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    • 专利摘要:
    It is an object of the present invention to provide a salt capable of producing a resist pattern with satisfactory pattern margin melting (PCM), a quencher and a resist composition. The present invention relates to a salt, a deactivating agent as well as a resist composition comprising the same, said salt being represented by the formula (I) as defined in claim 1 where, in the formula (I), R1, R2 and R3 each independently represent a halogen atom, an alkyl fluoride group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, and -CH2- included in the hydrocarbon group may be replaced by - O- or -CO-, m1, m2 and m3 represent an integer of 0 to 4, and when m1, m2 and / or m3 are 2 or more, a plurality of R1, a plurality of R2 and / or, a plurality of R3 may be the same or different from each other and X1 represents -CO- or -SO- or -SO2-.
    公开号:BE1027310B1
    申请号:E20205390
    申请日:2020-06-02
    公开日:2021-05-18
    发明作者:Katsuhiro Komuro；Yuki Takahashi；Koji Ichikawa
    申请人:Sumitomo Chemical Co；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a salt, a quencher quencher and a resist composition comprising the salt and a method for producing a resist pattern using the resist composition. BACKGROUND OF THE INVENTION
    [0002] [0002] Patent document 1 mentions a resist composition comprising a salt having the following structural formula, a resin including a structural unit having a labile group in an acid medium, and an acid generator. / “Co, S
    [0003] [0003] Patent Document 1: JP 2017-202993 A Patent Document 2: JP 2018-066985 A Description of the Invention Problems to be Solved by the Invention
    [0004] An object of the present invention is to provide a salt capable of producing a resist pattern having a pattern margin melting (PCM - for "pattern collapse margin") better than that of a resist pattern formed from of a resist composition comprising the salts mentioned above.
    [0005] The present invention includes the following inventions.
    [1] [1] A salt represented by the formula (I): (Rm ° s 0 + a ©
    [2] [2] A deactivation agent comprising a salt according to [1].
    [3] [3] A resist composition comprising a deactivating agent according to
    [2] [2], a resin including a structural unit having an acid labile group, and an acid generator.
    [4] [4] The resist composition according to [3], wherein the resin comprising a structural unit including an acid labile group includes at least one resin selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by the formula (a1-2): Ja fe Je RS 0 =} i La NP | N ru (CH Re “(Hat LA bar tat-t) (ai-2} where, in formula (a1-1) and formula (a1-2), L ° * and L ° * each independently represent -O - or * -O- (CH>) 1-CO-O-, k1 represents an integer from 1 to 7, and * represents a binding site to -CO-, R ° * and R °° each independently represent an atom hydrogen or a methyl group,
    [5] [5] The resist composition according to [3] or [4], wherein the resin including a structural unit having an acid labile group includes a structural unit represented by the formula (a2-A): R350
    [6] [6] The resist composition according to any one of [3] to [5], wherein the acid generator includes a salt represented by formula (B1): Qb + OS [61 208 | AS, (B1) where, in formula (B1), QP! and QP each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, LP! represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CHz- included in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom included in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH> - included in the hydrocarbon group alicyclic can be replaced by -O-, -S (O) z- or -CO-, and Z 'represents an organic cation.
    [7] [7] The resist composition according to any one of [3] to [6], further comprising an acid generating salt having an acidity lower than that of an acid generated by the acid generator.
    [8] [8] A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to any one of [3] to [7] on a substrate, (2) a step drying the applied composition to form a composition layer, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and
    [0006] It is possible to produce a resist pattern with a satisfactory pattern margin melting (PCM) by using a resist composition containing a salt of the present invention.
    [0007] As used herein, the term "(meth) acrylate" means "at least one of: acrylate and methacrylate". Terms such as "(meth) acrylic acid" and "(meth) acryloyl" also have the same meaning.
    [0008] [0008] [Salt represented by formula (1)] The salt of the present invention relates to a salt represented by formula (I) (hereinafter sometimes referred to as "salt (I)>).
    [0009] Examples of the salt (T) include the salts represented by the following formulas.
    [0010] <Method for the synthesis of salt (I)> Salt (I) can be produced by mixing a salt represented by formula (Ia) in the presence of a basic catalyst in a solvent: (Rm (R m4 | Os co TT where x "(RS) m3 x! (RS) ma (RE) m2 (R2) 72 (Ia) (I) where all symbols are the same as defined above. Examples of the base include triethylamine , sodium hydroxide, potassium hydroxide and the like Examples of the solvent include chloroform and the like The reaction is generally carried out at a temperature in the range of 0 to 80 ° C for 0.5 to 24 hours.
    [0011] The salt represented by formula (Ia) can be produced by reacting a compound represented by formula (Ib) with a compound represented by formula (Ic) in the presence of trifluoromethanesulfonic acid and trifluoroacetic anhydride in a solvent: (R ') m 1 GU CF3SO3H ge. Cu ee Oo Q 3 O, S-CF> x "(RS) m N (RZ) m2 © oH or Aer SL (RS) m3 (RE) m2 (Ib) (Ic) (Ia) where all symbols are identical to those defined above.
    [0012] [0012] The salt (T) can also be obtained by reacting a salt represented by the formula (Id) in the presence of a basic catalyst in a solvent and by passing the product of the reaction through an exchange resin of ions (chlorine ion exchange resin), which is followed by treatment with a base and further by treatment with an aqueous solution of oxalic acid: (Rm Rm vn AD Os-crs8 TT ee CX, (RS ) ms SC (R °) m2 (R2) 72 (Id) (I) where all symbols are the same as defined above. Examples of the base include sodium hydroxide, potassium hydroxide and analogues.
    [0013] The salt represented by the formula (Id) can be obtained by reacting a compound represented by the formula (Ib) with a compound represented by the formula (Ie) in the presence = of trifluoromethanesulfonic acid and trifluoroacetic anhydride in a solvent: (Rm 9 Ram CF3SO4H CA M a CU od: he m Cote op otho, Sa. (RÈ) m2 (Ib) (Ie) (1-d) where all the symbols are identical to those defined above. Examples of the solvent include chloroform, acetonitrile and the like.
    [0014] <Deactivation agent, "Quencher"> The quencher of the present invention comprises a salt (I). The quencher can comprise one salt (I), or two or more salts (I).
    [0015] <Resist composition> The resist composition of the present invention includes a deactivating agent comprising a salt (I), a resin comprising a structural unit having an acid labile group (hereinafter sometimes referred to as "resin ( A) ”) and an acid generator (hereinafter sometimes referred to as“ acid generator (B) ”). The“ acid labile group ”means a group having a leaving group which is removed by contact with an acid. , thereby forming a hydrophilic group (eg, a hydroxy group or a carboxy group).
    [0016] [0016] <Deactivating agent (or quencher) (C)> Examples of the deactivating agent (C) include a basic organic compound containing nitrogen and an acid generating salt having an acidity lower than that of an acid generated by an acid generator (B) mentioned later (excluding a salt represented by formula (I)). It is particularly preferable to contain an acid generating salt having an acidity lower than that of an acid generated by the acid generator (B) such as an internal salt of weak acid (hereinafter sometimes called "internal salt. of weak acid (D) ”). Examples of an organic compound containing basic nitrogen include an amine and an ammonium salt. Examples of the amine include an aliphatic amine and an aromatic amine. Examples of an aliphatic amine include a primary amine, a secondary amine, and a tertiary amine.
    [0017] [0017] Examples of amines include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, la trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldildildildihexylamine, methyldildicycloldoldicylamine, methyldildicycloldohexylamine, methyldildicycloldoldicylamine, methyldildicycloldoldohexylamine, methyldyldicycloldoldohexylamine, methyldildicycloldoldohexylamine, methyldildicldicyclohexylamine, methyldildicycloldoldohexylamine ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, la = dicyclohexylmethylamine, la = tris [2- (2- (2- methoxyethoxy) é thyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4 "-diamino-1,2-diphenylethane, 4,4" -diamino-3,3 "-diméthyldiphenylmethane, 4, 4 "diamino-3,3" -diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-pyridyl) ethene, 1,2-di (4-pyridyl) ethene, 1,3-di (4-pyridyl) propane , 1,2-di (4-pyridyloxy) ethane, di (2-pyridyl) ketone, 4,4 "-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine , 2,2'-dipicolylamine, bipyridine and the like, preferably diisopropylaniline, and more preferably 2,6-diisopropylaniline.
