any one of formula (a1-1-1) to formula (a1-1-4) is still most preferred. HH Hs Hs Loof} Age} orgy DO D ° (a1-1-1) (a1-1-2) (a1-1-3) (a1-1-4) Hs HH TEST oft 1e DR OD > (a1- 1-5) (a1-1-6) (a1-1-7)
[0081] [0081] Examples of structural unit (a1-2) include a structural unit represented by any one of formula (a1-2-1) to formula (a1-2-12) and a structural unit in which a methyl group corresponding to R in the structural unit (a1-2) is substituted by a hydrogen atom and a structural unit represented by any one of formula (a1-2-2), formula (a1-2- 5), formula (a1-2-6) and formula (a1-2-10) to formula (a1-2-12) is preferred. tet JP JR St d O en O d O SS XS SO ODO O0 TO TO (a1-2-1) (a1-2-2) (a1-2-3) (a1-2-4) (a1-2- 5) (a1-2-6) Ae I get ee OO Ha #0 OOOOO AS O 5 O ' © © (a1-2-7) (a1-2-8) (a1-2-9) (a1-2 -10) (a1-2-11) (a1-2-12)
[0082] [0082] When the resin (A) includes a structural unit (a1-0), its total content is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 40 mol%. , based on all the structural units of the resin (A).
[0083] [0083] In the structural unit (a1), examples of the structural unit having a group (2) include a structural unit represented by the formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1- 4)>):
[0084] [0084] Examples of halogen atom in R232 and R233 include fluorine atom, chlorine atom and bromine atom.
[0085] [0085] Examples of *-X°*-(a2%2-X232),e- include *-O-, *-CO-O-, *-O-CO-, *-CO-0-A332- CO-0-, *-0-CO-A332-0-, *-0-A332-CO-0-, *-CO-0-A%32-0- CO- and *-0-CO-A332- 0-CO-. Of these, *-CO-0-, *-CO-0-A232-CO-0- or *-O-A332-CO-O- are preferred.
[0086] R33* is preferably a hydrogen atom, and R335 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a methyl group or an ethyl group.
[0087] [0087] -OC(R23%)(R235)-0-R23%6 in structural unit (a1-4) is removed by contact with an acid (e.g., p-toluenesulfonic acid) to form a group hydroxy.
[0088] The structural unit (a1-4) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646
[0089] [0089] The structural unit derived from a (meth)acrylic monomer having a group (2) also includes a structural unit represented by the formula (a1-5) (hereinafter sometimes referred to as “structural unit (a1-5) ").
[0090] [0090] The halogen atom includes a fluorine atom and a chlorine atom and is preferably a fluorine atom. Examples of the alkyl group having 1 to 6 carbon atoms optionally having a halogen atom include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl, a fluoromethyl group and a trifluoromethyl group.
[0091] In the formula (a1-5), R°® is preferably a hydrogen atom, a methyl group or a trifluoromethyl group, L° is preferably an oxygen atom, one of L°* and L” is preferably -O- and the other is preferably -S- s1 is preferably 1, sl' is preferably an integer from 0 to 2, and zt is preferably a single bond or *-CHz- CO-O-.
[0092] [0092] Examples of the structural unit (a1-5) include structural units derived from the monomers mentioned in JP 2010-61117 A. Among these structural units, the structural units represented by the formula (a1-5-1) to formula (a1-5-4) are preferred, and structural units represented by formula (a1-5-1) or formula (a1-5-2) are more preferred.
[0093] The structural unit (a1) also includes the following structural units.
[0094] [0094] <Structural Unit(s)> The structural unit(s) derives from a monomer having no acid-labile group (hereinafter referred to as "monomer(s)"). It is possible to use as monomer from which derives the structural unit (s), a monomer having no labile group in an acid medium known in the field of resist.
[0095] <Structural Unit (a2)> The hydroxy group belonging to the structural unit (a2) may be either an alcoholic hydroxy group or a phenolic hydroxy group.
[0096] In the structural unit (a2), examples of the structural unit having a phenolic hydroxy group include a structural unit represented by the formula (a2-A) (hereinafter sometimes referred to as "structural unit (a2-A )»):
[0097] [0097] Examples of the halogen atom in R°° and R°* include a fluorine atom, a chlorine atom and a bromine atom.
[0098] Examples of *-X2*!-(a252-X°52)p- include *-O-, *-CO-O-, *-0-CO-, *-CO-O-A3 - CO-O-, *-O-CO-A3 -O-, *-OA°* -CO-O-, *-CO-0-A°**-0- CO- and *-O-CO -A®%*-0-CO-. Of these, *-CO-0-, *-CO-O-A®%*-CO-0- or *-0-A 52-CO-0- are preferred.
[0099] Examples of structural unit (a2-A) include structural units derived from the monomers mentioned in JP 2010-204634 A and JP 2012-12577 A. Examples of structural unit (a2-A) include structural units represented by the formula (a2-2-1) to the formula (a2-2-16), and a structural unit in which a methyl group corresponding to R350 in the structural unit (a2-A) is substituted with a d hydrogen in the structural units represented by the formula (a2-2-1) to the formula (a2-2-16). The structural unit (a2-A) is preferably a structural unit represented by the formula (a2-2-1), a structural unit represented by the formula (a2-2-3), a structural unit represented by the formula ( a2-2-6 ) a structural unit represented by the formula (a2-2-8), structural units represented by the formula (a2-2-12) to the formula (a2-2-14), and a structural unit wherein a methyl group corresponding to R° in the structural unit (a2-A) is substituted by a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group in a structural unit represented by the formula (a2-2-1), a structural unit represented by the formula (a2-2-3), a structural unit represented by the formula (a2- 2-6), a structural unit represented by the formula (a2-2- 8) and structural units represented by formula (a2-2-12) to formula (a2-2-14), more preferably a structural unit represented by formula (a2-2 -3), a structural unit represented by the formula (a2-2-8), structural units represented by the formula (a2-2-12) to the formula (a2-2-14), and structural units in which a methyl group corresponding to R®° in the structural unit (a2-A) is substituted by a hydrogen atom in a structural unit represented by the formula (a2-2-3) or a structural unit represented by the formula ( a2-2-8) and the structural units represented by the formula (a2-2-12) to the formula (a2-2-14), and more preferably a structural unit represented by the formula (a2-2-8) and a structural unit in which a methyl group corresponding to R°°° in the structural unit (a2-A) is substituted by a hydrogen atom in a structural unit represented by the formula (a2-2-8). m E TPE AND tn PET ò Ô, OH OH & ZH & GH OH H OH du! (a2-2-1) (a2-2-2) (a2-2-3) (a2-2-4) (a2-2-5) (a2-2-6) (a2-2-7) ( a2-2-8) a ES OH On VO Su a. H' ef © ZH OF HF (a2-2-9) (a2-2-10) (82211) (22212) (a2-2-13) (a2-2-14) (a2-2-15) (a2 -2-16) When the structural unit (a2-A) is included in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, more preferably 15 to 65 mol%, and more preferably 20 to 60 mol%, based on all structural units.
