SALT, ACID GENERATOR, RESIST COMPOSITION AND METHOD FOR PRODUCING RESIST PATTERN

专利摘要:
An object of the present invention is to provide a salt and a resist composition comprising the salt capable of producing a resist pattern with satisfactory CD (CDU) uniformity. The invention relates to a salt represented by formula (I) as defined in claim 1, an acid generator and a resist composition which comprise the salt, wherein, in formula (I), R1 represents a fluorine or a fluorinated alkyl group; R2, R3 and R4 each represent a halogen atom, a fluorinated alkyl group or a hydrocarbon group; m2 and m3 represent an integer of 0 to 4; m4 represents an integer of 0 to 5; Q1 and Q2 each represent a fluorine atom or a perfluoroalkyl group; L1 represents a saturated hydrocarbon group, -CH2- included in the group may be replaced by -O- or -CO-, and a hydrogen atom included in the group may be substituted by a fluorine atom or a hydroxy group; Y1 represents a methyl group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent.
公开号:BE1028013B1
申请号:E20215083
申请日:2021-02-04
公开日:2022-01-26
发明作者:Yukako Anryu；Koji Ichikawa；Tatsuro Masuyama
申请人:Sumitomo Chemical Co；
IPC主号:

专利说明:

[0001] The present invention relates to a salt, an acid generator, a resist composition and a method for producing a resist pattern. State of the art
[0002] [0002] Patent document 1 mentions resist compositions each including, as acid generators, salts represented by the following formulae.
[0003] [0003] Patent document 1: JP 2017-003920 A Patent document 2: JP 2018-118962 A Description of the invention
[0004] The present invention proposes to provide a salt and a resist composition comprising the salt capable of producing a resist pattern with CD uniformity (CDU) which is better than that of a resist pattern formed from the compositions of resist comprising the salts mentioned above. Ways to solve problems
[0005] The present invention includes the following inventions.
[1] [1] A salt represented by the formula (I): (D) m2 &
[2] [2] The salt according to [1], wherein R2, R3 and R* each independently represents a fluorine atom, an iodine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
[3] [3] An acid generator comprising the salt according to [1] or [2].
[4] [4] A resist composition comprising the acid generator according to [3] and a resin having an acid labile group.
[5] [5] The resist composition according to [4], wherein the resin having an acid-labile group comprises at least one member selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by the formula (a1-2): FE} HS C Cc
[6] [6] The resist composition according to [4] or [5], wherein the resin having an acid labile group comprises a structural unit represented by the formula (a2-A): R250 tf} A250 | (a2-A)
[7] [7] The resist composition according to any one of [4] to [6], 5 further comprising an acid-generating salt having an acidity lower than that of an acid generated from the acid generator.
[8] [8] A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to any one of [4] to [7] onto a substrate, (2) a step drying the applied composition to form a layer of composition, (3) a step of exposing the layer of composition, (4) a step of heating the exposed layer of composition, and (5) a step of developing the heated composition layer.
[0006] It is possible to provide a resist pattern with satisfactory CD (CDU) uniformity by using a resist composition comprising a salt of the present invention.
[0007] [0007] In the present description, “(meth)acrylic monomer” means at least one selected from the group consisting of a monomer having a structure of “CH; =CH-CO-" and a monomer “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 similarly exemplified.In the groups mentioned herein, the groups capable of having a linear structure and a branched structure,
[0008] <Salt represented by Formula (I)> The salt of the present invention is a salt represented by formula (I) (hereinafter sometimes referred to as "salt (T)"). In salt (I), the side with a negative charge is sometimes called the "anion (T)", and the side with a positive charge is sometimes called the "cation (Do. (R2)m2@
[0009] In formula (I), the fluorinated alkyl group having 1 to 4 carbon atoms as for Rt, R2, R and R* represents an alkyl group having 1 to 4 carbon atoms which has a fluorine atom, and examples thereof include a perfluoroalkyl group having 1 to 4 carbon atoms (a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl, a nonafluorobutyl group) and a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group and a 3,3,4,4,4-pentafluorobutyl group and the like. The number of carbon atoms of the fluorinated alkyl group is preferably 1 to 3, and more preferably 1 or 2.
[0010] R* is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a fluorine atom or a trifluoromethyl group, and even more preferably a trifluoromethyl group.
[0011] [0011] In the formula (I), the iodine atom can be bonded to the ortho position, the meta position or the para position of the benzene ring with respect to S”. Of these, the iodine atom is preferably bonded to the meta position or the para position, and more preferably to the para position of the benzene ring with respect to S*. R* can be attached to the ortho position, the meta position or the para position of the benzene ring with respect to S*. Of these, R* is preferably bonded to the meta position or the para position, and more preferably to the para position, of the benzene ring relative to S*. R°, R} and R* can each be attached to the ortho position, the meta position or the para position of the benzene ring with respect to S*. Of these, R2 is preferably bonded to the meta position or the para position of the benzene ring to S*. When R! is bonded to the para position of the benzene ring relative to S*, R* is more preferably bonded to the meta position of the benzene ring relative to S*. R is preferably bonded to the ortho or meta position of the benzene ring relative to S*. When the iodine atom is bonded to the para position of the benzene ring relative to S*, R is more preferably bonded to the position ortho of the benzene ring to S*. R* is preferably bonded to the meta position or the para position, and more preferably at least to the para position of the benzene ring relative to S*.
[0012] [0012] Examples of the cation in the salt (I) include the cations represented by the following formula (I-c-1) to formula (I-c-20) and the like.
[0013] Among these, the cations represented by the formula (Ic-1) to the formula (Ic-6), the formula (Ic-13), the formula (Ic-14), the formula (Ic-17 ) and formula (Ic-18) are preferred, cations represented by formula (Ic-1) to formula (Ic-4), formula (Ic-13), formula (Ic-14), formula (Ic-17) and formula (Ic-18) are more preferred, cations represented by formula (Ic-1), formula (Ic-3), formula (Ic-13), formula (Ic- 14), Formula (Ic-17) and Formula (Ic-18) are more preferred, and the cations represented by Formula (Ic-1), Formula (Ic-13), Formula (Ic-14) , Formula (Ic-17) and Formula (Ic-18) are more preferred.
[0014] [0014] Examples of the perfluoroalkyl group having 1 to 6 carbon atoms such as Qt and Q include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluorohexyl group. Preferably, Q* and Q* are each independently a fluorine atom or a trifluoromethyl group, and more preferably, they are both fluorine atoms.
[0015] [0015] Examples of the divalent saturated hydrocarbon group in L' 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. Specific examples include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane group -1,6-diyl, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane group -1,11-diyl, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane group -1,16-diyl and a heptadecan-1,17-diyl group;
[0016] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by L! is replaced by -O- or -CO- includes, for example, a group represented by any one of formula (b1-1) 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.
[0017] [0017] X b3 OL O * mit, mba 1 > DS, be” 21077
[0018] [0018] 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.
[0019] [0019] LP is preferably a single bond.
[0020] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by L! is replaced by -O- or -CO- is preferably a group represented by formula (b1-1) or formula (b1-3).
[0021] [0021] Examples of the group represented by the formula (b1-1) include the groups represented by the formula (b1-4) to the formula (b1-8). 9 OX 1911 1 612 A LÉ, Ae” Ar So _ (b1-4) (b1-5)° (b1-6) 9 x À, 1216 9 -O AA ee ee (b1-7) 5 (b1-8 )
[0022] [0022] LPS is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
[0023] [0023] Examples of the group represented by the formula (b1-3) include the groups represented by the formula (b1-9) to the formula (b1-11). + Ox N AD
[0024] [0024] 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.
[0025] Examples of alkylcarbonyloxy group include acetyloxy group, propionyloxy group, butyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group and the like.
[0026] [0026] Examples of the group represented by the formula (b1-4) include the following: λ, O 0 O O CH3
[0027] Examples of the group represented by the formula (b1-5) include the following: O 0 0 0 A Aob. Athos. Aorta. AoA. X X "Gt, AA. A Lo where ON O Hs CH O
[0028] [0028] Examples of the group represented by the formula (b1-6) include the following: 0 À Ps * À, * Al * o TT pr Ay CH CH; CH; 0 0 Oo © A AÆotiser * Athos Abo + “Kotiso- * O CO + AA} Af}
[0029] [0029] Examples of the group represented by the formula (b1-7) include the following: xx xx ANA + xx. Se ese CR vu
[0030] [0030] Examples of the group represented by the formula (b1-8) include the following: "YO Q ee DEE OC mo” Ö oo T Oo Ö - O
[0031] [0031] Examples of the group represented by the formula (b1-2) include the following: A HAE Hos m + A À EAA, Hr A AA
[0032] [0032] Examples of the group represented by the formula (b1-9) include the following:
[0033] [0033] Examples of the group represented by the formula (b1-10) include the following: Hs Hs Hs LEA ah ek LO LA xk Hs kk Hs #x AO x H xx * * Ten H H
[0034] [0034] Examples of the group represented by the formula (b1-11) include the following:
[0035] The examples of alicyclic hydrocarbon group represented by Y! 5 include groups represented by formula (Y1) to formula (Y11) and formula (Y36) to formula (Y38).
[0036] [0036] 2000900 Ab D 02 03) VA) (Y5) (19) M (y8) (9) 10) MN) „I , + CN é Al *_e A + en 9 9 de SCA A £) ok 04 DO 129 (1) (14 (Y15) (Y16) (17) (Y18) (119) (20) 2 (Y22) * *__ *_ | TO j A + * O OD OP 40 #0 (Y23) (Y24 ) (v25) v26) (27 (v28) 029 01309) 039), (Y32) (vas) * O TO x O0 Nt A oO 9 O
[0037] The alicyclic hydrocarbon group represented by Y! is preferably a group represented by any one of formula (Y1)
[0038] [0038] Examples of the methyl group substituent represented by Y! include halogen atom, hydroxy group, alicyclic hydrocarbon group having 3 to 16 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms, glycidyloxy group, -(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, 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 may be replaced by -O-, -SO-- or -CO-, and a hydrogen atom included in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a hydroxy group or a fluorine atom, and j represents an integer from 0 to 4).