    [0018] [0018]
    [0019] The acidity in a salt generating an acid having an acidity lower than that of an acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). generating an acid having an acidity lower than that of an acid generated from the acid generator (B), the acid dissociation constant of an acid generated from the salt usually responds to the following inequality: - 3 <pKa, preferably -1 <pKa <7, and more preferably 0 <pKa <5. Examples of an acid generating salt having an acidity lower than that of an acid generated from the acid generator (B) include the salts represented by the following formulas, a salt represented by the formula (D) mentioned in JP 2015 -147926 A (hereinafter sometimes called “weak acid internal salt (D)”, and the 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 generating an acid having an acidity lower than that of an acid generated from the acid generator (B) is preferably a salt generating a carboxylic acid having an acidity lower than that of a acid generated from the acid generator (B) (a salt having a carboxylic acid anion) and more preferably an internal salt of weak acid (D).
    [0020] Examples of the weak acid internal salt (D) include the following salts. in Dn sam Se ”zoo pe ss, Jan, + aw“ pe / pq Rn; SN, + SA, + JA, AT 6 LPC Ni JE 4 2 uv GAT; A Jp TA% VAT IT We & 4> = Bir er # # ET zoo ”1, FRS PS GERT BC A = a, aa MOLEN, = A OD OD O0 At HG Sn SER RO wee goa” Foe AA, Oe, ze , mn, 0 th};
    [0021] When the salt (I) and the quencher (C) are included as deactivating agent, a ratio between the content of salt (T) and that of the quencher (C) (mass ratio; salt (I ): quencher (C)) is generally between 1:99 and 99: 1, preferably between 2:98 and 98: 2, more preferably between 5:95 and 95: 5, more preferably between 10:90 and 90:10 and more preferably between 15:85 and 85:15.
    [0022] In the resist composition of the present invention, the salt (I) content is usually 0.001 to 20% by mass, preferably 0.005 to 15% by mass, and more preferably from 0.01 to 10. % by mass, based on the solids content of the resist composition. When the deactivating agent comprises the deactivating agent (C), the content of the deactivating agent (C) is preferably about 0.01 to 15% by weight, more preferably about 0.01 to 10%. by weight, more preferably from 0.01 to 5% by weight, and more preferably from 0.01 to 3% by weight, based on the solids content of the resist composition.
    [0023] <Resin A> The resin (A) comprises a structural unit having a labile group in an acid medium (hereinafter sometimes called "structural unit (a1)"). It is preferable that the resin (A) further includes a structural unit other than the structural unit (a1). Examples of structural unit other than structural unit (a1) include a structural unit having no acid labile group (hereinafter sometimes referred to as "structural unit (s)"), a structural unit other than l structural unit (a1) and structural unit (s) (for example, a structural unit having a halogen atom mentioned later (hereinafter sometimes referred to as "structural unit (a4)>)), a structural unit having a later mentioned non-leaving hydrocarbon group (hereinafter sometimes referred to as "structural unit (a5)") and other structural units derived from monomers known in the art.
    [0024] <Structural Unit (a1)> The structural unit (a1) is derived from a compound comprising a labile group in an acidic medium (hereinafter sometimes called "monomer (a1)").
    [0025] Examples of the alkyl group for R ° *, R22 and R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group and the like. .
    [0026] Examples of the hydrocarbon group for R °, R ° 2 and R ° include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and groups obtained by combining these groups.
    [0027] Examples of group (1) include the following groups.
    [0028] Specific examples of group (2) include the following groups. * represents a binding site.
    [0029] The monomer (a1) is preferably a monomer having a labile group in an acidic medium and an unsaturated ethylenic bond, and more preferably a (meth) acrylic monomer having a labile group in an acidic medium.
    [0030] Among the (meth) acrylic monomers having a labile group in an acid medium, those having an alicyclic hydrocarbon group having 5 to 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.
    [0031] The structural unit derived from a (meth) acrylic monomer having a group (1) is a structural unit represented by the formula (a1-0) (hereinafter sometimes called structural unit (a1-0)), a structural unit represented by formula (a1-1) (hereinafter sometimes called structural unit (a1-1)) or a structural unit represented by formula (a1-2) (hereinafter sometimes called structural unit (a1- 2)).
    [0032] [0032] R20! R ° * and R °° are preferably a methyl group.
    [0033] The structural unit (a1-0) includes, for example, a structural unit represented by any one of the formula (a1-0-1) to the formula (a1-0-12) and a structural unit wherein a methyl group corresponding to R * ° in structural unit (a1-0) is substituted with a hydrogen atom and is preferably a structural unit represented by any one of the formula (a1-0-1 ) to the formula (a1- 0-10).
    [0034] The structural unit (a1-1) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646 A. Among these structural units, a structural unit represented by any one of the formula (a1 -1-1) to the formula (a1-1-4) and a structural unit in which a methyl group corresponding to R ** in the structural unit (a1-1) is substituted with a hydrogen atom are preferred, and a structural unit represented by any one of formula (a1-1-1) to formula (a1-1-4) is more preferred.
    [0035] Examples of structural unit (a1-2) include a structural unit represented by any one of formula (a1-2-1) to formula (a1-2-6) and a structural unit in which a methyl group corresponding to R® in the structural unit (a1-2) is substituted with a hydrogen atom, and a structural unit represented by any one of the formula (a1-2-2), the formula ( a1-2-5) and the formula (a1-2-5) is preferred.
    [0036] When the resin (A) includes a structural unit (a1-0), its content is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 40 mol%, on the basis of all the structural units of the resin (A).
    [0037] In structural unit (a1), examples of structural unit having a group (2) include a structural unit represented by formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1-4) ) "):
    [0038] Examples of the alkyl group in R °° and R23 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and more preferably a methyl group.
    [0039] In formula (a1-4), R °° is preferably a hydrogen atom, R233 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group and an ethoxy group, and more preferably a methoxy group, 1a is preferably 0 or 1, and more preferably 0, R ° 3 * is preferably a hydrogen atom, and R ° 3 ° is preferably an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group, and more preferably a methyl group or an ethyl group.
    [0040] The structural unit (a1-4) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646 A. The structural unit preferably includes the structural units represented by the formula (a1-4- 1) with the formula (a1-4-12) and a structural unit in which a hydrogen atom corresponding to R ° in the structural unit (a1-4) is substituted with a methyl group, and more preferably the units structures represented by the formula (a1-4-1) to the formula (a1-4-5) and the formula (a1-4-10).
    [0041] When the resin (A) includes the structural unit (a1-4), the content is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, more preferably 20 to 85 mol%, of more preferably 20 to 70 mol%, and more preferably 20 to 60 mol%, based on the total of all structural units of the resin (A).
    [0042] 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) "). {8 R® Et {= 0 151 Nas To Co (a1-5) 65 | Vist | In formula (a1-5), R ° 8 represents an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, a hydrogen atom or a halogen atom, Z represents a single bond or * - (CHz>) n3-CO-L ° * -, h3 represents an integer from 1 to 4, and * represents a binding site at L ° *, L ° t, L ° 2, L53 and L ** each independently represent -O- or -S-, s1 represents an integer of 1 to 3, and sl 'represents an integer of 0 to 3.
    [0043] The halogen atom includes a fluorine atom and a chlorine atom and is preferably a fluorine atom. Examples of an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a group. octyl, a fluoromethyl group and a trifluoromethyl group.