[0100] [0100] Examples of the structural unit having an alcoholic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as “structural unit (a2-1)” ).
[0101] In the formula (a2-1), L°* is preferably -O- or -O-(CHz); -CO- O- (fl represents an integer from 1 to 4), and more preferably - O-, R31* is preferably a methyl group, R2!5 is preferably a hydrogen atom, RS is preferably a hydrogen atom or a hydroxy group, and o1 is preferably an integer from 0 to 3, and more preferably 0 or 1.
[0102] [0102] The structural unit (a2-1) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646 A. A structural unit represented by any one of the formula (a2-1-1) to the formula (a2-1-6) is preferred, a structural unit represented by any one of the formula (a2-1-1) to the formula (a2-1-4) is more preferred, and a structural unit represented by formula (a2-1-1) or formula (a2-1-3) is more preferred.
[0103] [0103] <Structural unit (a3)> The lactone ring belonging to the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring or an α-valerolactone ring, or a condensed ring one monocyclic lactone ring and the other ring. Preferably, a γ-butyrolactone ring, an adamantanelactone ring or a bridged ring including a γ-butyrolactone ring structure (eg, a structural unit represented by the following formula (a3-2)) is exemplified. The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3) or the formula (a3-4). These structural units may be included alone, or two or more structural units may be included: not Ra19 fe fo | | _ - - CHz-C, en >} Len + tt > + 2 =>] 1/24 = xas a6 La7 (RE pi ('as IS (Ra) FRS) O (RZ) 01 5 > O — 1 (a3 -1) (a3-2) (a3-3) (a3-4) where in formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3- 4),
[0104] [0104] Examples of the aliphatic hydrocarbon group in R°*, R222, R223 and R225 include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and a tert-butyl group.
[0105] [0105] Examples of alkanediyl group in L® and L® include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4 -diyl, pentane-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane group - 1,2-diyl, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
[0106] In formula (a3-1) to formula (a3-3), preferably, L°* to L°° are each independently -O- or a group in which k3 is an integer from 1 to 4 in *-O-(CH2)(3-CO-O-, more preferably -O- and *-O-CH2-CO-O-, and more preferably an oxygen atom, RAS at R°2! are preferably a methyl group, preferably, R°° and R223 are each independently a carboxy group, a cyano group or a methyl group, and preferably, p1, q1 and r1 are each independently an integer from 0 to 2, and preferably still 0 or 1.
[0107] [0107] In the formula (a3-4), R** is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or a group ethyl, and more preferably a hydrogen atom or a methyl group, R22 is preferably a carboxy group, a cyano group or a methyl group,
[0108] [0108] Examples of structural unit (a3) include structural units derived from monomers mentioned in JP 2010-204646 A, monomers mentioned in JP 2000-122294 A and monomers mentioned in JP 2012-41274 A. structure (a3) is preferably a structural unit represented by any one of formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula ( a3- 2-2), the formula (a3-3-1), the formula (a3-3-2) and the formula (a3-4-1) to the formula (a3-4-12), and the units structural groups in which the methyl groups corresponding to R°1$, R°1°, R220 and R°°* in the formula (a3-1) to the formula (a3-4) are substituted with hydrogen atoms in the structural units above.
[0109] [0109] <Structural unit (a4)> Examples of structural unit (a4) include the following structural unit: R41 Hs Le O (a4)
[0110] [0110] Examples of the chain saturated hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group. Examples of 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 bond).
[0111] Examples of structural unit (a4) include a structural unit represented by at least one structural unit selected from the group consisting of formula (a4-0), formula (a4-1), formula (a4- 2), the formula (a4-3) and the formula (a4-4):
[0112] [0112] Examples of the alkanediyl group in L* include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group and butane-1,4-diyl group; and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl.
[0113] Examples of perfluoroalkanediyl group in L* include difluoromethylene group, perfluoroethylene group, perfluoropropane-1,1-diyl group, perfluoropropane-1,3-diyl group, perfluoropropane-1,2-diyl group, a perfluoropropane-2,2-diyl group, a perfluorobutane-1,4-diyl group, a perfluorobutane-2,2-diyl group, a perfluorobutane-1,2-diyl group, a perfluoropentane-1,5-diyl group, a perfluoropentane-2,2-diyl group, a perfluoropentane-3,3-diyl group, a perfluorohexane-1,6-diyl group, a perfluoro-hexane-2,2-diyl group, a perfluorohexane-3,3- diyl, a perfluoroheptane-1,7-diyl group, a perfluoroheptane-2,2-diyl group, a perfluoroheptane-3,4-diyl group, a perfluoroheptane-4,4-diyl group, a perfluorooctane-1,8- diyl, a perfluorooctane-2,2-diyl group,
[0114] [0114] L® is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
[0115] [0115] Examples of the structural unit (a4-0) include the following structural units, and the structural units in which a methyl group corresponding to R° in the structural unit (a4-0) is substituted with a hydrogen in the following structural units: Le ue Le rj P+ nn 1 Re UT, (a4-0-1) (a4-0-2) (a4-0-3) (a4-0-4) Loss pst tst tr, Fs nr FC pd F3 pr, 8F47 @+07) (04-0-8) (a4-0-9) ho 0) (a4-0-11) (a4-0-12) ter TT A WET CS a pl F F sF13
[0116] [0116] Ha paf | The} Aa (a4-1)
[0117] [0117] Examples of the saturated hydrocarbon group in R** include a chain saturated hydrocarbon group and a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and the groups formed by combining these groups.
[0118] [0118] Examples of the chain saturated hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group.