[0039] [0039] Examples of halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.
[0040] [0040] Examples of Y* include the following.
[0041] 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, and more preferably an adamantyl group which may have a substituent, and -CHz- included in the alicyclic hydrocarbon group or the adamantyl group may be replaced by -CO-, -S( O)2- or -CO -. Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or groups represented by formula (Y42) and formula (Y100) to formula (Y114).
[0042] [0042] The anion in the salt (I) is preferably anions represented by the formula (IA-1) to the formula (IA-59) [hereinafter sometimes called "anion (IA-1)" according to the number of formula], and more preferably an anion represented by any one of formula (IA-1) to formula (IA-4), formula (IA-9), formula (IA-10) , Formula (IA-24) to Formula (IA-33), Formula (IA-36) to Formula (IA-40), and Formula (IA-47) to Formula (IA-59).
[0043] [0043]
[0044] [0044]
[0045] [0045]
[0046] [0046] 1 O CH 035 ï O os YT < [A41 0 O O 0 (1-a-25) © Ò (I-A-26)
[0047] [0047] O0 0 RS | pig - œ Vo. A41 a’ to L LL ÿ + * TT L 705 O O _ Q Q 0 (I-A-31) 0875 UT (I-A-30) 8 (I-A-32) O0 0
[0048] [0048] AR} ai 0° a! 0° Î _ O _ BE AO os
[0049] [0049] O. O Ô oO O O O ò O 5 > AT > > O Q1 Q2 O Q1 Q2 Oo Cu „SM SEM (I-A-50) © (I-A-51) 9 (I-A-52) Q, Oo a! @ 9 Oo 0 - Oo. a: 02 kp So o | LA41 0 en al 02 O Ô ” 8 o,s (I-A-53) 0 (I-A-55) (I-A-54) °
[0050] [0050] O Oo OH Q1 Q2 X Q1 Q2 To _ Oo - O oO 5 Lou
[0051] [0051] R to RU each independently represent, for example, an alkyl group having 1 to 4 carbon atoms, and preferably a methyl group or an ethyl group. R® is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or groups formed in combining these groups, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. LA is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Qt and Q* are the same as defined above.
[0052] Preferred anions in salt (I) are anions represented by formula (I-a-1) to formula (I-a-38). HO 0 Fe AN FF From O -03S | XT "028 O 035 Ö (I-a-1) © (I-a-2) (I-a-3)
[0053] [0053]
[0054] [0054]
[0055] [0055]
[0056] Of these, an anion represented by any one of formula (Ia-1) to formula (Ia-3), formula (Ia-7) to formula (Ia-19) and formula (Ia-22) to formula (Ia-38) is preferred.
[0057] [0057] Specific examples of the salt (I) include the salts obtained by optionally combining the cations and anions mentioned above. Specific examples of salt (T) are shown in the following table. In the following table, the respective symbol represents symbols conferred on structures having the anions and cations mentioned above. For example, salt (I-1) is a salt composed of an anion represented by the formula (I-a-1) and a cation represented by the formula (I-c-1) and is the following salt. CF3 CG
[0058] Among these salts, salt (I) preferably includes salt (I-1) to salt (I-5), salt (1-13) to salt (1-25), salt (1- 30) to salt (I-34), salt (I-42) to salt (1-54), salt (1-59) to salt (I-63), salt (I-71) to salt ( 1-83), salt (1-88) to salt (I-92), salt (I-100) to salt (I-112), salt (I-117) to salt (I-121), salt (I- 129) to salt (I-141), salt (I-146) to salt (I-150), salt (I-158) to salt (I- 170), salt (I- 175) to salt (I-179), salt (I-187) to salt (I-199), salt (I- 204) to salt (I-208), salt (I-216) to salt ( I-228), salt (I-233) to salt (I 237), salt (I-245) to salt (I-257), salt (I-262) to salt (I-266), salt (I- 274) to salt (I-286), salt (I-291) to salt ( I-295), salt (I-303) to salt (I- 315), salt (I-320 ) to salt (1-324), salt (1-332) to salt (I-344), salt (I-349) to salt (I-353), salt (I-361) to salt (I -373), salt (1-378) to salt (I-382), salt (I-390) to salt (I-402), salt (I-407) to salt (I-411), salt (I-419) to salt (1-431), salt (I-436) to s el (I-440), salt (I-448) to salt (I-460), salt (I-465) to salt (1-480), salt (I-481) to salt (I-486 ), salt (I-494) to salt (I-506), salt (I-511) to salt (I-516), salt (I-524) to salt (I-536), salt ( I-541) to salt (I-546), salt (I-554) to salt (I-566), salt (I-571) to salt (I-576) and salt (1-584) to salt (I-596).
[0059] <Process for producing Salt (T)> Salt (T) can be produced by reacting a salt represented by the formula (Ia) with a salt represented by the formula (Ib) in a solvent in the presence of a basic catalyst: (RÈ) m2 (R2)m2
[0060] [0060] Examples of the salt represented by the formula (I-a) include the salts represented by the following formulas, which are readily available in the market and can also be easily produced by a known production method.
[0061] <Acid Generator> The acid generator of the present invention is an acid generator comprising the salt (I). Salt (I) may be used alone, or two or more of these salts may be used in combination. The acid generator of the present invention may comprise, in addition to the salt (I), an acid generator known in the resin field (hereinafter sometimes referred to as "acid generator (B)"). The acid generator (B) can be used alone, or two or more acid generators can be used in combination.
[0062] A nonionic or ionic acid generator can be used as acid generator (B). Examples of nonionic acid generator include sulfonate esters (e.g., ester 2-
[0063] [0063] Specific examples of the acid generator (B) include compounds generating acid upon exposure to radiation mentioned in JP 63-26653 A, JP 55-164824 A, JP 62-69263 A, JP 63-146038 A , JP 63-163452 A, JP 62-153853 A, JP 63-146029 A, US Patent No.
[0064] The acid generator (B) is preferably an acid generator containing fluorine, and more preferably a salt represented by the formula (B1) (hereinafter sometimes called "acid generator (B1) "): Qh + -0.S [61 21 OS AS, (B) des where, in the formula (B1), QPt and Q° each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms , LP! represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CHz- included in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom included in the hydrocarbon group 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 alicyclic hydrocarbon group may be replaced by -O-, -S(O)2- or -CO-, and Z1* represents a cat organic ion.
[0065] [0065] Examples of the perfluoroalkyl group represented by Q1 and QP2 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group. and a perfluorohexyl group.
[0066] [0066] Examples of divalent saturated hydrocarbon group in LP include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, or the divalent saturated hydrocarbon group may be a group formed by combining two or more of these groups in combination.
[0067] The group in which -CH>- included in the divalent saturated hydrocarbon group represented by LP! is replaced by -O- or -CO- includes, for example, a group represented by any one of formula (b1-1) to formula (b1-3). In the groups represented by formula (b1-1) to formula (b1-3) and the groups represented by formula (b1-4) to formula (b1-11) which are specific examples thereof, * and ** represent a bond, and * represents a bond to -Y.
[0068] [0068]
[0069] In the groups represented by formula (b1-1) to formula (b1-3), when -CHz- included in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of atoms of carbon before replacement is taken as the number of carbon atoms of the saturated hydrocarbon group.
[0070] [0070] LP is preferably a single bond.
[0071] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by L' is replaced by -O- or -CO- is preferably a group represented by formula (b1-1) or formula (b1 - 3). Examples of the group represented by the formula (b1-1) include the groups represented by the formula (b1-4) to the formula (b1-8): O O X b11 1.912 A, Ae * ARR x (b1-4) (b1-5)° (b1-6)
[0072] [0072] Examples of the group represented by the formula (b1-3) include the groups represented by the formula (b1-9) to the formula (b1-11).
[0073] [0073] In groups represented by formula (b1-9) to formula (b1-11), when a hydrogen atom included in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before the substitution is taken as the number of carbon atoms of the saturated hydrocarbon group.
[0074] [0074] Examples of the group represented by the formula (b1-4) include the following:
[0075] [0075] Examples of the group represented by the formula (b1-5) include the following:
[0076] [0076] Examples of the group represented by the formula (b1-6) include the following: Oo 9 . Q ‚ Oo Ny op 4 oi SE x Ke “Aotho* 3 3 3
[0077] [0077] Examples of the group represented by the formula (b1-7) include the following: H 0 Ark Ash sis AN CHs O0 A
[0078] [0078] Examples of the group represented by the formula (b1-8) include the following: x SO D Ô ak x 7 O
[0079] [0079] Examples of the group represented by the formula (b1-2) include the following: pr Ho Ar a ve R CH3 CH 3 CH 4 Ha u A, Ao sk
[0080] [0080] Examples of the group represented by the formula (b1-9) include the following:
[0081] [0081] Examples of the group represented by the formula (b1-10) include the following:
[0082] [0082] Examples of the group represented by the formula (b1-11) include the following: CH3 0 O Q 9 OAN otho AA AA oto oto
[0083] [0083] Examples of the alicyclic hydrocarbon group represented by Y include groups represented by formula (Y1) to formula (Y11) and by formula (Y36) to formula (Y38).
[0084] [0084]
[0085] [0085] Examples of halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.
[0086] [0086] Examples of Y include the following.
[0087] [0087] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, more preferably a alicyclic hydrocarbon having 3 to 18 carbon atoms which may have a substituent, more preferably an adamantyl group which may have a substituent, and -CH>- constituting the alicyclic hydrocarbon group or the adamantyl group may be replaced by -CO-, -S(O)2- or -CO-. Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or groups represented by formula (Y42) and formula (Y100) to formula (Y114).