    [0044] The structural unit (a1-5) includes, for example, the structural units derived from the monomers mentioned in JP 2010-61117 A. Among these structural units, the structural units represented by the formula (a1-5-1) to formula (a1-5-4) are preferred, and structural units represented by formula (a1-5-1) or formula (a1-5-2) are more preferred.
    [0045] When the resin (A) includes the structural unit (a1-5), the content is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, more preferably 5 to 40 mol%, and more preferably 5 to 30 mol%, based on all the structural units of the resin (A).
    [0046] The structural unit (a1) also includes the following structural units. tai ter ter ta tar ter Te k 0H) DD on KM (a1-3-1) (a1-3-2) (a1-3-3) (a1-3-4) (a1-3-5) 01739) ern
    [0047] When the resin (A) includes the structural units mentioned above as (a1-3-1) to (a1-3-7), the content is preferably 10 to 95 mol%, more preferably 15 to 90 mole%, more preferably 20 to 85 mole%, more preferably 20 to 70 mole%, and more preferably 20 to 60 mole%, based on all the structural units of the resin (A).
    [0048] <Structural unit (s)> The structural unit (s) is derived from a monomer having no labile group in an acidic medium (hereinafter sometimes called "monomer (s)"). It is possible to use, as the monomer from which the structural unit (s) is derived, a monomer having no acid labile group known in the resist field.
    [0049] [0049] - <Structural unit (a2)> The hydroxy group possessed by the structural unit (a2) can be an alcoholic hydroxy group or a phenolic hydroxy group.
    [0050] In structural unit (a2), examples of structural unit having a phenolic hydroxy group include a structural unit represented by formula (a2-A) (hereinafter sometimes referred to as "structural unit (a2-A) "): R250
    [0051] Examples of the halogen atom in R °° include a fluorine atom, a chlorine atom and a bromine atom.
    [0052] Examples of * -X °° 1- (A252-X252) pp ”include * -O-, * -CO-O-, * - O-CO-, * -CO-0-A252-CO- 0-, * -0-CO-A352-0-, * -OA ° -CO-O-, * -CO-0-A% - O-CO- and * -0-CO-A ° 2- 0-CO-. Of these, * -CO-O-, * -CO-0-A92-CO-0- or * -O-A352-CO-O- are preferred.
    [0053] [0053]
    [0054] [0054] A is preferably a single bond, * -CO-O- or * -CO-O- A252-CO-O-, more preferably a single bond, * -CO-O- or * -CO-O- CH2-CO -O-, and more preferably a single bond or * -CO-O-.
    [0055] [0055] mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.
    [0056] Examples of structural unit (a2-A) include structural units derived from the monomers mentioned in JP 2010-204634 A and JP 2012-12577 A.
    [0057] 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.
    [0058] [0058] Examples of a structural unit having an alcoholic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)" ).
    [0059] In formula (a2-1), L® is preferably -O- or -O- (CH2) j- CO-O- (fl represents an integer from 1 to 4), and more preferably -O -, R ! is preferably a methyl group, R3! 5 is preferably a hydrogen atom, RS is preferably a hydrogen atom or a hydroxy group, and ol is preferably an integer of 0 to 3, and more preferably 0 or 1.
    [0060] The structural unit (a2-1) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646 A. A structural unit represented by any one of the formula (a2-1-1) to formula (a2-1-6) is preferred, a structural unit represented by any one of formula (a2-1-1) to formula (a2- 1-4) is more preferred, and a structural unit represented by formula (a2-1-1) or formula (a2-1-3) is more preferred. Ha CH; Ho H Hz CH; Ho H [ters he H +5 WB # 5 PS + za Dos Dos Le Dos> 9 5 9
    [0061] When the resin (A) includes the structural unit (a2-1), the content is usually 1 to 45 mol%, preferably 1 to 40 mol%, more preferably 1 to 35 mol%, and preferably further 1 to 20 mol%, and more preferably 1 to 10 mol%, based on all structural units of the resin (A).
    [0062] <Structural unit (a3)> The lactone ring carried by the structural unit (a3) can be a monocyclic ring such as a B-propiolactone ring, a y-butyrolactone ring or a ò-valerolactone ring, or a condensed ring a monocyclic lactone ring and the other ring.
    [0063] The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3) or the formula (a3-4). These structural units can be included alone, or two or more structural units can be included: pais ie fe fe | Tt Tet Tl tor al TOS Ue: SZ es (R222) 41 (Ra23) a wi o7 © DX 9 DX od G
    [0064] Examples of the aliphatic hydrocarbon group in R ° *, R322 R ° 23 and R22 include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and a tert-butyl group.
    [0065] In the formula (a3-1) to the formula (a3-3), preferably, L **, L °, and L ° ® are each independently -O- or a group in which k3 is an integer of 1 to 4 in * -O- (CH2) ç3-CO-O-, more preferably -O- and * -O-CH> -CO-O-, and more preferably an oxygen atom, R218 R319 R220 and R22! are preferably methyl, preferably R * and R223 are each independently a carboxy group, a cyano group or a methyl group, and preferably, p1, q1 and r1 are each independently an integer of 0 to 2, and more preferably 0 or 1.
    [0066] In formula (a3-4), R ** is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or a group ethyl, and more preferably a hydrogen atom or a methyl group, R22 is preferably a carboxy group, a cyano group or a methyl group, L ”is preferably -O- or * -OL ° 8-CO-O -, and more preferably -O-, -0-CH2-CO-0- or -0-C: H4-CO-0-, and wl is preferably an integer from 0 to 2, and more preferably 0 or 1. In particular, the formula (a3-4) is preferably the formula (a3-4) ':
    [0067] Examples of structural unit (a3) include structural units derived from the monomers mentioned in JP 2010-204646 5 A, from the monomers mentioned in JP 2000-122294 A and from the monomers mentioned in JP 2012-41274 A. The structural unit (a3) is preferably a structural unit represented by any one of the formula (a3-1-1), the formula (a3-1-2), the formula (a3-2-1), the formula (a3- 2-2), the formula (a3-3-1), the formula (a3-3-2) and the formula (a3-4-1) to the formula (a3-4-12), and the structural units in which the methyl groups corresponding to R ° * $, RP, R220 and R2 * in the formula (a3-1) in the formula (a3-4) are substituted with hydrogen atoms in the structural units ci -above.
    [0068] [0068] Hz Hs CH3 Hz Hs Hs Hz CHz on} An or} Een eci
    [9] [9] 9 A 0,0 ve O, © AI SI Be a Ô (99471) (e3-4-5) 343) (23-44) N (a3-4.5) 9949 Hz HH H2 Ha Ha C2CHs 2 CHs [ 2 CH, c2CHs {4 DO ae Be SE be ON
    [0069] When the resin (A) includes the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, and more preferably 10 to 60 mol%, based on of all the structural units of the resin (A).
    [0070] [0070] <Structural unit (a4)> Examples of structural unit (a4) include the following structural units:
    [0071] Examples of the chain hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group , a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group.
    [0072] Examples of structural unit (a4) include a structural unit represented by at least one selected from the group consisting of formula (a4-0), formula (a4-1), formula (a4-2) , the formula (a4-3) and the formula (a4-4):
    [0073] Examples of the divalent aliphatic saturated hydrocarbon group in L ‘° include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl and butane-1,4-diyl group; and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and group 2-methylpropane-1,2-diyl.
    [0074] [0074] L “is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
    [0075] Examples of structural unit (a4-0) include the following structural units, and structural units in which a methyl group corresponding to R ° in the structural unit (a4-0) in the following structural units is substituted with a hydrogen atom: Hz Hz Hz Ha Hs Hs erb 3e za F3 Pr, Ed F2HC F3 F2H (a4-0-5) (a4-0-6) (a4-0-1) (a4-0-2 ) (a4-0-3) (a4-0-4)
    [0076] [0076] H, Ra41 Le ST
    [0077] Examples of the saturated hydrocarbon group in R * include a chain saturated hydrocarbon group and a monocyclic or polycyclic saturated alicyclic hydrocarbon group, and groups formed by combining these groups.