[0119] [0119] Examples of the substituent belonging to R°* include at least one selected from the group consisting of a halogen atom and a group represented by the formula (a-g3). Examples of halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom, and fluorine atom is preferred: % ——X2a43—pa45 (ag 3) where, in the formula (a-g3), X represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-
[0120] [0120] Examples of the aliphatic hydrocarbon group in A include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group; monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* represents a bond). í CD 0-09-6000
[0121] [0121] R°*2 is preferably an aliphatic 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). When R°* is an aliphatic hydrocarbon group having a halogen atom, an aliphatic hydrocarbon group having a fluorine atom is preferred, a perfluoroalkyl group or a perfluorocycloalkyl group is further preferred, a perfluoroalkyl group having 1 to 6 carbon atoms is more preferred, and a perfluoroalkyl group having 1 to 3 carbon atoms is particularly preferred. Examples of perfluoroalkyl group include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group and perfluorooctyl group. Examples of perfluorocycloalkyl group include perfluorocyclohexyl group and the like.
[0122] [0122] When R** is an aliphatic hydrocarbon group having the group represented by formula (a-g3), R°° is more preferably a group represented by formula (a-g2): + —A216_x244__pa47 (a- g2) where, in the formula (a-g2), A°*° represents a divalent aliphatic hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, X21* represents **-O-CO- or * *-CO-O- (** represents a binding site at A°°), A represents a saturated hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, the total number of carbon atoms of A°°, A and X°** is 18 or less, and at least one of A°* and A°* to at least one halogen atom, and * represents a bond to a carbonyl group.
[0123] [0123] The number of carbon atoms of the aliphatic hydrocarbon group of A is preferably 1 to 6, and more preferably 1 to 3.
[0124] [0124] Preferred structures of the group represented by formula (a-g2) are the following structures (* represents a bond to a carbonyl group).
[0125] [0125] Examples of alkanediyl group in A * include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane- 1,5-diyl and a hexane-1,6-diyl group; and branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group and a 2-methylbutane-1,4-diyl group. Examples of the substituent in the alkanediyl group such as A * include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. A*! is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.
[0126] [0126] Examples of the divalent saturated hydrocarbon group represented by A A23 and A7* in the group represented by formula (a-g1) include a linear or branched alkanediyl group and a monocyclic divalent alicyclic hydrocarbon group, and groups formed by combining an alkanediyl group and a divalent alicyclic hydrocarbon group. Specific examples thereof include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1- methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like. Examples of the substituent of the divalent saturated hydrocarbon group represented by A22, A and A°** include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. s is preferably 0.
[0127] In the group represented by 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 bond, and ** represents a bond to -O-CO-R2*2. O O 0 O 2 Ö O O. x ko O Kk x xx * O kk Et ASS SA SNS O Ö O 0 Ö
[0128] [0128] Examples of the structural unit represented by the formula (a4-1) include the following structural units, and the structural units in which a methyl group corresponding to A°* in the structural unit represented by the formula (a4- 1) in the following structural units is substituted with a hydrogen atom. H H H H Hs Hs ch CH + CH + CH + summer Jets
[0129] [0129]
[0130] The structural unit represented by formula (a4-1) is preferably a structural unit represented by formula (a4-2): Hs RB
[0131] [0131] Examples of the alkanediyl group for L** include the same groups as those mentioned for Aê**, Examples of the saturated hydrocarbon group of R include the same groups as those mentioned for R°*, The alkanediyl group in L* is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.
[0132] [0132] 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 structural unit (a4-2) is substituted with a hydrogen atom is also exemplified as a structural unit represented by (a4-2):
[0133] [0133] Ho OR" At 7 O 5 € 7 (a4-3) a O un X where, in the formula (a4-3), RF represents a hydrogen atom or a methyl group, L° represents an alkanediyl group having 1 to 6 carbon atoms, AS represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms optionally having a fluorine atom,
[0134] Examples of the alkanediyl group in L° include the same as those mentioned as alkanediyl group A°# The divalent saturated hydrocarbon group optionally having a fluorine atom in Af!3 is preferably a divalent saturated hydrocarbon group HN optionally having a fluorine atom. fluorine atom or a divalent alicyclic hydrocarbon group optionally having a fluorine atom, and more preferably a perfluoroalkanediyl group.
[0135] [0135] Examples of a saturated hydrocarbon group and a saturated hydrocarbon group optionally having a fluorine atom for Alt include the same groups as those mentioned for R°#2. Of these groups, preferred are fluorinated alkyl groups such as a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3 group, 3,3-pentafluoropropyl, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3 group, 3,4,4,5,5,5-nonafluoropentyl, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorooctyl group; a cyclopropylmethyl group, a cyclopropyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group, a perfluorocyclohexyl group, an adamantyl group, an adamantylmethyl group, an adamantyldimethyl group, a norbornyl group, a norbornylmethyl group, a perfluoroadamantyl group, a perfluoroadamantylmethyl and the like.
[0136] [0136] In the formula (a4-3), L° is preferably an ethylene group. The divalent saturated hydrocarbon group of Af is preferably a group including a divalent HN hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a divalent chain hydrocarbon group having 2 to 3 carbon atoms.
[0137] [0137] The structural unit represented by the formula (a4-3) includes, for example, structural units represented by the formula (a4-1"-1) to the formula (a4-1'-11). structural unit in which a methyl group corresponding to R” in a structural unit (a4-3) is substituted with a hydrogen atom is also exemplified as a structural unit represented by (a4-3).
[0138] [0138]
[0139] [0139] Examples of the saturated hydrocarbon group of R2* include those which are the same as the saturated hydrocarbon group represented by R°*2, RP2 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic 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 having a fluorine atom.
[0140] [0140] The structural unit represented by the formula (a4-4) includes, for example, the following structural units and the structural units in which a methyl group corresponding to R* in the structural unit (a4-4) is substituted with a hydrogen atom in the structural units represented by the following formulas.
[0141] <Structural unit (a5)> Examples of the non-leaving hydrocarbon group belonging to the structural unit (a5) include groups having a linear, branched or cyclic hydrocarbon group. Of these, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. The structural unit (a5) includes, for example, a structural unit represented by the formula (a5-1): 51 Hz 6 (a5-1)
[0142] [0142] The alicyclic hydrocarbon group in R° can be monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon group includes, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group. The polycyclic alicyclic hydrocarbon group includes, for example, an adamantyl group and a norbornyl group.
[0143] [0143] Examples of the divalent saturated hydrocarbon group in L” include a divalent chain saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and a divalent chain saturated hydrocarbon group is preferred.