[0088] [0088]
[0089] [0089] OH Oo a'! oz eG b1 b2 Q Q ‚ar OC has! ‚a _ O - On - O 035 SLA O+S LA Sr <, A41 3 Sr 3 "N 038 ï L q (B1-A-1) (B1-A-2) (B1-A-3) el Qr2 el Qr2 ri Qh!Q°2 _ BC = BC oe RO
[0090] [0090] OH
[0091] [0091]
[0092] [0092]
[0093] [0093] ar Qb O CH er ab 9 CH3 - On A41 7o Aen o:S L Oo 3 O O > 9 O œ1-a-05) © (B1-A-26) ©
[0094] [0094]
[0095] [0095] Ri3 Qb! Q°2 SL, _ O 0.870 038
[0096] [0096]
[0097] The anion in the salt represented by the formula (B1) preferably includes anions represented by the formula (B1a-1) to the formula (B1a-38).
[0098] [0098]
[0099] [0099] ok kf H
[0100] Of these, an anion represented by any one of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula (B1a-19) and formula (B1a-22) to formula (B1a-38) is preferred.
[0101] [0101] Examples of organic cation of Z1* include organic onium cation, organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation and organic phosphonium cation. Of these, an organic sulfonium cation and an organic iodonium cation are preferred, and an arylsulfonium cation is more preferred. Specific examples thereof include a cation represented by any one of formula (b2-1) to formula (b2-4) (hereinafter sometimes referred to as "cation (b2-1)" depending on the number of the formula).
[0102] [0102] (RE1S) 0 (REP) 2 Rb4 (RP ) m2 Rb9 o © © Rs WJ | io 1, ng to (RP) Ö P (b2-1) (b2-2) (b2-3) The B) (9 / p2 14u2+1) (b2-4) In formula (b2-1) to formula (b2-4) , RP* to RP each independently represent a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms or an aromatic hydrocarbon group having 6 to 36 carbon atoms, a hydrogen atom included in the chain hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, a hydrogen atom included in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group, and a hydrogen atom included in the aromatic hydrocarbon group may be substituted with an atom e of halogen, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkyl fluoride group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms,
[0103] 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. (b2-c-1) (b2-c-2) (b2-c-3) (b2-c-4) (b2-c-5) (b2-c6) | (b2-c-7) (b2-c-8) 6 © pl -C4Hg -C‚Hg + + + CH, ® © 44 «05 02 OO, aon GL DAA H c- -C,H, | (b2-c-14) (b2-C-9) (b2-6-10) 621) 68072) (62-013)
[0104] [0104] OH OCHs | X CG © ABB 829% {Sb Hol_S— p VS + FH + ' + + © A © À ® © ö a O0 G (b2-c-15) (b2c19) 217) 0201) (92019) (b2-c- 21) (b2-c-22) € ® © (b2-c-20) +) € + + + © S Ss © © © Dl DS Os U) (2) (7 (62-023) (b2-024 ) (b2-028) (b2-c-26) (02027) (92047) (b2-c-48) (b2-c-49) F3 R (y (5 (4 HS + { > + | G > + (2 @ (4 F3 F FF (b2-c-51) (b2-c-52) (b2-c-53)
[0105] [0105] Examples of cation (b2-2) include the following cations. O0 XK} CAM DOF (b2-c-28) (b2-c-29) (b2-c-30) (b2-c-50)
[0106] [0106] Examples of cation (b2-3) include the following cations. O 45 20 oP 607 0” (b2-c-31) (b2-c-32) (b2-c-33) (b2-c-34)
[0107] [0107] Examples of cation (b2-4) include the following cations. 3 0-0 40-00 Oe ASX 00 (b2-c-35) (b2-c-36) (b2037) U (b2-c-38) HaC HC Hs > Zoe Zoo 30-0 We u (b2-c -40) Ha (b2-c-41) “© t-C4Ho tC4Hs joo 200 Zoon (2 (9 (2 (b2-c-44) Ha (b2-c-42) (b2-c-43) t- CaHo t-CaHo 30-0 Zoe 000 (y (y U) t-Cao (b2-c-45) Cal (b2-c-46) (b2-c-54)
[0108] [0108] The acid generator (B) is a combination of the aforementioned anion and the aforementioned organic cation, and these may be optionally combined. The acid generator (B) preferably includes a combination of an anion represented by any one of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (Bla-16), formula (B1a-18), formula (B1a-19) and from formula (B1a-22) to formula (B1a-38) with a cation (b2-1), a cation (b2-3), a cation (b2-4).
[0109] [0109] 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.
[0110] [0110] CH, Q 5 „OL SM X VE TT JC
[0111] [0111] AK I A 2 VL TR OTR > À (B1-13) (B1-14) (B1-15) PPS Ô (B1-17) v, (B1-18) (B1-16)
[0112] [0112]
[0113] [0113] Oo © Ç À @ À (5 „os À O + AN CF3 S Fe 0750 ò 5 FOT Le os XL os PPT (B1-28) (8129) OS È (B1-30) F Oo Va Oe Loco FF FF i
[0114] [0114]
[0115] [0115] see! A Oo, Ö (© À, Oo Q ch A 14 À ON ve _ Q N X pr ç (B1-41) (B1-42) O X x Q © CO OO, 9
[0116] [0116]
[0117] [0117] When salt (I) and acid generator (B) are included as the acid generator, a ratio of the content of salt (I) and that of acid generator (B) (mass ratio; salt (I): generating acid (B)) is usually 1:99 to 99:1, preferably 2:98 to 98:2, more preferably 5:95 to 95:5, more preferably 10 :90 to 90:10, and more preferably from 15:85 to 85:15. In the resist composition of the present invention, the total content of the acid generator is preferably 1 mass part or more and 45 mass parts or less, more preferably 1 mass part or more and 40 mass parts or less, and more preferably 3 parts by mass or more and 35 parts by mass or less, based on 100 parts by mass of the resin (A) mentioned below.
[0118] <Resist composition> The resist composition of the present invention includes an acid generator including a salt (I) and a resin having an acid-labile group (hereinafter sometimes referred to as "resin (A)". "Acid-labile group" means a group having a leaving group which is removed by contact with an acid, thereby converting a constituent unit into a constituent unit having a hydrophilic group (e.g. a hydroxy group or a carboxy group The resist composition of the present invention preferably includes a deactivating agent such as an acid-generating salt having a lower acidity than an acid generated from the acid generator (hereinafter sometimes referred to as "deactivating agent"). quencher (C)”), and preferably includes a solvent (hereinafter sometimes referred to as “solvent (E)”).
[0119] [0119] — <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) further includes 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 referred to as sometimes “structural unit
[0120] <Structural unit (a1)> The structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter sometimes referred to as “monomer (a1)”). The acid-labile group contained in the resin (A) is preferably a group represented by formula (1) (hereinafter also referred to as group (1)) and/or a group represented by formula (2) (in the sequence also called group (2)): 1 Rat fo (Po) Fe 4) ma na Ras where, in the formula (1), R°*, R° and R23 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 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms , or a group obtained by combining these groups, and R°* and R°° are bonded to each other to form a nonaromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atoms to which R° * and R°° are linked, ma and na each independently represent 0 or 1, and at least one of ma and na represents 1, and * represents a binding site: O Rat . fee (2) na' Ra
[0121] [0121] 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, octenyl group, isooctenyl 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 bonding position). The number of carbon atoms of the alicyclic hydrocarbon group of R°*, R°° and R@ is preferably from 3 to 16.
[0122] [0122] Examples of the hydrocarbon group in RŸ, R° and R include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and groups formed by combining these groups.
[0123] [0123] Examples of group (1) include the following groups.
[0124] [0124] oro OQ ro or bb 30 + * * 2 © * * DTE ToT DH LD 25e AQ “0 ne At AA SS ( * * * x + . cr 0x * + bb reg HS EE OO Ô O © G 44044055 + — A Zn * DZ ( * O © ; AO AM 0 6 1 Ö 9 CA
[0125] [0125]
[0126] 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.
[0127] 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.
[0128] [0128] 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.
[0129] [0129] R20! R°* and R°° are hydrogen or methyl, and more preferably methyl.
[0130] [0130] The structural unit (a1-0) includes, for example, a structural unit represented by any one of the formula (a1-0-1) to the formula (a1-0-18) and a structural unit wherein a methyl group corresponding to R*° in the structural unit (a1-0) is substituted by a hydrogen atom and is preferably a structural unit represented by any one of the formula (a1-0-1 ) to the formula (a1-0-10), the formula (a1-0-13) and the formula (a1-0-14).
[0131] [0131] The structural unit (a1-1) includes, for example, structural units derived from the monomers mentioned in JP 2010-204646 A. Among these structural units, a structural unit represented by any one of the formula (a1-1-1) to the formula (a1-1-7) and a structural unit in which a methyl group corresponding to R** in the structural unit (a1-1) is substituted by a hydrogen atom are preferred, and a structural unit represented by any one of formula (a1-1-1) to formula (a1-1-4) is more preferred. The Hs The Hs The Hs EE Hs Hey Hs Ob eg: (a1-1-1) (a1-1-2) (a1-1-3) (a1-1-5) (a1-1-6) (a1 -1-7) (a1-1-4)
[0132] [0132] Examples of structural unit (a1-2) include a structural unit represented by any one of formula (a1-2-1) to formula (a1-2-12) and a structural unit in which a methyl group corresponding to R® in the structural unit (a1-2) is substituted by a hydrogen atom and a structural unit represented by any one of formula (a1-2-2), formula (a1-2 -5), formula (a1-2-6) and formula (a1-2-10) to formula (a1-2-12) is preferable.
[0133] [0133]
[0134] [0134] 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)>):
[0135] [0135] Examples of the halogen atom in R°°° and R°* include a fluorine atom, a chlorine atom and a bromine atom.
[0136] [0136] 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-A% 32-0-CO-. Of these, *-CO-0-, *-CO-0-A332-CO-0- or *-O-A3*2_-CO-O- are preferable.