    [0078] Examples of the substituent carried by R ° * include at least one selected from the group consisting of a halogen atom and a group represented by the formula (a-g3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred:
    [0079] Examples of saturated hydrocarbon group in A® ** ° include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, group octyl, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group; monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* represents a binding site): Examples of a group formed by combination include a group obtained by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, and include an alkanediyl group-alicyclic hydrocarbon group, an alicyclic hydrocarbon group-alkyl group, an alkanediyl group-alicyclic hydrocarbon group-alkyl group and the like.
    [0080] 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).
    [0081] When R2 * is a saturated hydrocarbon group having the group represented by the formula (a-g3), R ** is more preferably a group represented by the formula (a-g2): + —A246 - xa44 _ — _ Aa47 (ag 2) where , in formula (a-g2), A3 * ° represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, X represents ** - O-CO- or ** - CO-O- (** represents a binding site at A ° * °), A7 represents a saturated aliphatic hydrocarbon group having 1 to 17 carbon atoms optionally having a d atom 'halogen,
    [0082] The number of carbon atoms of the saturated hydrocarbon group for A ° * ° is preferably 1 to 6, and more preferably 1 to 3.
    [0083] The preferred structure of the group represented by the formula (a-g2) is the following structure (* is a carbonyl group binding site).
    [0084] Examples of alkanediyl group in A ! include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group and hexane-1 group, 6-diyl; and branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
    [0085] Examples of divalent saturated hydrocarbon group represented by A3% 2, A and A ** in the group represented by the formula
    [0086] In a group represented by the formula (a-g1), examples of the group in which X ** is -O-, -CO-, -CO-O- or -O-CO- include the following groups. In the following examples, * and ** each represent a binding site, and ** is a -O-CO-R® ** binding site, 0 Ae Ao OS De
    [0087] Examples of structural unit represented by formula (a4-1) include the following structural units, and structural units in which a methyl group corresponding to A® * in the structural unit represented by formula (a4- 1) in the following structural units is substituted with a hydrogen atom.
    [0088] [0088] Hs Hs Hs Ha H B} of} PF Ps fr 1 O O 0 9 7 ko X 3 + +, O F
    [0089] Examples of structural unit represented by formula (a4-1) include a structural unit represented by formula (a4-2): Hz fs TT
    [0090] Examples of the alkanediyl group having 1 to 6 carbon atoms of L ** include the same groups as those mentioned for the alkanediyl group A *, Examples of the saturated hydrocarbon group of R include the same groups as those mentioned for R ° 2.
    [0091] The structural unit represented by the formula (a4-2) includes, for example, the structural units represented by the formula (a4-1-1) to the formula (a4-1-11). A structural unit in which a methyl group corresponding to R in the structural unit (a4-2) is substituted with a hydrogen atom is also exemplified as the structural unit represented by the formula (a4-2).
    [0092] Examples of the structural unit (a4) include a structural unit represented by the formula (a4-3): Ho RP PD
    [0093] Examples of the alkanediyl group in L ° include those which are the same as mentioned in the alkanediyl group in the divalent saturated hydrocarbon group of A @ *, The divalent saturated hydrocarbon group optionally having a fluorine atom in A ** is preferably a divalent aliphatic saturated hydrocarbon group optionally having a fluorine atom and a divalent alicyclic saturated hydrocarbon group optionally having a fluorine atom, and more preferably a perfluoroalkanediyl group.
    [0094] In formula (a4-3), L ° is preferably an ethylene group.
    [0095] The structural unit represented by the formula (a4-3) includes, for example, the structural units represented by the formula (a4-1 "-1) to the formula (a4-1'-11). A structural unit in which a methyl group corresponding to R ”in the structural unit (a4-3) is substituted with a hydrogen atom is also exemplified as the structural unit represented by the formula (a4-3).
    [0096] It is also possible to cite by way of example, as structural unit (a4), a structural unit represented by the formula (a4-4): + RC
    [0097] Examples of the saturated hydrocarbon group for R22 include those which are the same as the saturated hydrocarbon group represented by R2 * 2. R ° 2 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and more preferably an alkyl group having 1 to 6 carbon atoms having a fluorine atom.
    [0098] In the formula (a4-4), Af ! is preferably - (CH2); 1-, more preferably an ethylene group or a methylene group, and more preferably a methylene group.
    [0099] 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.
    [0100] [0100] When the resin (A) includes the structural unit (a4), the content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and more preferably 3 to 10 mol%, on the basis of basis of all the structural units of the resin (A).
    [0101] [0101] <Structural unit (a5)> Examples of a non-leaving hydrocarbon group carried by the structural unit (a5) include groups having a linear, branched or cyclic hydrocarbon group. Of these, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group.
    [0102] The alicyclic hydrocarbon group in R can be monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon group includes, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. The polycyclic alicyclic hydrocarbon group includes, for example, an adamantyl group and a norbornyl group.
    [0103] [0103] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by L ° ”is replaced by -O- or - CO- includes, for example, the groups represented by the formula (L1-1) at formula (L1-4). In the following formulas, * and ** each represent a binding site, and * represents an oxygen atom binding site.
    [0104] [0104] L is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
    [0105] [0105] The group represented by the formula (L1-1) includes, for example, the following divalent groups.
    [0106] [0106] The group represented by the formula (L1-2) includes, for example, the following divalent groups.
    [0107] [0107] The group represented by the formula (L1-3) includes, for example, the following divalent groups. OA AS M0 ak, A * ck „SS O a * XE ok” DoY OA, 2%
    [0108] [0108] The group represented by the formula (L1-4) includes, for example, the following divalent groups. O kk NGA ”AT A AG x x x Q xk OT DAT DH
    [0109] [0109] L ° ”is preferably a single bond or a group represented by the formula (L1-1).
    [0110] [0110] Examples of structural unit (a5-1) include the following structural units and structural units in which a methyl group corresponding to R ° in the structural unit (a5-1) in the following structural units is substituted with a hydrogen atom. H3 H3 Hs Hz Hz H Hs [and 0 “rt 0 te o ton: {ett O Te ° ooo (a5-1-1) (a5-1-2) (a5-1-3) (a5-1-4 ) (a5-1-5) (25-16)
    [0111] [0111] <Structural unit (II)> The resin (A) can further include a structural unit which is decomposed by exposure to radiation to generate an acid (hereinafter sometimes referred to as "structural unit (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.
    [0112] [0112] The structural unit having a sulfonate group or a carboxylate group in a side chain is preferably a structural unit represented by the formula (II-2-A "):
    [0113] [0113] Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
    [0114] [0114] X represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X * represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X ° represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X ° represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 'represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms.
    [0115] [0115] Examples of the organic cation of ZA * include an organic onum cation, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation and an organic phosphonium cation. Among these organic cations, an organic sulfonium cation and an organic iodonium cation are preferred, and an arylsulfonium cation is more preferred. Specific examples thereof include a cation represented by any one of formula (b2-1) to formula (b2-4) (hereinafter sometimes referred to as "cation (b2-1)" depending on the number. the formula).
    [0116] [0116] PIE (R ”) m2 (R °% n2 89 9 RS O0) D2s * -CH-C — RP12 Rb6 À 4 Rb10 pb11 (b2-1) (b2-2) (b2-3) ( RES 2 (RP) +4 eu AR s + (b2-4)
    [0117] The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.
    [0118] [0118] Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-methyladamantan-2-yl group, a 2-ethyladamantan-2- group. yl, 2-isopropyladamantan-2-yl group, methylnorbornyl group, isobornyl group and the like. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.