[0144] [0144] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by L°° is replaced by -O- or -CO- includes, for example, the groups represented by the formula (L1-1) at formula (L1-4). In the following formulas, * and ** each represents a bond, and * represents a bond to an oxygen atom. xt 42 2 LX4 <5 6 At x 1 129 ge Ae LA De Sp IT > (L1-1) (L1-2) (L1-3) (L1-4) In the formula (L1-1), X represents * -O-CO- or *-CO-O- (* represents a binding site to L), L* represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms, L* represents a single bond or a hydrocarbon group saturated divalent aliphatic having 1 to 15 carbon atoms, and the total number of carbon atoms of L* and L* is 16 or less. In the formula (L1-2), LS represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms, L* represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms, and the total number carbon atoms of L3 and L** is 17 or less. In the formula (L1-3), L* represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms, L$ and LY each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms , and the total number of carbon atoms of L°, L® and L” is 15 or less. In the formula (L1-4),
[0145] [0145] Lt is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
[0146] The group represented by formula (L1-1) includes, for example, the following divalent groups.
[0147] The group represented by formula (L1-2) includes, for example, the following divalent groups.
[0148] The group represented by formula (L1-3) includes, for example, the following divalent groups. CH 0.0 Lo
[0149] The group represented by the formula (L1-4) includes, for example, the following divalent groups. OA | GT AG xx Q x x # © 9 AJ d ID 9
[0150] [0150] Examples of the structural unit (a5-1) include the following structural units and the structural units in which a methyl group corresponding to R° in the structural unit (a5-1) is substituted with a hydrogen atom in the following structural units.
[0151] [0151] The structural unit (a6) is a structural unit having a -SO group, and preferably has a -SO>- group in the side chain. The structural unit having -SO>- group can have linear structure having -SO>- group, branched structure having -
[0152] [0152] Examples of the sultone ring include the rings represented by the following formulas (T1-1), (T1-2), (T1-3) and (T1-4). The binding site can be at any position. The sultone ring may be a monocyclic type, but is preferably a polycyclic type. The polycyclic sultone ring means a bridging ring containing -SO2-O- as a group of atoms constituting the ring, and examples thereof include the rings represented by the formulas (T1-1) and (T1-2). Like the ring represented by the formula (T1-2), the sultone ring may further contain a heteroatom in addition to -SO2-O- as a group of atoms constituting the ring. Examples of heteroatom include oxygen atom, sulfur atom or nitrogen atom, and oxygen atom is preferable.
[0153] [0153] The sultone ring may have a substituent, and examples thereof include, a halogen atom, a hydroxy group, a cyano group or an alkyl group having 1 to 12 carbon atoms, which may have a halogen or a hydroxy group, examples thereof include an alkoxy group having 1 to 12, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, a alkoxycarbonyl group having 2 to 12 carbon atoms and an alkylcarbonyl group having 2 to 4 carbon atoms.
[0154] [0154]
[0155] [0155] A sultone ring having no substituent is preferable from the viewpoint that the monomer from which structural unit (a6) is derived can be produced easily.
[0156] [0156] As the sultone ring, the ring represented by the formula (T1) is more preferable.
[0157] [0157] Examples of the ring represented by formula (T1") and the ring represented by formula (T1) include the following rings. The binding site is at any position.
[0158] [0158] The structural unit having a sultone ring preferably has the following groups. * represents the binding site in the following groups. ; . Ha. HsC, /CHs Hs * CHs H,C HaC * CH3 d H3C d H3C 70 F0 Ds T =0 Ba TF0 d oi PP a
[0159] [0159] The structural unit having an -SOz- group more preferably has a group derived from a polymerizable group. Examples of the polymerizable group include vinyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, acryloylthio group, methacryloylthio group and the like. Among these, the monomer which leads to the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, and more preferably a (meth)acrylic monomer.
[0160] The structural unit (a6) is preferably a structural unit represented by the formula (Tx). X-ray GT
[0161] [0161] Examples of the halogen atom of R* include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0182] [0182] Examples of the divalent saturated hydrocarbon group of A' include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and these groups. A combination of two or more of these may be used.
[0163] [0163] Examples of R*, X!! and ma are the same as those in formula (T1').
[0164] [0164] Examples of structural unit (a6) include the following structural units. Le H + H + A Le H Le: H À == O Oo NH (8) f HN (a6-1) à &° &° _ 0 (a6-2) (a6-3) (a6-4) ( a6-5) d (a6-6) © ZY | j Fo 8 © (a6-8) 0 (6.9) (a6-10) 60” (a6-12)
[0165] Among these, the structural units represented by the formula (a6-1), the formula (a6-2), the formula (a6-6), the formula (a6-7), the formula (a6- 8) and formula (a6-12) are preferable, and structural units represented by formula (a6-1), formula (a6-2), formulas (a6-7) and (a6-8) are preferable again.
[0166] <Structural unit (ST)> The resin (A) may further include a structural unit which is decomposed by exposure to radiation to generate an acid (hereinafter sometimes referred to as "structural unit (ST)"). Specific examples of the structural unit (IT) include the structural units mentioned in JP 2016-79235 A, and a structural unit having a sulfonate group or a carboxylate group and an organic cation in a side chain or a structural unit having a group sulfonio and an organic anion in a side chain are preferred.
[0187] [0187] The structural unit having a sulfonate group or a carboxylate group and an organic cation in a side chain is preferably a structural unit represented by the formula (II-2-A"):
[0168] [0168] Examples of the halogen atom represented by RS include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0169] [0169] 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.
[0170] [0170] Examples of ZA" in formula (II-2-A") include those which are identical to the Z1* cation in the acid generator (B1).
[0171] The structural unit represented by the formula (II-2-A") is preferably a structural unit represented by the formula (II-2-A): RIIS
[0172] The structural unit represented by formula (II-2-A) is preferably a structural unit represented by formula (II-2-A-1): RIII3 IN
[0173] [0173] The structural unit represented by the formula (II-2-A-1) is more preferably a structural unit represented by the formula (II-2-A-2): ; RS
[0174] [0174] 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): RIl4 er ‚RI (II-1-1 ) o70—A"1-Ri1FS< R!l2
[0175] [0175] Examples of the structural unit including a cation in the formula (II-1-1) include the following structural units, and the structural units in which a group corresponding to the methyl group of R"* is substituted by a hydrogen, a fluorine atom, a trifluoromethyl group and the like.