[0137] [0137] Examples of the alkanediyl group in A include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2- diyl, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group. A is preferably a methylene group or an ethylene group.
[0138] [0138] A is preferably a single bond, *-CO-O- or *-CO-O- A232-CO-O-, more preferably a single bond, *-CO-O- or *-CO-O -CHz-CO-O-, and more preferably a single bond or *-CO-O-.
[0139] la is preferably 0, 1 or 2, more preferably 0 or 1, and more preferably 0.
[0140] [0140] 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.
[0141] [0141] The structural unit (a1-4) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646 A. The structural unit preferably includes the structural units represented by the formula (a1-4- 1) to the formula (a1-4-18) and a structural unit in which a hydrogen atom corresponding to R222 in the constitutional unit (a1-4) is substituted with a methyl group, and more preferably structural units represented by the formula (a1-4-1) to the formula (a1-4-5), the formula (a1-4-10), the formula (a1-4-13) and the formula (a1-4-14 ).
[0142] [0142] When the resin (A) includes the structural unit (a1-4), the content is preferably 3 to 80 mol%, more preferably 5 to 75 mol%, more preferably 7 to 70 mol%, of more preferably 7 to 65 mol%, and more preferably 10 to 60 mol% based on the total of all structural units of the resin (A).
[0143] [0143] 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) "). | Ho ia |
[0144] [0144] The halogen atom includes a fluorine atom and a chlorine atom and is preferably a fluorine atom is preferred.
[0145] [0145] 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.
[0146] [0146] When the resin (A) includes the structural unit (a1-5), the content is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, more preferably 5 to 40 mol%, and more preferably 5 to 30 mol%, based on all structural units of resin (A).
[0147] The structural unit (a1) also includes the following structural units. ve val FO SO FO 49 de x O0 bd D DOS (a1-3-1) (a1-3-2) (a1-3-3) (a1-3-4) (a1-3-5) (a1- 3-6) (a1-3-7)
[0148] [0148] When the resin (A) includes the structural units mentioned above such as (a1-3-1) to (a1-3-7), the content is preferably 10 to 95 mol%, more preferably 15 to 90 mol% mol%, more preferably 20 to 85 mol%, more preferably 20 to 70 mol%, and more preferably 20 to 60 mol%, based on all structural units of the resin (A ).
[0149] The structural unit (a1) also includes the following structural units. H Ha CH Light 18} HE O O O
[0150] [0150] <Structural Unit(s)> The structural unit(s) derives from a monomer having no acid-labile group (hereinafter referred to as "monomer(s)"). It is possible to use as the monomer from which the structural unit(s) derives, a monomer having no acid-labile group known in the resist field. The structural unit(s) preferably has a hydroxy group or a lactone ring. When a resin comprising a structural unit having a hydroxy group and not having an acid-labile group (hereinafter sometimes referred to as "structural unit (a2)") and/or a structural unit having a lactone ring and does not having no acid-labile group (hereinafter sometimes referred to as "structural unit (a3)") is used in the resist composition of the present invention, it is possible to improve the resolution of a resist pattern and the adhesion to a substrate.
[0151] <Structural Unit (a2)> The hydroxy group belonging to the structural unit (a2) may be either an alcoholic hydroxy group or a phenolic hydroxy group. When a resist pattern is produced from the resist composition of the present invention, in the case of using, as an exposure source, high energy rays such as a KrF (248 nm) excimer laser , electron beam or extreme ultraviolet (EUV) light, the structural unit (a2) having a phenolic hydroxy group is preferably used, and it is more preferable to use the mentioned structural unit (a2-A) below as structural unit (a2). When using an ArF (193 nm) excimer laser or the like, a structural unit (a2) having an alcoholic hydroxy group is preferably used, and the structural unit (a2-1) mentioned later is preferably still used as structural unit (a2). The structural unit (a2) can be included alone, or two or more structural units can be included.
[0152] [0152] 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 )»): R250
[0153] [0153] Examples of the halogen atom in R3 and R°* include a fluorine atom, a chlorine atom and a bromine atom.
[0154] [0154] Examples of *-X2*!-(a252-X°52)p- include *-O-, *-CO-O-, *-0-CO-, *-CO-O-A3 - CO-O-, *-O-CO-A3 -O-, *-OA°* -CO-O-, *-CO-0-A°**-0- CO- and *-O-CO -A®%*-0-CO-. Of these, *-CO-O-, *-CO-O-A®%*-CO-0- or *-O-A®*-CO-O- is preferred.
[0155] [0155]
[0156] A2°0 is preferably a single bond, *-CO-O- or *-CO-O-A3*-CO-0-, more preferably a single bond, *-CO-O- or *- CO-O-CH>-CO-O-, and more preferably a single bond or *-CO-O-.
[0157] [0157] mb is preferably 0, 1 or 2, more preferably 0 or 1, and more preferably 0.
[0158] Examples of structural unit (a2-A) include structural units derived from monomers mentioned in JP 2010-204634 A and JP 2012-12577 A.
[0159] [0159] Examples of structural unit (a2-A) include structural units represented by formula (a2-2-1) to formula (a2-2-16), and a structural unit in which a corresponding methyl group to R20 in the structural unit (a2-A) is substituted with a hydrogen atom 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), and structural units represented by the formula (a2-2-12) to the formula (a2-2-14), and a unit structure in which a methyl group corresponding to R°° in the structural unit (a2-A) is substituted by a hydrogen atom in these structural units.
[0160] [0160] When the structural unit (a2-A) is included in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 10 to 70 mol. %, more preferably 15 to 65 mol%, and more preferably 20 to 65 mol%, based on all structural units.
[0161] [0161] 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)" ).
[0162] In the formula (a2-1), L°* is preferably -O- or -O-(CH2); -CO- O- (fl represents an integer from 1 to 4), and more preferably - O-, R31* is preferably a methyl group, R2!5 is preferably a hydrogen atom, RS is preferably a hydrogen atom or a hydroxy group, and ol is preferably an integer from 0 to 3, and more preferably 0 oul.
[0163] [0163] 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. Ha CH Hs H Hz CH, Hs H H;Hs HF Ze EE ES + Don Don Do Dos = >
[0164] [0164] When the resin (A) includes the structural unit (a2-1), the content is usually 1 to 45 mol%, preferably 1 to 40 mol%, more preferably 1 to 35 mol%, more preferably from 1 to 20 mol%
[0165] [0165] <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.
[0166] 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: pars Ra19 fe 7 tot} odt test te} 5 es 2 G 2 Ra25) A 2 (Ra ® (RS JT wr
[0167] [0167] Examples of the aliphatic hydrocarbon group in R°*, R222, R223 and R°°° include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec -butyl and a tert-butyl group.
[0168] [0168] Examples of alkanediyl group in L® and L® include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4 group -diyl, pentane-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane group - 1,2-diyl, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
[0169] 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.
[0170] [0170] In the formula (a3-4), R** is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or a group ethyl, and more preferably a hydrogen atom or a methyl group, R225 is preferably a carboxy group, a cyano group or a methyl group, L” is preferably -O- or *-OL°8-CO-O -, and more preferably -O-, -0-CH2-CO-0- or -0-C:H4-CO-0-, and wl is preferably an integer from 0 to 2, and more preferably 0 or .
[0171] [0171] Examples of structural unit (a3) include structural units derived from monomers mentioned in JP 2010-204646 A, monomers mentioned in JP 2000-122294 A and monomers mentioned in JP 2012-41274 A. The unit 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 units in which the methyl groups corresponding to R213, RS, R#20 and R2 * in the formula (a3-1) to the formula (a3-4) are substituted with hydrogen atoms in the above structural units .
[0172] [0172] Hz = | = = S = = + rot 0 Li 5 Frs 0 Ie 0 Ao 0 Lens 0 Ts 0 Jon 0
[0173] [0173] When the resin (A) includes the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, and more preferably 10 to 60 mol%, based on all the structural units of the resin (A).
[0174] [0174] <Structural unit (a4)> Examples of structural unit (a4) include the following structural units: ve O (a4)
[0175] [0175] 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.
[0176] [0176] Examples of the structural unit (a4) include a structural unit represented by the formula (a4-0), a structural unit represented by the formula (a4-1), and a structural unit represented by the formula (a4-4 ): R54 bont (4-0) d O 4 / | Sa Les where, in the formula (a4-0), R°* represents a hydrogen atom or a methyl group, L“ represents a single bond or an alkanediyl group having 1 to 4 carbon atoms,
[0177] [0177] 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.
[0178] [0178] Examples of perfluoroalkanediyl group in L“ include difluoromethylene group, perfluoroethylene group, perfluoroethylfluoromethylene group, perfluoropropane-1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane-2 group, 2-diyl, 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 group, 2-diyl, a perfluoropentane-3,3-diyl group, a perfluorohexane-1,6-diyl group, a perfluoro-hexane-2,2-diyl group, a perfluorohexane-3,3-diyl group, a perfluoroheptane- 1,7-diyl, a perfluoroheptane-2,2-diyl group, a perfluoroheptane-3,4-diyl group, a perfluoroheptane-4,4-diyl group, a perfluorooctane-1,8-diyl group, a perfluorooctane- 2,2-diyl, perfluorooctane-3,3-diyl group, perfluorooctane-4,4-diyl group and the like.
[0179] [0179] L® is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
[0180] [0180] Examples of the structural unit (a4-0) include the following structural units, and structural units in which a methyl group corresponding to R°* in the structural unit (a4-0) is substituted with a hydrogen in the following structural units:
[0181] [0181] RA41 H2 VS
[0182] [0182] 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.
[0183] [0183] 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.
[0184] [0184] 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: + —X243—pa45 (ag 3) where in the formula (a-g3), X represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-, A: represents a saturated hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, and * represents a binding site at R2*2.
[0185] [0185] Examples of the saturated hydrocarbon group in A include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group; monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* represents a bonding site).