    [0119] [0119] Examples of an aromatic hydrocarbon group include aryl groups such as phenyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group and examples of the aromatic hydrocarbon group having a chain hydrocarbon group include a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a p- group. ethylphenyl, a p-tert-butylphenyl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, and the like and examples of the aromatic hydrocarbon group having an alicyclic hydrocarbon group include a p-cyclohexylphenyl group, a p-adamantylphenyl group and the like.
    [0120] [0120] Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.
    [0121] The ring formed by bonding R ° * and RP with one another, with the sulfur atoms to which R® * and R ”are linked, can be a monocyclic, polycyclic, aromatic, non-aromatic ring, saturated or unsaturated. This ring includes a ring having 3 to 18 carbon atoms and is preferably a ring having 4 to 18 carbon atoms. The sulfur-containing ring includes a 3- to 12-membered ring and is preferably a 3- to 7-membered ring and includes, for example, the following rings and the like. * represents a binding site.
    [0122] [0122] The cycle formed by combining RP and RP! ° together can be a monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated ring. This ring includes a 3 to 12 membered ring and is preferably a 3 to 7 membered ring. The ring includes, for example, a thiolan-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, a 1,4-oxathian-4-ium ring and the like. The ring formed by combining RE “and RP! 2 together can be a monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated ring. This ring includes a 3 to 12 membered ring and is preferably a 3 to 7 membered ring. Examples of these include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, an oxoadamantane ring and the like.
    [0123] 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.
    [0124] [0124] b2-c-21 -c- b2-c-23 b2-c-24) (b2-c-25 (02021) (b2-c-22) (2023) (02024) (02028) (b2- c-26) (b2-c-27) 5 [0125] Examples of cation (b2-2) include the following cations and the like. + + + DOD dd OO (b2-c-28) (b2-c-29 ) (b2-c-30)
    [0126] [0126] Examples of cation (b2-3) include the following cations and the like.
    [0127] [0127] Examples of cation (b2-4) include the following cations and the like. OO Sen OO G (b2-c-35) © (b2-c-36) (0 (b2-c-37) N HzC, Hs SE Zoon LOO HaC, © (b2-c-38) HA (b2-c -39) U (b2-c-40) Q 3 5) tC4He + S: (À SE JOO 3 O0 HC (b2-c-41) N (b2-c-42) ® (62-c-43) t -C4Hg t-C4H9 t-C4Ha Sen ASS OO G (b2-c-44) © (b2-c-45) (y (b2-c-46) tC4He t-C4Ho
    [0128] [0128] The structural unit represented by the formula (II-2-A ") is preferably a structural unit represented by the formula (II-2-A): RS
    [0129] [0129] The structural unit represented by the formula (II-2-A) is preferably a structural unit represented by the formula (II-2-A-1): RB
    [0130] [0130] The structural unit represented by the formula (II-2-A-1) is preferably a structural unit represented by the formula (II-2-A-2): RS A}
    [0131] [0131] The structural unit represented by the formula (II-2-A ") includes, for example, the following structural units, structural units in which a group corresponding to a methyl group of RS is substituted by an atom of hydrogen, a halogen atom (for example, a fluorine atom) or an alkyl group having 1 to 6 carbon atoms which may optionally have a halogen atom (for example, a trifluoromethyl group, etc.) and the structural units mentioned in WO 2012/050015 A. ZA ”represents an organic cation.
    [0132] [0132] The structural unit having a sulfonio group and an organic anion in a side chain is preferably a structural unit represented by the formula (II-1-1): R'l4 Len RIB (I1-1-1) OO —A "—RH-87 plz
    [0133] [0133] Examples of a structural unit including a cation in the formula (II-1-1) include the following structural units and structural units in which a group corresponding to R! * Is substituted by a hydrogen atom, a fluorine atom, a trifluoromethyl group or the like. H3 Hz Hs Hs Hs Hz re "E 7" E TE Jess
    [0134] [0134] Examples of the organic anion represented by A include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion and a carboxylic acid anion. The organic anion represented by A is preferably a sulfonic acid anion, and the sulfonic acid anion is preferably an anion included in the subsequently mentioned salt represented by the formula (B1).
    [0135] [0135] Examples of the sulfonylimide anion represented by A include the following. Fa CF Fa2 £ C —CFs E - 2 025 Cs O2 CF ie CF2 028 Fa O, S — C | Len ol Lt O2S-CF3 Os Re O3S-CF2 Fo O, S — CF, O, S — CF, Fs F, 0-C —CF3
    [0136] [0136] Examples of the sulfonylmethide anion include the following. £ F3 F2 -CF3 O, S CF; O, S-CF, bone, ©, | F2 0, | - F4C, Fo O2 | F, C-S 5 FsC-C-S = FXX-C-S “O, S-CF3 O2S-GF2 O25-CFs CF F, C-CF;
    [0137] [0137] Examples of the carboxylic acid anion include the following. O 0 0 D _ Ho HC A HEA een Oe
    [0138] [0138] Examples of structural unit represented by formula (II-1-1) include structural units represented by the following formulas.
    [0139] When the structural unit (IT) is included in the resin (A), the content of the structural unit (IT) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and more preferably 3 to 10 mol%, based on all the structural units of the resin (A).
    [0140] [0140] The resin (A) can include structural units other than the structural units mentioned above, and examples of such structural units include structural units well known in the art.
    [0141] The resin (A) is preferably a resin composed of a structural unit (a1) and a structural unit (s), that is to say a copolymer of a monomer (a1) and a monomer (s).
    [0142] [0142] <Resin other than resin (A)> Regarding the resist composition of the present invention, the resin other than resin (A) can be used in combination. The resin other than the resin (A) includes, for example, a resin including a structural unit (a4) or a structural unit (a5) (hereinafter sometimes called resin (X)). The resin (X) is preferably a resin including a structural unit (a4), in particular. In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, and more preferably 45 mol% or more, based on the total of all the structural units of the resin (X). Examples of a structural unit, which may be further included in the resin (X), include a structural unit (a1), a structural unit (a2), a structural unit (a3), and structural units derived from other monomers. known. In particular, the resin (X) is preferably a resin composed only of one structural unit (a4) and / or one structural unit (a5). The respective structural unit constituting the resin (X) can be used alone, or two or more structural units can be used in combination. By using a monomer from which these structural units are derived, it is possible to produce a resin by a known polymerization process (eg, radical polymerization process). The content of the respective structural units included in the resin (X) can be adjusted according to the amount of the monomer used in the polymerization.
    [0143] [0143] When the resist composition includes the resin (X), the content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, more preferably 1 to 40 parts by mass, more preferably 1 to 30 parts by mass, and more preferably 1 to 8 parts by mass, based on 100 parts by mass of the resin (A).
    [0144] [0144] The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less. , based on the solid component of the resist composition. When including resins other than resin (A), the total content of resin (A) and resins other than resin (A) is preferably 80% by mass or more and 99% by mass or less, and more preferably 90 wt% or more and 99 wt% or less, based on the solid component of the resist composition. The solid component of the resist composition and the content of the resin can be measured by a known analytical means such as liquid chromatography or gas chromatography.
    [0145] [0145] <Acid Generator (B)> A nonionic or ionic acid generator can be used as an acid generator (B). Examples of the nonionic acid generator include sulfonate esters (eg, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (eg, disulfone, ketosulfone, sulfonyldiazomethane) and the like. Typical examples of the ionic acid generator include onium salts containing an onium cation (eg, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the anion of the onium salt include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion and the like.
    [0146] [0146] The acid generator (B) is preferably an acid generator containing fluorine, and more preferably a salt represented by formula (B1) (hereinafter sometimes called “acid generator (B1). "): + -O, S 7 LM + - 3 dy (B1) 1 where, in formula (B1), Q% and Q ° each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms , LP Represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CHz- included in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom included in the hydrocarbon group saturated divalent may be substituted with a fluorine atom or a hydroxy group, Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH> - included in the alicyclic hydrocarbon group can be replaced by -O-, -S (O) 2- or -CO-, and Z * represents an org cation anique.