[0176] [0176] Examples of the organic anion represented by A include a sulfonic acid anion, a sulfonylimide anion, a sulfonyl methide anion and a carboxylic acid anion. The organic anion represented by A' is preferably a sulfonic acid anion, and the sulfonic acid anion is preferably an anion included in the salt represented by the above-mentioned formula (B1).
[0177] [0177] Examples of the sulfonylimide anion represented by A″ include the following. LL 427 O28-CF3 ae 025 O2S—CF2 O,S—CF, F3 F» -GF2 CF3
[0178] [0178] Examples of the sulfonyl methide anion include the following. £F3 FafTCF3 O,S CF; O4S-CF> O,S-CF, ©, | F2 0, L FC, F2 O2 L F,C—S 5 FsC-C-S “9 FX—C-S “ O,S—CF3 O2S-GF2 025-GF2 CF3 F,C—CF3
[0179] [0179] Examples of the carboxylic acid anion include the following. O Oo 0 D _ HC0- HA HEA ons -
[0180] [0180] Examples of the structural unit represented by the formula (IT-1-1) include the following.
[0181] The resin (A) may include structural units other than the aforementioned structural units, and examples of the structural units include the structural units well known in the art.
[0182] The resin (A) is preferably a resin composed of a structural unit (a1) and a structural unit (s).
[0183] The respective structural units constituting the resin (A) may be used singly, or two or more structural units may be used in combination. By using a monomer from which these structural units are derived, it is possible to produce these structural units by a known polymerization process (eg, a radical polymerization process). The content of respective structural units included in the resin (A) can be adjusted depending on the amount of monomer used in the polymerization.
[0184] <Resin other than Resin (A)> The resist composition of the present invention may use the resin other than Resin (A) in combination.
[0185] [0185] The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less. , based on the solid component of the resist composition. When including resins other than resin (A), the total content of resin (A) and resins other than resin (A) is preferably 80% by mass or more and 99% by mass or less, and more preferably 90 mass% or more and 99 mass% or less, based on the solid component of the resist composition. In the present description, "the solid content of the resist composition" means the total content of the constituents of the resist composition from which the solvent (E) mentioned below is removed. 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.
[0186] [0186] <Solvent (E)> The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more and 99% by mass or less. The content of the solvent (E) can be measured, for example, by a means of analysis known as liquid chromatography or gas chromatography.
[0187] [0187] <Deactivating agent (C) ("quencher")> Examples of the deactivating agent (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). When the resist composition includes the quenching agent, the content of the quenching agent (C) is preferably about 0.01 to 15% by weight, more preferably about 0.01 to 10% by weight. , more preferably about 0.1 to 5% by mass, and more preferably about 0.1 to 3% by mass, based on the amount of the solid component of the resist composition.
[0188] [0188] The acidity in an acid-generating salt having a lower acidity than an acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). Regarding the acid-generating salt having a lower acidity than an acid generated from the acid generator (B), the acid dissociation constant of an acid generated from the salt usually satisfies the inequality following: -3 < pKa, preferably -1 < pKa < 7, and more preferably 0 < pKa < 5.
[0189] [0189] Examples of the weak acid inner salt (D) include the following salts.
[0190] <Other Components> The resist composition of the present invention may also include components other than the above-mentioned components (hereinafter sometimes referred to as "other components (F)"). The other components (F) are not particularly limited and it is possible to use various additives known in the field of resists, for example sensitizers, dissolution inhibitors, surfactants, stabilizers and colorants.
[0191] <Preparation of resist composition> The resist composition of the present invention can be prepared by mixing a salt (I), a resin (A) and an acid generator (B) and if necessary, resins other as resin (A), solvent (E), deactivating agent (C) and other components (F). The mixing order of these components is any order and it is not particularly limited. It is possible to select, as the temperature during mixing, an appropriate temperature of 10 to 40°C, depending on the type of the resin, the solvent solubility (E) of the resin and the like. It is possible to choose, as the mixing time, an appropriate time from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited and it is possible to use mixing with agitation. After mixing the respective components, the mixture is preferably filtered through a filter having a pore diameter of about 0.003 to 0.2 µm.
[0192] <Method for producing a resist pattern> The method for producing a resist pattern of the present invention includes: (1) a step of applying the resist composition of the present invention to a substrate, (2) a step of drying the applied composition to form a layer of composition, (3) a step of exposing the layer of composition, (4) a step of heating the exposed layer of composition, and (5) a step of development of the heated composition layer.
[0193] [0193] (Applications) The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) or resist composition for UVE exposure, in particular an electron beam (EB) resist composition or resist composition for UVE exposure, and the composition of resist is useful for fine processing of semiconductors.
[0194] 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.
[0195] Example 1: Synthesis of the carboxylate represented by the formula (1-1) K,CO3 > CH la 9 (I-1-a) (l-1-b) 2.50 parts of a compound represented by the formula (I-1-a), 6.10 parts of potassium carbonate, 8.22 parts of iodine and 12.50 parts of methanol were mixed, followed by stirring at 23°C for 30 minutes. To the thus obtained mixed solution, 30 parts of saturated aqueous sodium hydrogen sulfate solution and 60 parts of chloroform were added, followed by stirring at 23°C for 30 minutes and then isolation with separation to obtain an organic layer. To the organic layer thus obtained, 30 parts of ion-exchanged water was added, followed by stirring at 23°C for 30 minutes and then isolating by separation to obtain an organic layer. This water washing operation was repeated five times. The organic layer thus obtained was concentrated and then the concentrated mixture was isolated using a column (silica gel 60 N (spherical, neutral) 100-210 µm; manufactured by Kanto Chemical Co., Inc., solvent of development: n-heptane/ethyl acetate = 1/1) to obtain 1.84 parts of a salt represented by the formula (I-1-b).