[0186] [0186] R°*2 is preferably a saturated hydrocarbon group optionally having a halogen atom, and more preferably an alkyl group having a halogen atom and/or a saturated hydrocarbon group having a group represented by the formula ( a-g3).
[0187] When R°* is a saturated hydrocarbon group having the group represented by formula (a-g3), R°° is more preferably a group represented by formula (a-g2): + —A216_x244__pa47 (a- g2) where, in the formula (a-g2), A°*° represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, X21* represents **-O-CO- or * *-CO-O- (** represents a binding site 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°* has at least one halogen atom, and * represents a bonding site to a carbonyl group.
[0188] [0188] The number of carbon atoms of the saturated hydrocarbon group of A3' is preferably 1 to 6, and more preferably 1 to 3.
[0189] [0189] The preferred structure of the group represented by the formula (a-g2) is the following structure (* represents a bonding site to a carbonyl group).
[0190] [0190] 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 represented by 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.
[0191] [0191] Examples of the divalent saturated hydrocarbon group represented by A A23 and A * in the group represented by formula (a-g1) include a linear or branched alkanediyl group and a monocyclic divalent alicyclic saturated hydrocarbon group, and divalent saturated hydrocarbon groups formed by combining an alkanediyl group and a saturated hydrocarbon group divalent alicyclic. 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.
[0192] [0192] In the group represented by the formula (a-g1), examples of the group in which X** is -O-, -CO-, -CO-O- or -O-CO- include the following groups. In the following examples, * and ** each represent a binding site, and ** represents a binding site at -O-CO-R°*,
[0193] [0193] 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. Hs Hz CHs Hz Hz Hs er: er Pl ere er: er:
[0194] [0194] Hs Hz Hs Hs Hs Hs PR Pt and Te TEE
[0195] [0195] Examples of the structural unit represented by the formula (a4-1) include a structural unit represented by the formula (a4-2) and a structural unit represented by the formula (a4-3): Hz RS 7 o (a4-2) [44
[0196] [0196] Examples of the alkanediyl group having 1 to 6 L*% carbon atoms include the same groups as those mentioned for
[0197] [0197] The structural unit represented by the formula (a4-2) includes, for example, the structural units represented by the formula (a4-1-1) to the formula (a4-1-11). A structural unit in which a methyl group corresponding to RË in the structural unit (a4-2) is substituted with a hydrogen atom is also exemplified as a structural unit represented by (a4-3):
[0198] [0198] Hz RI7
[0199] [0199] Examples of the alkanediyl group in L° include those which are the same as those mentioned in the alkanediyl group of A**,
[0200] The divalent saturated hydrocarbon group optionally having a fluorine atom in A is preferably a divalent chain saturated hydrocarbon group optionally having a fluorine atom and a divalent alicyclic hydrocarbon group optionally having a fluorine atom, and more preferably a perfluoroalkanediyl group.
[0201] [0201]
[0202] [0202] 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 chain saturated hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a divalent chain saturated hydrocarbon group having 2 to 3 carbon atoms. The saturated hydrocarbon group of A* is preferably a group including a chain saturated hydrocarbon group having 3 to 12 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a group including a hydrocarbon group saturated hydrocarbon group having 3 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms. Of these groups, Af!* is preferably a group including an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.
[0203] [0203] 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).
[0204] It is also possible to cite by way of example, as structural unit (a4), a structural unit represented by the formula (a4-4):
[0205] [0205] Examples of the saturated hydrocarbon group of R* include those which are the same as the saturated hydrocarbon group represented by R°*2, RP2 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and more preferably an alkyl group having 1 to 6 atoms carbon having a fluorine atom.
[0206] [0206]
[0207] [0207] 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.
[0208] [0208] When the resin (A) includes the structural unit (a4), the content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and more preferably 3 to 10 mol%, on the basis of all the structural units of the resin (A).
[0209] <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):
[0210] [0210] 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.
[0211] [0211] 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.
[0212] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by L°° is replaced by -O- or -CO- includes, for example, groups represented by formula (L1-1) at formula (L1-4). In the following formulas, * and ** each represent a binding site, and * represents a binding site to an oxygen atom.
[0213] [0213] 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.
[0214] The group represented by the formula (L1-1) includes, for example, the following divalent groups. ON, A A, A, A, A,
[0215] The group represented by formula (L1-2) includes, for example, the following divalent groups.
[0216] The group represented by the formula (L1-3) includes, for example, the following divalent groups.
[0217] The group represented by the formula (L1-4) includes, for example, the following divalent groups.
[0218] L°° is preferably a single bond or a group represented by the formula (L1-1).
[0219] [0219] 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.
[0220] [0220]
[0221] <Structural unit (II)> The resin (A) may further include a structural unit which is decomposed by exposure to radiation to generate an acid (hereinafter sometimes referred to as "structural unit (IT)"). Specific examples of the structural unit (IT) include the structural units mentioned in JP 2016-79235 A, and a structural unit having a sulfonate group or a carboxylate group and an organic cation in a side chain or a structural unit having a group sulfonio and an organic anion in a side chain are preferred.
[0222] 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"):
[0223] [0223] Examples of the halogen atom represented by RS include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0224] [0224] Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X!B include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, or a combination thereof.
[0225] [0225] Those in which -CHz- included in the saturated hydrocarbon group are replaced by -O-, -S- or -CO- include, for example, divalent groups represented by formula (X1) to formula (X53) .
[0227] [0227] Examples of the organic cation represented by ZA' include organic onium cation, organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation and organic phosphonium cation. Among these organic cations, an organic sulfonium cation and an organic iodonium cation are preferred, and an arylsulfonium cation is more preferred. Specific examples thereof include a cation represented by any one of the formula (b2-1) to the above-mentioned formula (b2-4) (hereinafter sometimes referred to as "cation (b2-1)" according to formula number).
[0228] The structural unit represented by the formula (II-2-A") is preferably a structural unit represented by the formula (II-2-A):
[0229] [0229] Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by R', RIM Q and Q include those which are the same as the perfluoroalkyl group having 1 to 6 carbon atoms represented by Q” mentioned later.
[0230] The structural unit represented by the formula (II-2-A) is preferably a structural unit represented by the formula (II-2-A-1): RI!!!3
[0231] [0231] Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by RIP include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec -butyl, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. Examples of divalent saturated hydrocarbon group represented by X include those which are the same as the divalent saturated hydrocarbon group represented by XE,
[0232] The structural unit represented by the formula (II-2-A-1) is preferably a structural unit represented by the formula (II-2-A-2):
[0233] [0233] The structural unit represented by the formula (II-2-A") includes, for example, the following structural units, the structural units in which a group corresponding to the methyl group of RIP is substituted by an alkyl group having 1 to 6 carbon atoms optionally having a hydrogen atom, a halogen atom (for example, a fluorine atom) or a halogen atom (for example, a trifluoromethyl group, etc.) and the structural units mentioned in WO 2012/050015 A. ZA” represents an organic cation.
[0234] [0234] 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): R!14 ef RIS (II-1- 1) O OTA RS 4
[0235] [0235] Examples of the structural unit including a cation in the formula (II-1-1) include the following structural units, the structural units in which a group corresponding to the methyl group of R"* is substituted by an atom of hydrogen, a halogen atom (for example, a fluorine atom) or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom (for example, a trifluoromethyl group etc.).
[0236] [0236] 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 examples of the sulfonic acid anion include those which are the same as an anion represented by the aforementioned formula (B1).
[0237] [0237] Examples of the sulfonylimide anion represented by A include the following. F2 fFs F2£-C —CFs E 9257 CF3 0257 CF2 0257 CF2 O,S—ÇCF, o,s LL LOT} oder, O2S-CFs 025-GF2 04 de, zn. F, LF; F,C-C-CF3 F2
[0238] [0238] Examples of the sulfonyl methide anion include the following.
[0239] [0239] Examples of the carboxylic acid anion include the following. nt mo A, Horn a ALL mot, DD ‘ eu OH CHs Ö wok, EFF RER À, A, 4 i "CO OH F'EPFFR FF
[0240] [0240] Examples of the structural unit represented by formula (II-1-1) include structural units represented by the following formulas. Hz Hs Hz Hz Hz Hz { Л 4 { £ EF & KF SF He toer OT X STE OC OC eue Hz E © Je tot = O TE F H
[0241] [0241] When the structural unit (IT) is included in the resin (A), the content of the structural unit (IT) is preferably 1 to 20 mol%, more preferably 2 to 15 mol®%, and more preferably 3 to 10 mol%, based on all structural units of resin (A).
[0242] 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.
[0243] The resin (A) is preferably a resin composed of a structural unit (a1) and a structural unit (s), that is to say a copolymer of a monomer (al) and d a monomer(s).
[0244] 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.
[0245] <Resin other than resin (A)> The resist composition of the present invention may include the resin other than resin (A).
[0246] The resin (X) is preferably a resin including a structural unit (a4), in particular.
[0247] [0247] The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less. , based on the solid component of the resist composition. When including resins other than resin (A), the total content of resin (A) and resins other than resin (A) is preferably 80% by mass or more and 99% by mass or less, and more preferably 90 mass% or more and 99 mass% or less, based on the solid component of the resist composition. The solid component of the resist composition and the content of the resin can be measured by a known analytical means such as liquid chromatography or gas chromatography.
[0248] [0248] <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. Examples of solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; and cyclic esters such as γ-butyrolactone. Solvent (E) can be used alone, or two or more solvents can be used.