    [0147] [0147] Examples of the perfluoroalkyl group represented by rQ "* and QP2 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl and a perfluorohexyl group Preferably, QP 1 and Q 2 are each independently a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.
    [0148] [0148] 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. Specific examples thereof 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-1,6-diyl group, heptan-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group , an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group , a hexadecane-1,16-diyl group and a heptadecane-1,17-diyl group; branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2 group , 4-diyl, a 2-… methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group and a 2-methylbutane-1,4- group diyl; monocyclic divalent alicyclic saturated hydrocarbon groups which are cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group and cyclooctane-1,5 -diyl; and polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornan-1,4-diyl group, norbornan-2,5-diyl group, adamantane-1,5-diyl group and adamantane-2,6-diyl group.
    [0149] [0149]
    [0150] [0150] N O 03 ax LO 1:05 x Oo x No A; ba T _ DS, be ”077
    [0151] In the groups represented by the formula (b1-1) in the formula (b1-3), when -CHz- included in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of atoms of carbon before replacement is taken as the number of carbon atoms of the saturated hydrocarbon group.
    [0152] [0152] 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 © Ate x A * ud sr RS (o1-4) (b1-5) ° (b1-6) D X b16 O Ao Oe Ao Oe NM b18 "*
    [0153] [0153] Examples of the group represented by the formula (b1-3) include the groups represented by the formula (b1-9) to the formula (b1-11). A ASS OS; _ AA I
    [0154] [0154] In the groups represented by the formula (b1-9) in the formula (b1-11), when a hydrogen atom included in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before the substitution is taken as the number of carbon atoms of the saturated hydrocarbon group.
    [0155] [0155] Examples of an alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.
    [0156] [0156] Examples of the group represented by the formula (b1-4) include the following: Q 0 Q 0 CH;
    [0157] [0157] Examples of the group represented by the formula (b1-5) include the following: AN Ah Ath Ao A Ad Sa ANSE À va As A Ö ij CHs CHs No. 2 3 CHs 3, APM N Ati AA AA “OO ; Yo. Ie eN 79.0 | Ö Ç T y ï +
    [0158] [0158] Examples of the group represented by the formula (b1-6) include the following: Loto Acte tuna ZA ZN
    [0159] [0159] Examples of the group represented by the formula (b1-7) include the following: CHs Ee Aak. Ag Q x Q Ede x AD AAST LAS op Je Ad CS AIA
    [0160] [0160] Examples of the group represented by the formula (b1-8) include the following: sek Lx, x Vo Pa DEAN Le
    [0161] [0161] Examples of the group represented by the formula (b1-2) include the following: LA he Saut AH TO HA PE, X tho Ge Ho HD A x HA. A, A alt A ak; ‘° Do CH3
    [0162] [0162] Examples of the group represented by the formula (b1-9) include the following:
    [0163] [0163] Examples of the group represented by the formula (b1-10) include the following:
    [0164] [0164] F F3 F Fa of Fe OE F3 hole "6 4 & to CHs OH O
    [0165] [0165] Examples of the group represented by the formula (b1-11) include the following: Hs F F F F
    [0166] [0166] Examples of the alicyclic hydrocarbon group represented by Y include the groups represented by formula (Y1) to formula (Y11) and formula (Y36) to formula (Y38). When -CH; - included in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -S (O) 2- or -CO-, the number may be 1, or 2 or more. Examples of such groups include groups represented by formula (Y12) to formula (Y35) and formula (Y39) to formula (Y41). > On NA M1) (2) (13) (Y4) V5) (19) mm (Y8) (Y9) (Y10) (11) Oo. N eh, 0 PAP OM KR 7 OO (via) (113 019 015) 018) (0117) 0118) (v19) (van, (2) N22) ODS dd HD AD GC 575 67 DSO 4) 4) My to 70 (Y23) (Y24) (26) (v26) (v27) (28) (129) (Y30) vat) x (32)>) D 500 OP 20 M; (Y33) (Y34) (Y35) (Y36) (Y37) (Y38) (Y39) (Y40) O (Yy41) The alicyclic hydrocarbon group represented by Y is preferably a group represented by any one of the formula ( Y1) to formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31) and formula (Y39) to formula (Y41), more preferably a group represented by formula (Y11), formula (Y15), formula (Y16), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) or formula (Y40), and more preferably a group represented by formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) or formula (Y40). The alicyclic hydrocarbon group represented by Y is a spiro ring including an oxygen atom in the formula (Y28) in the formula (Y35), the formula (Y39) in the formula (Y40) and the like, the alkanediyl group between two atoms oxygen preferably has one or more fluorine atoms. Among the alkanediyl groups included in a ketal structure, it is preferred that a methylene group adjacent to the oxygen atom is not substituted with a fluorine atom.
    [0167] [0167] Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a group glycidyloxy, a group - (CHz); - CO-OR® * or a group - (CH2); a-0-CO-RP!
    [0168] [0168] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
    [0169] [0169] Examples of Y include the following CHa CH3 H3C-, CH3 OH 0 NV NN IN IN) NS oH -—- E UV A acdddge da 6: O CH EE € 4 wl
    [0170] [0170] Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an adamantyl group which may have a substituent, and -CHz- constituting the alicyclic hydrocarbon group or the adamantyl group may be replaced by -CO-, -S (O) 2- or -CO-. Y is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, or groups represented by the following formulas.
    [0171] The anion in the salt represented by the formula (B1) is preferably an anion represented by the formula (B1-A-1) to the formula (B1-A-55) [hereinafter sometimes referred to as "anion (B1-A-1) "according to the number of the formula], and more preferably an anion represented by any one of the formula (B1-A-1) to the formula (B1-A-4), the formula (B1- A-9), formula (B1-A- 10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40) and formula (B1-A-47) to formula (B1-A-55).
    [0172] [0172]
    [0173] [0173] a9! op ° al! os TL) Y _ 0387 Sa 7 0:57 SS 0 abt 02 9 © FTF FF ö _ So Ao 035 Sp (B1-A-13) (B1-A-14) O 0 (B1-A-15) OH 9 X OH b1 b2 el Qb BETA en OX PSE 0 0:57> Ö (B1-A-16) Ö (B1-A-18) (B1-A-17)
    [0174] [0174] OH OH
    [0175] [0175] e! OO © ar! ab R7 Qb1 d OPL d - On, A4 ja LA = LA O: S L 038 07 So 038 O Ö Qb2 È Qb2 (B1-A-33) (B1-A-34) (B1-A-35) F F
    [0176] [0176]
    [0177] Preferred anions in the salt represented by formula (B1) are anions represented by formula (B1a-1) through formula (B1a-34). HO
    [0178] [0178] Ay DM De es O O F F F
    [0179] [0179] Among these, anion represented by any one of the formula (B1a-1) to the formula (B1a-3) and of the formula (B1a-7) to the formula (B1a-16), the formula (B1a-18), formula (B1a-19) and formula (B1a-22) to formula (B1a-34) is preferable.
    [0180] [0180] Examples of the organic cation of Z * include an organic cation onium, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation and an organic phosphonium cation, and include those identical to the organic cation ZA ” in the structural unit represented by the formula (1I-2-A '). Among them, an organic sulfonium cation and an organic iodonium cation are preferable, and an arylsulfonium cation is more preferable.
    [0181] [0181] The acid generator (B) is a combination of the aforementioned anions and the aforementioned organic cations, and these can optionally be combined. Examples of the acid generator (B) are preferably combinations of an anion represented by any one of formula (B1a-1) to formula (B1a-3) and formula (B1a-7) to formula (B1a-16), formula (Bla 18), formula (Bla-19) and from formula (B1a-22) to formula (B1a-34) with a cation (b2-1) or a cation (b2-3).