[0196] Example 2: Synthesis of the carboxylate represented by the formula (I-17) N * + + COOMe 9 9 9 Q 0 0 CF3S0x D CF OF, y (I-1-0) (I-17-d) ( I-17-e) NaOH Oxalic acid _ © oo (1-17) 0.11 part of a compound represented by the formula (I-1-c), 10 parts of chloroform, 0.046 part of a compound represented by formula (I-17-d) and 0.08 part of trifluoromethanesulfonic acid were mixed, followed by stirring at 23°C for 30 minutes and then cooling to 5°C. To the mixture thus obtained, 0.11 part of trifluoroacetic acid was added dropwise, followed by stirring at 23°C for 6 hours. To the mixture thus obtained, 10 parts of ion-exchanged water was added, followed by stirring at 23°C for 30 minutes, followed by isolation by separation to obtain an organic layer. To the organic layer thus obtained, 20 parts of a 5% aqueous sodium hydroxide solution was added, followed by stirring at 23°C for 30 minutes and then isolation by separation to obtain a organic layer. The organic layer thus obtained was concentrated and the concentrate was passed through an ion-exchange resin (Aldrich (QAE Sephadex (registered trademark) A-25 in chloride form)) using methanol as a developing solvent. The thus treated solution was concentrated, then 10 parts of chloroform and 10 parts of 5% aqueous sodium hydroxide solution were added, followed by stirring at 23°C for 30 minutes and then isolation by separation to obtain an organic layer. To the organic layer thus obtained, 10 parts of ion-exchanged water was added, followed by stirring at 23°C for 30 minutes and then isolating by separation to obtain an organic layer. This water washing operation was repeated five times. The organic layer thus obtained was concentrated, to obtain 0.04 part of a salt represented by the formula (I-17).
[0197] Example 3: Synthesis of the carboxylate represented by the formula (I-39) K,CO3 > CH la 9 (|-1-a) (l-1-b) 50 parts of a compound represented by the formula ( I-1-a), 120.73 parts of potassium carbonate, 162.60 parts of iodine and 750 parts of methanol were mixed, followed by stirring at 23°C for 3 hours. To the thus obtained mixed solution, 167 parts of an aqueous solution of sodium hydrogen sulfate and 550 parts of chloroform were added, followed by stirring at 23°C for 30 minutes and then isolation by separation to obtain an organic layer. To the organic layer thus obtained, 300 parts of ion-exchanged water was added, followed by stirring at 23°C for 30 minutes and then isolating by separation to obtain an organic layer. This water washing operation was repeated five times. The organic layer thus obtained was concentrated to obtain 56.89 parts of a salt represented by the formula (I-1-b).
[0198] Example 4: Synthesis of the carboxylate represented by the formula (I-23) Ss * 8 * COOMe at 70 © Q Oo © CF:807 ) Ar (I-1-c) (1-39-d) (l -23-e) NaOH Oxalic acid _ LS © COO (1-23) 2.70 parts of a compound represented by formula (I-1-c), 10 parts of chloroform, 1.11 parts of a compound represented by formula (I-23-d) and 1.88 parts of trifluoromethanesulfonic acid were mixed, followed by stirring at 23°C for 30 minutes and then cooling to 5°C. To the mixture thus obtained, 2.64 parts of trifluoroacetic anhydride were added dropwise, followed by stirring at 23°C for 6 hours. To the mixture thus obtained, 18 parts of ion-exchanged water was added, followed by stirring at 23°C for 30 minutes, followed by isolation by separation to obtain an organic layer. To the organic layer thus obtained, 10 parts of a 5% aqueous sodium hydroxide solution was added, followed by stirring at 23°C for 30 minutes and then isolation by separation to obtain a organic layer. The organic layer thus obtained was concentrated and the concentrate was passed through an ion-exchange resin (Aldrich (QAE Sephadex (registered trademark) A-25 in chloride form)) using methanol as a developing solvent. The thus treated solution was concentrated, then 10 parts of chloroform and 10 parts of ion-exchanged water were added, followed by stirring at 23°C for 30 minutes followed by isolation with separation to obtain an organic layer. To the organic layer thus obtained, 10 parts of a 5% oxalic acid aqueous solution was added, followed by stirring at 23°C for 30 minutes and then isolating by separation to obtain a layer. organic. To the organic layer thus obtained, 10 parts of ion-exchanged water was added, followed by stirring at 23°C for 30 minutes and then isolating by separation to obtain an organic layer. This water washing operation was repeated three times. The organic layer thus obtained was concentrated, to obtain 1.28 parts of a salt represented by the formula (I-23). MASS (ESI spectrum (+)):333.1 [M+H]"
[0199] [0199] Example 5: Synthesis of a carboxylate represented by the formula (1-40)
[0200] Example 6: Synthesis of a carboxylate represented by the formula (1-37) Ss + {ES * COOMe 6 70 Q oO O CF3SO3 (l-1-0) (l-37-d) CF (L- 37-e) NaOH Oxalic acid — 9 coo cr) (1-37) 10 parts of a compound represented by formula (I-1-c), 30 parts of chloroform, 6.28 parts of a compound represented by formula (I-37-d) and 6.97 parts of trifluoromethanesulfonic acid were mixed, followed by stirring at 23°C for 30 minutes and then cooling to 5°C. To the mixture thus obtained, 9.76 parts of trifluoroacetic anhydride were added dropwise, followed by stirring at 23°C for 6 hours. To the mixture thus obtained, 65 parts of ion-exchanged water was added, followed by stirring at 23°C for 30 minutes, followed by separation isolation to obtain an organic layer.
[0201] [0201] Synthesis of a resin The compounds (monomers) used in the synthesis of a resin (A) are illustrated below. In the following, these compounds are referred to as “(a1-1-3) monomer” according to the formula number. H Hs Hz H3 Hz CH= CH; CH ch YO “oo 9 da a‘ Yo SA < OH SI a (a1-1-3) (21-26) (a1-4-2) (a1-4-13) (e213) (23-42)
[0202] [0202] Synthesis Example 1 [Synthesis of Resin A1] A monomer (a1-4-2), a monomer (a1-1-3) and a monomer (a1-2-6) were used as monomers, these monomers were mixed in a molar ratio of 38:24:38 [monomer (a1-4-2): monomer (a1-1-3): monomer (a1-2-6)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile was added as an initiator in the amount of 7 mol% based on the total molar number of all monomers, and the mixture was polymerized by heating at 85°C for about 5 hours. To the polymerization reaction solution thus obtained, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added in an amount of 2.0 times the total mass of all monomers, thereby was followed by stirring for 6 hours and further isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and collection to obtain resin A1 (copolymer) having a mass average molecular weight of approximately 5.3 x 103 with a yield of 78%. This A1 resin has the following structural units.