[0249] [0249] <Deactivating agent (C) ("quencher")> Examples of 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 0.01 to 7% by weight, and more preferably about 0.1 to 3% by weight, based on the amount of the solid component of the resist composition. Examples of the basic nitrogen-containing organic compound include an amine and an ammonium salt. Examples of amine include aliphatic amine and aromatic amine. Examples of aliphatic amine include primary amine, secondary amine and tertiary amine. Examples of amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline , diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine , ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine,
[0250] 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. acid (B) include salts represented by the following formulas, a salt represented by the formula (D) mentioned in JP 2015-147926 A (hereinafter sometimes referred to as "weak acid inner salt (D)"), and salts mentioned in JP 2012-229206 A, JP 2012-6908 A, JP 2012-72109 A, JP 2011-39502 A and JP 2011-191745 A. The salt is preferably a salt generating a carboxylic acid having an acidity lower than that an acid generated from the acid generator (B) (a salt having a carboxylic acid anion) and more preferably an inner fa acid salt able (D). 3 <q
[0251] [0251] Examples of the weak acid inner salt (D) include the following salts. 007 “00 _ + 007 oo” AO DO cock I) + er HO 007 oo” oo oo 007 007 050 F5 650-0150 e Br CI 007 oo oo 00" oo no, 0-0 de do Ho SG AE oo 00” oo” oo PO Ho SOL OA HO
[0252] [0252] <Other components> The resist composition of the present invention may also include components other than the components mentioned above (hereinafter sometimes referred to as "other components (F)"). The other components (F) do not are not particularly limited and it is possible to use various additives known in the art of resists, for example sensitizers, dissolution inhibitors, surfactants, stabilizers and colorants.
[0253] <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), resins other than resin (A), a solvent (E), a deactivating agent (C) and other components (F). The mixing order of these components is any order and it is not particularly limited. It is possible to select, as the temperature during mixing, an appropriate temperature of 10 to 40°C, depending on the kind of the resin, the solvent solubility (E) of the resin and the like. It is possible to choose, as mixing time, an appropriate time of 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited and it is possible to use mixing with agitation. 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.
[0254] [0254] <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. The resist composition can typically be applied to a substrate by means of conventionally used apparatus, such as a spinner. Examples of substrate include inorganic substrates such as a silicon wafer. Prior to application of the resist composition, the substrate may be washed, and an organic antireflection film may be formed on the substrate.
[0255] [0255] (Application) The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) or resist composition for UVE exposure, in particular an electron beam (EB) resist composition or resist composition for UVE exposure, and the composition of resist is useful for fine processing of semiconductors.
[0256] [0256]
[0257] [0257] Example 1: Synthesis of the salt represented by the formula (1-3) > 9 VE CF3803 | ei od — VE eK CF3 CF3 (I-3-a) (I-3-b) (1-3) 6.74 parts of a salt represented by the formula (I-3-a), 4.25 parts of a salt represented by formula (I-3-b) and 60 parts of chloroform were mixed, followed by stirring at 23°C for 2 hours. To the mixture thus obtained, 30 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated and 20 parts of tert-butyl methyl ether and 20 parts of n-heptane were added to the concentrated residue, followed by stirring at 23°C for 30 minutes and further filtration to obtain 6.72 parts of a salt represented by formula (I-3).
[0258] [0258] MASS (ESI spectrum (+)): M* 525.0 MASS (ESI spectrum (-)): M° 323.0
[0259] Example 2: Synthesis of the salt represented by the formula (I-465) 3 CF3 = -S=0 _L © b ® ® Fa CF3 (I-3-a) (T-465-b) (1-465 ) 6.74 parts of a salt represented by the formula (I-3-a), 4.49 parts of a salt represented by the formula (I-465-b) and 60 parts of chloroform were mixed, which which was followed by stirring at 23°C for 2 hours. To the mixture thus obtained, 30 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated and 25 parts of tert-butyl methyl ether and 15 parts of n-heptane were added to the concentrated residue, followed by stirring at 23°C for 30 minutes and further filtration to obtain 6.61 parts of a salt represented by formula (I-465).
[0260] [0260] MASS (ESI spectrum (+)): M* 525.0 MASS (ESI spectrum (-)): M° 347.0
[0261] [0261] Example 3: Synthesis of the salt represented by the formula (1-13)
[0262] [0262] MASS (ESI spectrum (+)): M* 525.0 MASS (ESI spectrum (-)): M 467.1
[0263] Example 4: Synthesis of the salt represented by the formula (I-5) 3 CF3 Oes, Le - of. EF ora |) oss - Oss LO Var F3 Fa (I-3-a) (T-5-b) (1-5) 6.74 parts of a salt represented by the formula (1-3-a), 6.41 parts of a salt represented by the formula (1-5-b) and 60 parts of chloroform were mixed, followed by stirring at 23°C for 2 hours. To the mixture thus obtained, 30 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated, and 20 parts of tert-butyl methyl ether and 20 parts of n-heptane were added to the concentrated residue, followed by stirring at 23°C for 30 minutes and further by filtration to obtain 7.28 parts of a salt represented by formula (I-5).
[0264] [0264] MASS (ESI spectrum (+)): M* 525.0 MASS (ESI spectrum (-)): M° 517.1
[0265] [0265] Example 5: Synthesis of the salt represented by the formula (I-63) F
[0266] [0266] MASS (ESI spectrum (+)): M* 425.0 MASS (ESI spectrum (-)): M° 517.1
[0267] [0267] Example 6: Synthesis of the salt represented by the formula (I-71)
[0268] [0268] MASS (ESI spectrum (+)): M* 425.0 MASS (ESI spectrum (-)): M 467.1
[0269] [0269] Example 7: Synthesis of the salt represented by the formula (1-361) pr MgBr N s=|s]=-6 — CF3 | Q | Cra' (I-361-a) (I-361-b) (I-361-c) | | | © OT Ao 5 RC CF3SO; (I1-361-d) (I1-361-e) (I-361-F)
[0270] [0270] MASS (ESI spectrum (+)): M* 582.9 MASS (ESI spectrum (-)): M 467.1
[0271] [0271] Example 8: Synthesis of the salt represented by the formula (I-390) © | MgBr | © Mg ZnBr, “|G (GQ) F T F 72 (I-390-a) (I-390-b) (I-390-c) MO + ; SPOT ee$; F- + CF3SO; (I-361-d) (I-361-e) Ö | (I-390-f) 4.51 parts of a compound represented by formula (I-390-a) and 9.02 parts of tetrahydrofuran were mixed, and after stirring at 23°C for 30 minutes, the mixture cooled to 10°C was added dropwise to 0.63 part of magnesium to obtain a Grignard solution represented by the formula (I-390-b). To the thus obtained Grignard solution represented by the formula (I-390-b), 1.97 part of zinc bromide was further added, followed by stirring at 50°C for 3 hours to obtain a solution containing a compound represented by formula (I-390-c). 2.93 parts of a compound represented by formula (I-361-d), 7.16 parts of a compound represented by formula (I-361-e) and 10 parts of tetrahydrofuran were mixed, and after stirred at 23°C for 30 minutes, a solution containing a compound represented by the formula (I-390-c) was added. To the reaction mixture thus obtained, 2.87 parts of a compound represented by formula (I-361-e) was further added, followed by stirring at 23°C for 18 hours. To the reaction mixture thus obtained, 5 parts of 1N hydrochloric acid and 30 parts of chloroform were added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 15 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated and 30 parts of tert-butyl methyl ether was added to the concentrated residue, followed by stirring at 23°C for 30 minutes and further filtration to obtain 0.75 part of a salt represented by the formula (I-390-f). | | Fr © ER: + 5 And _ O F_ > +7 VE” era oss À, je PE ee. a-290-2) 3 | (I-390) 0.68 part of a salt represented by the formula (I-390-f), 0.57 part of a salt represented by the formula (I-13-b) and 20 parts of chloroform have mixed, followed by stirring at 23°C for 2 hours. To the mixture thus obtained, 10 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was repeated three times. The organic layer thus obtained was concentrated, and 5 parts of tert-butyl methyl ether and 15 parts of n-heptane were added to the concentrated residue, followed by stirring at 23°C for 30 minutes and further by filtration to obtain 0.67 part of a salt represented by formula (I-390).
[0272] [0272] MASS (ESI spectrum (+)): M* 532.9 MASS (ESI spectrum (-)): M 467.1
[0273] [0273] Example 9: Synthesis of the salt represented by the formula (1-494) F F F
[0274] [0274] MASS (ESI spectrum (+)): M* 496.9 MASS (ESI spectrum (-)): M 467.1
[0275] Synthesis Example 1: Synthesis of the salt represented by the formula (IX-4) 3 F3 @ NEE 9 € CF3 er + O rat —> CF; to, n DAA OL id E Fa F3 (IX-4-a) (I-5-b) (IX-4) 5.47 parts of a salt represented by the formula (IX-4-a), 6, 41 parts of a salt represented by the formula (I-5-b), 50 parts of chloroform and 20 parts of ethyl acetate were mixed, followed by stirring at 23°C for 2 hours . To the mixture thus obtained, 30 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated, and 30 parts of tert-butyl methyl ether were added to the concentrated residue, followed by stirring at 23°C for 30 minutes, removing the supernatant and further concentration to obtain 3.22 parts of a salt represented by formula (IX-4).