    [0182] [0182] Examples of the acid generator (B) are preferably those represented by formula (B1-1) to formula (B1-48). Of these, those containing an arylsulfonium cation are preferred, and those represented by formula (B1-1) to formula (B1-3), formula (B1-5) to formula (B1-7), formula (B1-11) to formula (B1-14), formula (B1-20) to formula (B1-26), formula (B1-29) and formula (B1-31) to formula ( B1-48) are particularly preferable.
    [0183] [0183] I KF © AOF X CD AT Oo TD Oo ”, LA
    [0184] [0184]
    [0185] [0185] Oo LF 9 @ F O Oo F
    [0186] [0186]
    [0187] [0187] In the resist composition of the present invention, the content of acid generator is preferably 1 part by mass or more and 45 parts by mass or less, preferably 1 part by mass or more and 40 parts by mass or less, 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). The resist composition of the present invention can include either the acid generator (B) alone or a plurality of acid generators.
    [0188] [0188] <Solvent (E)> The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more and 99% by mass or less. The content of the solvent (E) can be measured, for example, by a known analytical means such as liquid chromatography or gas chromatography.
    [0189] [0189] <Other components> The resist composition of the present invention may also include components other than the components mentioned above (hereinafter sometimes referred to as "other components (F)"), if necessary. The other components (F) are not particularly limited and it is possible to use various additives known in the field of resists, for example sensitizers, dissolution inhibitors, surfactants, stabilizers and dyes.
    [0190] [0190] <Preparation of resist composition> The resist composition of the present invention can be prepared by mixing a salt (I), a resin (A), an acid generator (B), and if necessary, resins other than resin (A), a solvent (E), a deactivating agent (C) and other components (F). The order of mixing these components is any order and is not particularly limited. It is possible to choose, as the temperature during mixing, a suitable temperature of 10 to 40 ° C, depending on the type of the resin, the solvent solubility (E) of the resin and the like. It is possible to choose, as the mixing time, an appropriate time of 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited and it is possible to use mixing with stirring. After mixing the respective components, the mixture is preferably filtered through a filter having a pore diameter of about 0.003 to 0.2 µm.
    [0191] [0191] <Method for producing a resist pattern> The method for producing a resist pattern of the present invention includes: (1) a step of applying the resist composition of the present invention to a substrate, (2) a step of drying the composition applied to form a composition layer, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and (5) a step of development of the heated composition layer.
    [0192] [0192] (Applications) The resist composition of the present invention is suitable as a resist composition for exposure to a KrF excimer laser, a resist composition for exposure to an ArF excimer laser, a resist composition for exposure to an ArF excimer laser. electron beam (FE) or a resist composition for exposure to extreme ultraviolet (UVE), and more suitable as a resist composition for exposure to an electron beam (FE) (or EB for "electron beam") or as a The resist composition for exposure to UVE and the resist composition is useful for the fine processing of semiconductors.
    [0193] The present invention will be described more specifically by way of examples. The percentages and the parts expressing the contents or the amounts used in the examples are by weight unless otherwise indicated.
    [0194] [0194] Example 1: synthesis of the salt represented by formula (I-4)
    [0195] [0195] Example 2: synthesis of the salt represented by formula (I-13)
    [0196] [0196] Example 3: synthesis of the salt represented by formula (I-14)
    [197] [197] Example 4: Synthesis of the salt represented by the formula (I-15) 0 0 MeO COOMe CF: SO: H CE3SO7 5 + yo O MeO COOMe 9 Me er, „X (1-15-b) (1- 13-c) Me
    [0198] [0198] Example 5: Synthesis of the salt represented by the formula (I-17) COQ De CF3SO3H UD CF2SO7 S + Meo 9 O Meo. OOMe Ad 9 (1-17-b) (13-c) OMe 0
    [0199] [0199] Example 6: Synthesis of the salt represented by the formula (I-21) CO MeO OOMe | CF: S0: H CO CF, S0- 9 + BEE oo MeO OOMe 9 OMe Ar, MeO (I-21-b) (1-13-c) OMe Lo NaOH ion exchange resin NaOH oxalic acid XX DO _ —_— —Pyi 5.05 Meo coo CF3S03 => Cl "y MeO Me (1-21) Ion exchange resin: Ion exchange resin / oxalic acid: oxalic acid) 3.84 parts of a compound represented by formula (I -21-b), 30 parts of chloroform, 3.30 parts of a compound represented by formula (I-13-c) and 4.37 parts of trifluoromethanesulfonic acid were mixed, which was followed by a stirring at 23 ° C for 30 minutes then cooling to 5 ° C. To the mixture thus obtained, 6.12 parts of trifluoroacetic anhydride was added dropwise over minutes, which was followed by stirring at 23 ° C. To the mixture thus obtained, 40 parts of ion-exchanged water was added and, after stirring at 23 ° C for 30 minutes, an organic layer was separated by separation. thus obtained, 35 parts of a solution of hydr 10% sodium oxide was added, and after stirring at 23 ° C for 30 minutes an organic layer was isolated by separation. This operation was performed twice. The organic layer thus obtained was concentrated and then the concentrate was passed through an ion exchange resin (Aldrich (chloride form QAE Sephadex® A-25)) using methanol as a developing solvent. The solution (which passed through the ion exchange resin) thus obtained was concentrated then 80 parts of chloroform and 40 parts of a 10% aqueous sodium hydroxide solution were added and, after stirring at 23 ° C for 30 minutes, an organic layer was isolated by separation. To the organic layer thus obtained 40 parts of a 5% aqueous solution of oxalic acid was added and, after stirring at 23 ° C for 30 minutes, an organic layer was isolated by separation. To the organic layer thus obtained, 40 parts of ion-exchanged water was added, and after stirring at 23 ° C for 30 minutes, an organic layer was isolated by separation. This water washing operation was carried out five times. After the organic layer thus obtained was concentrated, 30 parts of t-butyl methyl ether was added to the residue thus obtained, which was followed by stirring at 23 ° C for 30 minutes and then filtration to obtain 3.88 parts of a salt represented by formula (I-21). MASS (ESI spectrum (+)): 459.1 [M + H] "
    [0200] [0200] Synthesis of Resin The compounds (monomers) used in the synthesis of the resin (A) are indicated below. Hereinafter, these compounds are referred to as “monomer (a1-1-3)” depending on the number of the formula. ae ok CH = 0 0 OÖ (a1-1-3) (a1-2-6) TT (a1-4-2)
    [0201] [0201] Synthesis Example 1 [Synthesis of Resin A1] A monomer (a1-4-2), a monomer (a1-1-3) and a monomer (a1-2-6) were used as monomers. , and these monomers were mixed in a molar ratio of 38:24:38 [monomer (a1-4-2): monomer (a1-1-3): monomer (a1-2-6)], and methyl isobutyl ketone was added to this mixture of monomers in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile as an initiator was added in an amount of 7 mol% based on the total molar number of all the monomers, which was followed by polymerization with heating at 85 ° C. for about 5 hours. To the polymerization reaction mixture thus obtained an aqueous solution of p-toluenesulfonic acid was added.
    [0202] [0202] <Preparation of Resist Compositions> As shown in Table 1, the following respective components were mixed and the mixtures thus obtained were filtered through a fluororesin filter having a pore diameter of 0.2 µm for preparing resist compositions.