[0203] [0203] Synthesis Example 2 [Synthesis of Resin A2] A monomer (a1-4-2) and a monomer (a1-2-6) were used as monomers, these monomers were mixed in a molar ratio of 38 :62 [(a1-4-2 monomer): (a1-2-6) monomer], and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile as an initiator was added in amounts of 7 mol% based on the total molar number of all monomers, and then polymerization was carried out by heating at 85°C for about 5 hours. To the polymerization reaction solution thus obtained, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added in an amount of 2.0 times the total mass of all monomers, thereby was followed by stirring for 6 hours and further isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and collection to obtain resin A2 (copolymer) having a mass-average molecular weight of about 5.4 x 10° with an efficiency of 89%. This A2 resin has the following structural units. E£cH, of 5 Fe A2
[0204] Synthesis Example 3 [Synthesis of Resin A3] A monomer (a1-1-3), a monomer (a1-2-6), a monomer (a2-1-3), a monomer ( a3-4-2) and a monomer (a1-4-2) as monomers, these monomers were mixed in a molar ratio of 20:35:3:15:27 [monomer (a1-1-3): monomer ( a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the molar number total of all monomers, then the mixture was polymerized by heating at 73°C for about 5 hours. To the polymerization reaction solution thus obtained, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added in an amount of 2.0 times the total mass of all monomers, thereby was followed by stirring for 12 hours and further isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and collection to obtain resin A3 (copolymer) having a weight-average molecular weight of about 5.3 x 10° with a yield of 63%. This A3 resin has the following structural units.
[0205] Synthesis Example 4 [Synthesis of Resin A4] A monomer (a1-1-3), a monomer (a1-2-6), a monomer (a2-1-3), a monomer ( a3-4-2) and a monomer (a1-4-13) as monomers, these monomers were mixed in a molar ratio of 20:35:3:15:27 [monomer (a1-1-3): monomer ( a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-13)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the molar number total of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. To the polymerization reaction solution thus obtained, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added in an amount of 2.0 times the total mass of all monomers, thereby was followed by stirring for 12 hours and further isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and collection to obtain resin A4 (copolymer) having a mass average molecular weight of about 5.1 x 10 with a yield of 61%. This A4 resin has the following structural units.
[0206] [0206] <Preparation of a resist composition> As shown in Table 1, the following components were mixed and the resulting mixture was filtered through a fluororesin filter having a pore diameter of 0.2 µm to prepare resist compositions. [Table 1] Composition of | _<_ generator sem | qender paps | 4 A1 = B1-43 = I-1 = o° oO a A1 = B1-43 = I-1 = C1 = ° o + A1 = B1-43 = [-1 = ° ° [-1 = + A2 = B1 -43 = ° ° Composition 4 10 parts 3.4 parts Da 110°C/120°C part + A1 = B1-43 = 1-17 = ° ° + A1 = B1-43 = 1-17 = C1 = ° ° + A1 = B1-43 = 1-17 = ° ° + A2 = B1-43 = 1-17 = ° ° N A2 = B1-43= [1-23 = ° ° + A2 = B1-43 = 1-37 = ° ° + A2 = B1-43 = 1-39 = ° ° + A2 = B1-43 = 1-40 = ° °ve A4 = B1-43 = I-1 = oo
[0207] [0207] <Resin> A1: Resin A1 <Acid generating salt (B)> B1-43: Salt represented by the formula (B1-43) (synthesized according to the examples of JP-2016-47815-A) Oo Os A0 X OO” |
[0208] [0208] (Evaluation of electron beam resist composition exposure, alkaline development) Each 6 inch (15.24 cm) diameter silicon wafer was treated with hexamethyldisilazane and then baked on a direct hot plate at 90°C for 60 seconds. A resist composition was applied by centrifugal application (“spin coating”) on the silicon wafer so that the thickness of the layer of composition became 0.04 μm. The coated silicon wafer was then prebaked on the direct hot plate at the temperature shown in the "PB" column of Table 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 depth/17 nm diameter) were written directly on the composition layer formed on the wafer while the exposure dose was changed in steps.
[0209] [0209] In the ansi resist pattern obtained after development, the exposure dose at which the diameter of the holes formed reached 17 nm was defined as the effective sensitivity.
[0210] [0210] <Evaluation of CD uniformity (CDU)> In the effective sensitivity, the hole diameter of 17 nm formed by using a mask having a 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 of the hole. The standard deviation was determined under the condition that the average diameter of 400 holes of the patterns formed using the mask having a hole diameter of 17 nm in the same wafer was considered as a population.
[0211] [0211] (Evaluation of resist composition exposure to electron beam: organic solvent development) Each 6 inch (15.24 cm) diameter silicon wafer was treated with hexamethyldisilazane then baked on a direct hot plate at 90°C for 60 seconds. A resist composition was applied by centrifugal application (“spin coating”) on the silicon wafer so that the thickness of the layer of composition became 0.04 μm. The coated silicon wafer was then prebaked on the direct hot plate at the temperature shown in the "PB" column of Table 1 for 60 seconds to form a composition layer. By means of a direct electron beam writing system ["ELS-F125 125 keV", manufactured by ELIONIX INC.], hole patterns (40 nm hole depth/17 nm diameter) were written directly on the composition layer formed on the wafer while the exposure dose was changed in stages after development.
[0212] [0212] In the ansi resist pattern obtained after development, the exposure dose at which the diameter of the holes formed reached 17 nm was defined as the effective sensitivity.
[0213] [0213] <Evaluation of CD uniformity (CDU)> In the effective sensitivity, the hole diameter of the pattern formed using a mask having a 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 of the hole. The standard deviation was determined under the condition that the average diameter of 400 holes of the patterns formed using the mask having a hole diameter of 17 nm in the same wafer was considered as a population.
[0214] Table 3 Compared to comparative compositions 7 and 8, compositions 13 to 19 show a low standard deviation, leading to a satisfactory evaluation of CD uniformity (CDU).
[0215] [0215] A resist composition including a salt (I) of the present invention makes it possible to obtain a resist pattern having a satisfactory CD (CDU) uniformity and is therefore useful for the fine processing of semiconductors and thus has a industrial utility.
[0216] [0216] Priority of Japanese Application No. 2020-086254, filed May 15, 2020, the contents of which are incorporated herein by reference, is claimed.