[0276] [0276] MASS (ESI spectrum (+)): M* 467.1
[0277] Synthesis Example 2: Synthesis of the salt represented by the formula (IX-5) F3 CF3 (25 Br + LA a — oo T° À 2 (IX-5-a) (I-5-b) (IX -5)
[0278] [0278] MASS (ESI spectrum (+)): M* 331.1 MASS (ESI spectrum (-)): M° 517.1
[0279] [0279] Synthesis Example 3: Synthesis of the salt represented by the formula (IX-6) | Te SH TS + X Oss —, +- (DTB + (2 AT OO ® (IX-6-a) (I-5-b) (IX-6)
[0280] [0280] MASS (ESI spectrum (+)): M* 389.0 MASS (ESI spectrum (-)): M° 517.1
[0281] [0281] Synthesis Example 4: Synthesis of the Salt Represented by Formula (IX-7)
[0282] [0282] MASS (ESI spectrum (+)): M* 317.1
[0283] [0283] Synthesis Example 5: Synthesis of the salt represented by the formula (TX-8)
[0284] [0284] MASS (ESI spectrum (+)): M* 281.1 MASS (ESI spectrum (-)): M° 517.1
[0285] [0285] Resin Synthesis The compounds (monomers) used in the synthesis of a resin (A) are illustrated below. In the following, these compounds are referred to as “(a1-1-3) monomer” according to the formula number. Hs Hs H Hs Hs ok Zi CH= CH HAT a Ö ; OÖ JA O 4 @ 00 do on (a1-1-3) (a1-2-6) 1 T OH L (a1-4-2) (a1-4-13) (a2-1-3) 0 ( a3-4-2)
[0286] [0286]
[0287] Synthesis Example 7 [Synthesis of Resin A2] 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 53:3:12:32 [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 total molar number of all the monomers, then the mixture was then 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 A2 (copolymer) having a mass average molecular weight of about 5.3 x 10° with an efficiency of 88%. This A2 resin has the following structural units. all tE soon to
[0288] Synthesis Example 8 [Synthesis of Resin A3] A monomer (a1-2-6), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (a1-2-6) were used. a1-4-13) as monomers, these monomers were mixed in a molar ratio of 53:3:12:32 [monomer (al-2-6): monomer (a2-1-3): monomer (a3-4 -2: monomer (a1-4-13)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitria and azobis (2,4 dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the total molar number of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. To the polymerization reaction solution thus obtained, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added in an amount of 2.0 times the total mass of all monomers, thereby was followed by stirring for 12 hours and further isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and recovery to obtain resin A3 (copolymer) having a mass average molecular weight of approximately 5.1 x 103 with 79% yield. This A3 resin has the following structural units.
[0289] [0289] <Preparation of Resist Composition> As shown in Table 2, the following components were mixed and the mixture thus obtained was filtered through a fluororesin filter having a pore diameter of 0.2 µm to prepare resist compositions.
[0290] [0290] Table 2 Composition of | Resin Gene- | Salt (I) Agent | PB/PEB acid deactivation resistor on (C Composition 1 | A1 = [3 = C1 = 100°C/ P 10 parts 1.5 part | 0.35 part | 130°C Composition 2 | A1 = 1-5 = C1 = 100°C/ p 10 parts 1.5 part | 0.35 part | 130°C p 10 parts 1.5 part | 0.35 part | 130°C Composition 4 | AL = [465 = 100°C / p 10 parts 1.5 part | 0.35 part | 130°C Composition 5 | A1 = 1-63 = C1 = 100°C/ p 10 parts 1.5 part | 0.35 part | 130°C Composition 6 | A1 = [71 = 100°C/ p 10 parts 1.5 part |0.35 part | 130°C p 10 parts 1.5 part |0.35 part | 130°C p 10 parts 1.5 part | 0.35 part | 130°C ns es [Fe [Es FE parts 1.5 part | 0.35 part | 130°C a es [m [Eee [202 10 10 parts 1.5 part | 0.35 part | 130°C as | re [ste [1 11 10 parts 1.5 part | 0.35 part | 130°C Fn as | | [ste [1 12 10 parts 1.5 part | 0.35 part | 130°C ee er | [in [Sas [2 13 10 parts 1.5 part | 0.35 part | 130°C ee [ee [an [one [2 14 10 parts 1.5 part | 0.35 part | 130°C TE ene [ien [his [ 8 10 parts 1.5 parts | 0.35 part | 130°C Ge ene | [ien [sion [8 16 10 parts 1.5 part | 0.35 part | 130°C Ge ene | [een [sion [8 17 10 parts 1.5 part | 0.35 part | 130°C Fa ee EE [Eee [202 18 10 parts 1.5 parts | 0.35 part | 130°C ae Ee 19 10 parts 1.5 parts | 0.35 part | 130°C Ge ene [ien [one [2 10 parts 1.5 part | 0.35 part | 130°C a ee EE 21 10 parts 1.5 parts | 0.35 part | 130°C a res [m ie [ar ame [0 22 10 parts 1.5 part | 0.35 part | 130°C Ingredients | A1 = Le RE C1 = 100°C/ Comparative 1 | 10 parts Ja tie 0.35 part | 130°C Composition A1 = Les c C1 = 100°C/ Comparative 2 | 10 parts Ja tie 0.35 part | 130°C Comparative 3 | 10 parts pa tie 0.35 part | 130°C Comparative 4 | 10 parts pa tie 0.35 part | 130°C at IX-2 = Composition A2 = 15 C1 = 100°C/ Comparative 5 | 10 parts Ja tie 0.35 part | 130°C
[0291] [0291] <Resin> A1 to A3: Resin A1 to Resin A3 <salt(I)> I-3: Salt represented by formula (I-3) I-5: Salt represented by formula (I-5) I -13: Salt represented by the formula (I-13) I-63: Salt represented by the formula (1-63)
[0292] [0292] (Evaluation of electron beam resist composition exposure, alkaline development) Each 6 inch (15.24 cm) diameter silicon wafer was treated with hexamethyldisilazane and then baked on a direct hot plate at 90°C for 60 seconds. A resist composition was applied by centrifugal application (“spin coating”) on the silicon wafer so that the thickness of the layer of composition became 0.04 μm. The coated silicon wafer was then prebaked on the direct hot plate at the temperature shown in the "PB" column of Table 2 for 60 seconds to form a composition layer.
[0293] [0293] In the resist pattern obtained after development, the exposure dose at which the diameter of the formed holes reached 17 nm was considered as an effective sensitivity.
[0294] [0294] <Evaluation of CD uniformity (CDU)> In the effective sensitivity, the diameter of holes of the resist pattern formed with 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 conditions where the average diameter of 400 holes around the patterns formed with a hole diameter of 17 nm in the same wafer was considered as a population. The results are shown in Table 2. The numerical value in the table represents the standard deviation (nm). Table 3 Comparing them with the comparative compositions 1 to 3 and the reference compositions 1 to 5, the compositions 1 to 9 showed a small standard deviation and a satisfactory evaluation of the CD uniformity (CDU).
[0295] [0295] (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 pre-baked on the direct hot plate at the temperature shown in column
[0296] [0296] In the resist pattern obtained after development, the exposure dose at which the diameter of the formed holes reached 17 nm was considered as an effective sensitivity.
[0297] [0297] <Evaluation of CD uniformity (CDU)> In the effective sensitivity, the hole diameter of the resist pattern formed with 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 conditions where the average diameter of 400 holes around the patterns formed with a hole diameter of 17 nm in the same wafer was considered as a population.
[0298] [0298] A salt and a resist composition including the salt are capable of producing a resist pattern with satisfactory CD (CDU) uniformity, and are therefore suitable for semiconductor fine processing, and are therefore very useful in an industrial point of view.

权利要求:
Claims (21)
[1]
1. A salt represented by the formula (I): (R) m2 &
At 1 go (R3)ms (Rm where, in the formula (I), R* represents a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, R2, R3 and R* each independently represent a fluorine atom halogen, a fluorinated alkyl group having 1 to 4 carbon atoms or a hydrocarbon group having 1 to 12 carbon atoms, and -CHz- included in the hydrocarbon group may be replaced by -O- or -CO-, m2 represents a integer from 0 to 4, and when m2 is 2 or more, a plurality of R may be the same or different, m3 represents an integer from 0 to 4, and when m3 is 2 or more, a plurality of R* may be the same or different, m4 represents an integer of 0 to 5, and when m4 is 2 or more, a plurality of R* may be the same or different, Qt and Q each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, Lt represents a saturated hydrocarbon group having 1 to 24 carbon atoms, -CH:- included in the saturated hydrocarbon group é can be replaced by -O- or -CO-, and a hydrogen atom included in the saturated hydrocarbon group can be replaced by a fluorine atom or 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 alicyclic hydrocarbon group may be replaced by -O-, -SO2- or - CO-.
[2]
2. The salt according to claim 1, wherein R* represents a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
[3]
3. The salt according to claim 1, in which R°, R° and R° each independently represent a fluorine atom, an iodine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a hydroxy group or an alkoxy group having 1 to 3 carbon atoms.
[4]
4 The salt according to claim 3, wherein R2, R* and R* each independently represents a fluorine atom, an iodine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
[5]
5. The salt according to claim 1, wherein m2 and m3 each independently represents an integer from 0 to 2 and m4 represents an integer from 0 to 3.
[6]
6. The salt according to claim 1, wherein the iodine atom is bonded to the meta position or the para position of the benzene ring with respect to S*.
[7]
7. The salt according to claim 1, wherein R* is attached at the meta position or at the para position of the benzene ring with respect to S*.
[8]
8. The salt according to claim 1, wherein R° and R* are each independently bonded to the meta position or the para position of the benzene ring relative to S*, and R° is bonded to the ortho position or the para position. meta position of the benzene ring with respect to S*.
[9]
9. The salt according to claim 1, wherein the cation in the salt is represented by any one of formula (I-c-1) to formula (I-c-20):
Fa F3 Fr F Of o$ of of CF3 F (Ic-1) (Ic-2) (Ic-3) (Ie-4) F3 F > CG 0 I @ Oo — F3 F F3 F (Ic-5) ( Ic-6) (Ic-7) (Ic-8)
H H 0 F F os Ÿ "D D CF5 F3 Far
H H (I-c-9) (I-c-10) (I-c-11) (I-c-12) OT © ©; Of | + | + | | | ' Le- Le- (I-c-16) (I-e-13) (I-e-14) (I-c-15) F Fa F3 | F F
F F | + of ol Of | + C) | F F | the, e= (I-c-17) (I-c-18) (I-c-19) (I-e-20)
[10]
10. The salt according to claim 1, wherein L! is a group represented by any one of formula (b1-1) to formula (b1-3) Nr Sort , EVENING, pee ON 77 *
Ö (b1-1) (b1-2) (b1-3) where, * and ** represent a binding site, and * represents a binding site at —Y*, in the formula (b1-1), LP represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom, LP3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CHz- included in the saturated hydrocarbon group may be replaced with -O- or -CO-, and the total number of carbon atoms of LP and LP3 is 22 or less, in the formula (b1-2), LP* represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom, LP5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CHz- included in the saturated hydrocarbon group may be replaced by -O- or -CO-, and the total number of carbon atoms of L°* and LP is 22 or less, in the formula (b1-3) , LP represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, LP” represents a single bond or a divalent saturated hydrocarbon group having 1 at 23 carbon atoms, a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CHz- included in the saturated hydrocarbon group may be replaced with -O- or -CO -, and the total number of carbon atoms of L°° and LP” is 23 or less.