    [0220] [0220] Table 1 Table 1 Salt generator (I) Copes agent N Acid deactivating resin (C Composition | A1 = B1-43 = I-4 = 110 ° C / 1 10 parts | 3.4 parts 0 , 7 part 120 ° C Composition | A1 = B1-43 = 110 ° C / 2 10 parts | 3.4 parts 0.5 part 0.2 part 120 ° C Composition | A1 = B1-43 = [-13 = | 110 ° C / 3 10 parts | 3.4 parts 0.7 part 120 ° C Composition | A1 = B1-43 = 1-14 = 110 ° C / 4 10 parts | 3.4 parts 0.7 part 120 ° C Composition | A1 = B1-43 = [-15 = TT 110 ° C / 5 10 parts | 3.4 parts 0.7 part 120 ° C 6 10 parts | 3.4 parts 0.7 part 120 ° C Composition | A1 = B1-43 = I-21 = 110 ° C / 7 10 parts | 3.4 parts 0.7 parts 120 ° C Composition | A1 = B1-43 = IX-1 = 110 ° C / Comparative | 10 parts | 3 , 4 parts 0.7 part 120 ° C 1 Composition | A1 = B1-43 = IX-2 = 110 ° C / Comparative | 10 parts | 3.4 parts 0.7 part 120 ° C 2
    [0203] [0203] <Resin> A1: resin A1 <Acid generator (B)> B1-43: salt represented by formula (B1-43) (synthesized in accordance with the examples of JP 2016-47815 A) O
    [0204] [0204] (Evaluation of the exposure of the resist composition with an electron beam) Each 6 inch (15.24 cm) diameter silicon wafer was treated with hexamethyldisilazane and then baked on a hot plate. direct at 90 ° C for 60 seconds. A resist composition was applied by centrifugal application (“spin coating”) to the silicon wafer so that the thickness of the composition layer was 0.04 μm. The coated silicon wafer was precooked on the direct hot plate at the temperature shown in the "PB" column of Table 1 for 60 seconds to form a composition layer. By means of a direct electron beam writing system [“ELS-F125 125 keV”, manufactured by ELIONIX INC.], Line and space patterns (pitch: 60 nm / line width: 30 nm) were entered directly while the exposure dose was changed in stages.
    [0205] [0205] <Evaluation of pattern margin melting (PCM)> The line width of the line pattern becomes smaller when the exposure is performed with a higher exposure dose, and thus the disappearance of the pattern is likely to occur. The number indicates the minimum line width (nm) of the resist pattern without observing the disappearance of the pattern due to melting or peeling in the formed line pattern with an effective or greater sensitivity exposure dose. The results are shown in Table 2. Example 7 Composition 1 Example 8 Composition 2 Example 9 Composition 3 Example 10 Composition 4 Example 11 Composition 5 Example 12 Composition 6 Example 13 Composition 7 Composition Comparative Example 1 P. 26 Comparative 1 Composition Comparative Example 2 P. 28 Comparative 2
    [0206] [0206] A salt and resist composition comprising the salt of the present invention show satisfactory pattern margin melting and are therefore useful for fine processing of semiconductors.
    权利要求:
    Claims (13)
    [1]
    1. A salt represented by formula (I):
    GU x [Lo s.-O + x! M (RS) m3 (RE) m2 where, in formula (I), R *, R2 and R each independently represent a halogen atom, an alkyl fluoride group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, and -CH> - included in the hydrocarbon group may be replaced by -O - or -CO-, m1 represents an integer from 0 to 4, and when m1 is 2 or more, a plurality of R * may be the same or different from each other, m2 represents an integer from 0 to 4, and when m2 is 2 or more, a plurarity of R2 may be the same or different from each other, m3 represents an integer from 0 to 4, and when m3 is 2 or more, a plurarity of R * may be the same or different from each other , and xt represents -CO- or -SO- or SO ”.
    [2]
    2. The salt according to claim 1, wherein R * represents a fluorine atom, an alkyl fluoride group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3. with 10 carbon atoms, and -CH2- included in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O- or -CO-.
    [3]
    3. The salt according to claim 1, wherein R * and R * each independently represent a fluorine atom, an alkyl fluoride group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 4 carbon atoms. alicyclic hydrocarbon group having 3 to 10 carbon atoms and -CH: - included in the alkyl group and the alicyclic hydrocarbon group can be replaced by -O- or -CO-.
    [4]
    4. The salt of claim 1, wherein m1 represents an integer of 0 to 3
    [5]
    5. The salt of claim 1, wherein m2 and m3 each independently represent an integer of 0 to 2.
    [6]
    6. The salt of claim 1, the salt being represented by any one of formula (I-1) to formula (I-24) “es Ses ga A Ÿ se Ÿ 2 2553 Xx, = re E> Fe ï R Ad “A Ÿ> TL de ep ei è do, Pr À in = x vid at VS es On 04 we | 4 “a ee Pr Sr ee As AA tj 323 a ss a “a Le a $ OD„ 8 Ne ern Ÿ pa tb, gg uu F1 gg Ee te, TT> EG> x TS CU OUR OE # © RR I 5 RO ON A »AA À dared Si gg Ç y A, AA Ste Be, Nr Ee {ij a {7% BE + a “> se À, + De 5 ta Fr gs + a gp
    ES AVS OS NS e = + to 5 PT A JD En 5, “5 8 dt u ze ER ds Si ET WIE}
    aa CT Ed À A Ko LS dd ol A ee 2000 0 240 a “es X 3 A a Ae“ er ve Der SS AA Sr ca FF Tr & 1 x [AA, &} ps iS] NS ER {bte} INR { 18 pau ”ep” ga a $ S Tx LS; y A 120 y Age ee and ee 5 FF 3 OPT Pf erg SE CEY se na DE Se an Le {37 04187 DIN 12; AND: er ”er er è. te U he 5 x H On | 0 4 A0 2 +2 À 2220 y se ”of mp ff ad SA = 5 783 N CR a U AM A ES gt Fe gi, À 5 x ee ph EP 59 Bx ë | ee: 2H ST 53-241
    [7]
    7. A deactivating agent comprising a salt according to any one of claims 1 to 6.
    [8]
    8. A resist composition comprising the deactivating agent of claim 7, a resin including a structural unit having an acid labile group, and an acid generator.
    [9]
    9. The resist composition of claim 8, wherein the resin including a structural unit having an acid labile group includes at least one resin selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by the formula (a1-2):; nes RES Ha / Ms / CO © = 9 (st 182 AT> (CH TD CHA gas PAPE Sant ge Tros} AJ Ya {at-15 {ai-2} where, in the formula (a1-1) and the formula (a1-2), L ° * and L ° * each independently represent -O- or * -O- (CH2) k1-CO-O-, k1 represents an integer from 1 to 7, and * represents a binding site to -CO-, R ° * and R °° each independently represent a hydrogen atom or a methyl group, R °° and R ° each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group obtained by combining these groups, m1 represents an integer from 0 to 14, nl represents an integer from 0 to 10, and nl 'represents an integer from 0 to 3.
    [10]
    10. The resist composition of claim 8, wherein the resin comprising a structural unit having an acid labile group comprises a structural unit represented by the formula (a2-A):
    FL Jaso | 7 (a2-A) en (RS} srib where, in the formula (a2-A), R250 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms optionally having one atom of halogen, R °°! represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms. carbon, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group, A2 ° 0 represents a single bond or * -X °° 1- (a252-x252) 5; and * represents a binding site to the carbon atom to which -R2 ° is attached, A represents an alkanediyl group having 1 to 6 carbon atoms, x °° 1 and X each independently represent -O-, -CO-O- or -O- CO-, nb represents 0 or 1, and mb represents an integer of 0 to 4, and when mb is an integer of 2 or more, a plurality of R ° ** may be the same or different from each other.
    [11]
    11. The resist composition of claim 8, wherein the acid generator includes a salt represented by formula (B1): oh Z 038, | A (B1) Ÿ y * a where in formula (B1), Q "* and Q ° each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, LP! Represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CHz- included in the saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH> - included in the alicyclic hydrocarbon group may be replaced by -O- , -S (O) 2- or -CO-, and Z 'represents an organic cation.
    [12]
    12. The resist composition of claim 8 further comprising an acid generating salt having an acidity lower than that of an acid generated by the acid generator.
    [13]
    13. A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition of claim 8 to a substrate, (2) a step of drying the applied composition to form a layer. composition, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and (5) a step of developing the heated composition layer.
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    法律状态:
    2021-06-28| FG| Patent granted|Effective date: 20210518 |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2019104595|2019-06-04|
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