权利要求:
Claims (22)
[1]
1. A carboxylate represented by formula (T):
AT
A O O (I)
D 0, X PMR ns where, in the formula (I), R1, R2 and R3 each independently represents a halogen atom, an alkyl fluoride group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and -CH>- included in the hydrocarbon group may be replaced by -O-, -CO-, -S- or -SO--, m1 represents an integer from 0 to 5, and when m1 is 2 or more, a plurality of R* may be the same or different from each other, m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R* may be the same or different each other, m3 represents an integer of 0 to 3, and when m3 is 2 or more, a plurality of R* may be the same or different from each other, and X} represents a bond, -CH> -, - O-, -S-, -CO-, -SO- or -SO- -.
[2]
2. The carboxylate according to claim 1, in which m1 represents an integer from 1 to 3.
[3]
3. The carboxylate of claim 2, wherein at least one R* binding site is bonded para to the S* binding site.
[4]
4. The carboxylate according to claim 2 or 3, in which at least one Rt represents:
either an alkyl group having 1 to 3 carbon atoms which may have an iodine atom and/or a fluorine atom, and in which a -CH2- included in this group can be replaced by -O- or -CO- or an branched alkyl group having 3 or 4 carbon atoms.
[5]
5, The carboxylate according to claim 4, wherein at least one R! represents an alkyl group having 1 to 3 carbon atoms in which one -CHz- included in this group is replaced by -O- attached to a benzene ring.
[6]
6. The carboxylate according to claim 4, wherein said alkyl group having 1 to 3 carbon atoms further has one or more fluorine atoms.
[7]
7. The carboxylate according to any one of claims 2 to 6, in which at least one R* represents a branched alkyl group having 3 or 4 carbon atoms.
[8]
8. The carboxylate according to any one of claims 2 to 7, in which m1 represents 2 or 3 and at least one R* represents an iodine atom or a methyl group.
[9]
9. The carboxylate according to claim 3, in which R* linked in the para position relative to the bonding site of S* represents an alkyl group having 1 to 3 carbon atoms which may have an iodine atom and/or a fluorine atom. and where one -CHz- included in this group is replaced by -O- attached to a benzene ring.
[10]
10. The carboxylate according to claim 9, wherein X* represents a single bond.
[11]
11. The carboxylate according to claim 1, said carboxylate being represented by the following formulae:
Ah U Dr ss y: È ASE Se TER RE SOS NRN PTE ao Sas, mm „en N ee gp + way 285 mi Dr Le ne eg En 1 KEN 3 Cr Y Das 5 Le te 0458: Le es U Ge ed a ER THE L. 3 H 2 4 year! A Ses hed ° © Ks MA ST Se” 4273 {305 {ER {Ka
[12]
12. The carboxylate according to claim 1, said carboxylate being represented by the following formulae: pn CF "+ 9 a Ei) _ Ï Le Ps Deeg SN per Ra > ar Ses fr ;: ON A ac De Su Die es tri 83- 373 99)
[13]
13. The carboxylate according to claim 1, said carboxylate being represented by the following formula:
5, 200 LA, in (1-40)
[14]
14. Deactivating agent comprising the carboxylate according to any one of claims 1 to 13.
[15]
15. A resist composition comprising the deactivating agent of claim 14, a resin including a structural unit having an acid labile group and an acid generator.
[16]
The resist composition according to claim 15, wherein the resin comprising a structural unit including an acid-labile group includes at least one structural unit selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by the formula (a1-2): Lt Ras ar pas C © }=0 | 70 | The { The / To. {CH} RA Fe £ 7 ï x, (a1-1} (a1-2) where, in formula (a1-1) and formula (a1-2), L°* and L° each independently represent - O- or *-O- (CHz)k1-CO-O-, k1 represents an integer from 1 to 7, and * represents a -CO- binding site, R°* and R® each independently represent a d atom hydrogen, a halogen atom or an alkyl group having 1 to 6 carbon atoms and which may have a halogen atom,
R°° and R each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or an 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.
[17]
17. The resist composition according to claim 15 or 16, wherein the resin including a structural unit having an acid labile group includes a structural unit represented by the formula (a2-A): R350
HL Im | (a2-A) Sn j OH ( RM) where, in the formula (a2-A), R°59 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, R®1 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms carbon, 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, A represents a single bond or *-X2*-(A252-X252) p", and * represents a bonding site to carbon atoms to which -R°° is bonded, A2 represents an alkanediyl group having 1 to 6 carbon atoms , x°°!1 and X252 each independently represent -O-, -CO-O- or -O-CO-
nb represents 0 or 1, and mb represents an integer of 0 to 4, and when mb is an integer of 2 or more, a plurality of R2! can be the same or different from each other.
[18]
18. The resist composition according to any one of claims 15 to 17, wherein the resin includes a structural unit (a3) represented by the formula (a3-4): got doubts} 5° B {a3-4} where , in the formula (a3-4), L represents -O-, *-OL°8-0-, *-OL°8-CO-O-, *-OL°8-CO-OL°°- 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 bonding site to a carbonyl group, R22* represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, R25 each independently represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, wl represents a an integer of 0 to 8, and when wl is 2 or more, a plurality of R°°* may be the same or different from each other.
[19]
19. The resist composition according to claim 18, in which the structural unit (a3) is represented by the following formulas:
Hs Ha Hz CH. Mo Cu Hz CH, Ha CHa 1 ot AH ci ‚Hs Cg 3 C * © , -; Hete HE HEE TE D >= a ó © ° © SI AA XJ (a3-4-45 : XG (23-46 {a3-4-13 (3:45 34 (a3-4-4) A (23.45) 23 -46} Lt!CHz ++ CH, Le zi Le Sl + 5 Le == ö À, OT © D © o S ba 1 he QYOQ be jr nd OD DH} 0 a X (83:47) (23-48 ) A°2 2 {a3-4-8} (224-191 (83-411) 5 (83-412)
[20]
20. The resist composition according to any one of claims 15 to 19, wherein the acid generator includes a salt represented by formula (B1):
QM Z* O3S | AN (B1) > Y Qb2 where, in the formula (B1), QP and Q” each independently represents 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 divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom included in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CHz- included in the hydrocarbon group alicyclic can be replaced by -O-, -SO>- or -CO-, and
Z' represents an organic cation.
[21]
21. The resist composition according to any one of claims 15 to 20, further comprising an acid generating salt having a lower acidity than an acid generated by the acid generator.
[22]
22. A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to any one of claims 15 to 21 to a substrate, (2) a step of drying the resist composition applied to form a composition layer, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and (5) a step of developing the heated composition layer .

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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JP2020086254|2020-05-15|

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