[11]
11. The salt according to claim 1, wherein Y* represents an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CHz- included in the alicyclic hydrocarbon group or the adamantyl group may be replaced by -CO -, -S02- or -CO-.
[12]
12. The salt according to claim 1, wherein the anion in the salt is represented by any one of formula (I-A-1) to formula (I-A-59): aL a 1 02 X QU 0° (KX os Cou _ sem - os O 0 O (I-A-1) (I-A-2) (I-A-3) . 1 2
Ö O O (I-A-4) (I-A-5) (I-A-6) i3 1 2 os TT LA41 3 8 Ö Ö O 9 (I-A-7) (I-A-8) (I-A-9) 9
OH Q! Pa OH - 1 2 0.57 Ip LA SZ X SL - | A41 _ Ö O-SzO 0.872 L Os
O (I-A-10) (I-A-11) (I-A-12) O OH © 1 Q2 al Mo -— So Ao - DS >| A41 035 09 O3S F F F F O al Q2 70 So Ao (I-A-13) 33 ET NF 0 (I-A-14) (I-A-15) OH 0° at 0° 1 me OH “0587540420 zo Lo on
Oh! a” O. (I-A-16) oe A (I-A-18)
O (I-A-17)
OH OH OH Q!_Q - 0:57 SC OS pa Q! Q oO Qt 0 7 0 OH oo 70:87 > Der 0 Lo (I-A-20) 33 F E ô (I-A-21) (I-A-19)
Oh al La OH Q! Q2 has! sn | _ Ee Yo os YT Rit (IA-22) (IA-23) (IA-24) 1 Q2 O CH3 ' SI A41 0 (ot O3S LO os YT | Ad ° 0 OO > (1-a-25) 9 Ô (IA-26) | | ( ke 1 1 1 2 O CH a Q Lou 3 Lum 970 | Lum 90 038 LO OS" |, (Oe 035° |, O—JCF3 O , 07 0 07 0 (IA-27) bo or (IA-28) © (IA-29) °
| Om 00 Ris | worse - Q Vo. A41 a’ A LL RC + “ os L - os ° 0 Ö A (I-A-31) os7 De (I-A-30) u (I-A-32) O0 0 T Spie O Oo QL 0 ß @ ô VE ô -0.s O, A41 - LA = LA! 3 O3S oo OsS7/, 07 0 0 VF Q° F (I-A-33) (I-A-34) (I-A-35)
PF
F OH 2 al 02 O ale al ‚a _ O _ O 7 os oa 0.57 os
O Ö O (I-A-36) (I-A-37) (I-A-38)
O Q 1 02 a! at Q! Q O ri 7 07 7 07 - bone
O O O (T-A-39) (I-A-40) (I-A-41) ri
TA ale ale Î - O _ O os 0.574
O O (I-A-42) (I-A-43) ale ale > aL b - O 035 2 “0.877 0:57 © 0
O O O
O (I-A-44) (I-A-45) (I-A-46)
O O Me A De X HO Po OH > j © 0, 9 > O 5 1 02 2 „+ Qt Q2 oF Q À oO Qt à O Or _ or _ oon ae - 035 Sr OS Lad
O O O (I-A-47) (I-A-48) (I-A-49)
0 0. oO A Ur N Pe O 0 ò O 5 al a D L [ oO a! a O Q! 0 O od 70 SE 70 SEM 9 ° Ö ° Ö (I-A-50) (I-A-51) (I-A-52)
0. Oo Q! see you! at Oo 9 og > € osn al to oO Ô 0 o,s (I-A-53) 0 (I-A-55) (I-A-54) ° O 9 OH 1 02 <> Q1 Q2 ae. eue - O - O sou OR Com OR
O O (I-A-56) 9 (I-A-57) 4+, bk 0 Oo
ST BE
DSA DSA 0 (IA-58) 0 (Ia-59) where, R to RÙ each independently represent an alkyl group having 1 to 4 carbon atoms, R® is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or groups formed by combining these groups, and LM! is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
[13]
13. The salt according to claim 1, wherein the anion in the salt is represented by any one of formula (I-a-1) to formula (I-a-38):
HO © FF AN EF A Fo 035 - 10 “048 O OS 6 (Ial) 9 (za-2) (Ia-3) FL F 0 FF 0 Fro 0. FL ‚F 0 O CH, - De - =- " 038 "CH, 048 - ° O3S O3S ql OO > 0 O-S50 > OO (Ia-6) (Ia-7) (Ia-4) (Ia-5)
CH Ao O CH, >, O 3 A 07 x o 035 0 Fe TV 9 9 4 0 NT O st 0 9 FE 0% (I-a-8) (I-a-9) (I-a-10) Neck,
OH N © 0 0.8 LA 3 O 035 Ö
F OO Sc (I-a-11) (I-a-12) (I-a-13)
F 000 F
BDD
FF - O 3 os Dr _ FF 4 re SC (I-a-14) O (I-a-15) (I-a-16)
OH 0 FF FF 0.6 0 © KO O "O3S 3 O
O (I-a-17) (I-a-18) (I-a-19)
LF se A JF F xe X E > we Lo -Æo OS (I-a-20) (I-a-21) Es 3 (I-a-22)
À A HO OH Ö , { , í &
FSF F FF “038 7 7038 (I-a-23) (I-a-24) (I-a-25)
FF - FF FF 07 ee 07 (I-a-26) (I-a-27) 9 (I-a-28) 3-0 X x“ Sa 0 Thu 3 O+S N T © (I-a-29) (I-a-30)
FE JF A 0 KF JO “10° FF "08 O+S | “10° O 035 Ö O3S CH3 Ô O _a-32 La 0 _a-34 (Ia-31) (Ia-32) (Ia-33) ( Ia-34)
THE
O QE oe 81° 035 OÖ (I-a-35) (I-a-36) HL wd
O Pe po 03S "035
Ö Ö (I-a-37) (I-a-38)
[14]
14. An acid generator comprising the salt according to claim 1. 5
[15]
15. A resist composition comprising the acid generator of claim 14 and a resin having an acid labile group.
[16]
16. A resist composition according to claim 15, wherein the resin having an acid-labile group comprises a structural unit represented by the formula (a2-1): a14 Ho
VS
O5 (a2-1) Ra15 T(CH3)o1
H Ra16 where, in formula (a2-1), L°* represents -O- or *-O-(CH>)x2-CO-O-, k2 represents an integer from 1 to 7, and * represents a site bond to -CO-, R2!* represents a hydrogen atom or a methyl group, R°15 and RE each independently represent a hydrogen atom, a methyl group or a hydroxy group, and 01 represents an integer of 0 at 10.
[17]
17. The resist composition according to claim 15, wherein the resin having an acid-labile group comprises at least one member selected from the group consisting of a structural unit represented by the formula (a1-1) and a structural unit represented by the formula (a1-2): PBE} HE C Cc
OO Lan La2 Joan pot ea nt' (a1-1) (a1-2) where, in formula (a1-1) and formula (a1-2), Lt 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 to -CO-, R°* and R® each independently represent a hydrogen atom or a methyl group , or an alkyl group having 1 to 6 carbon atoms and possibly having a halogen atom, R°° and R each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups, m1 represents an integer from 0 to 14, nl represents an integer from 0 to 10, and nl' represents an integer from 0 to 3.
[18]
18. The resist composition according to claim 15, wherein the resin having an acid labile group comprises a structural unit represented by the formula (a2-A):
Ho PP
I | (a2-A)
OH ( RS) where, in the formula (a2-A), R20 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, R° represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group, A20 represents a single bond or * -X®1_ (A22 p-, and * represents a bonding site at carbon atoms to which -R°® is bonded, A7 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 R °* can be the same or different from each other.
[19]
19. The resist composition according to claim 15, wherein the resin having an acid-labile group comprises a structural unit represented by any one of formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4):
Ra18 Ra19 7 7 test dot of DT = G a25) (R222)1 (R225) (REP) oO” © À 04, 7
Ô (a3-1) (a3-2) (a3-3) (23-4) where in the formula (a3-1), the formula (a3-2), the formula (a3-3) and the formula (a3-4), L°*, L° and L° each independently represent -O- or a group represented by *-O-(CH>)(3-CO-O- (k3 represents an integer from 1 to 7 ), L represents -O-, *-OL°8-0-, *-OL°8-CO-O-, *-OL°8-CO-OL°°- CO-O- or *-OL° 8-0-CO-L°°-0-, L® and L°° each independently represent an alkanediyl group having 1 to 6 carbon atoms, * represents a bonding site to a carbonyl group, RAS R°19 and RO each independently represent a hydrogen atom or a methyl group, R22* represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, X°* represents -CHz- or an oxygen atom, R°21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R322, R223 and R225 each independently represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, p1 represents an integer from 0 to 5, q1 represents an integer from 0 to 3, rl represents an integer from 0 to 3, w1 represents an integer from 0 to 8, and when pl, ql, rl and/or wl is/are 2 or more, a plurality of R*, R222, R223 and/or R°° may be the same or different from each other.
[20]
20. The resist composition of claim 15, further comprising an acid-generating salt having a lower acidity than an acid generated from the acid generator.
[21]
21. 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 20 to a substrate, (2) a step of drying the composition applied to form a composition layer, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and (5) a step of developing the composition layer heated.

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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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JP2020018904|2020-02-06|

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