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    • 专利摘要:
    One object is to provide a salt capable of producing a resist pattern with satisfactory CD uniformity (CDU), and a resist composition comprising the salt. The present invention relates to a salt represented by formula (I) as defined in claim 1 wherein in formula (I), R1, R2 and R3 each independently represent a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 12 carbon atoms, and -CH 2- 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 R1 may be the same or different from each other, m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R2 may be the same or different from each other, and m3 represents an integer of 0 to 4, and when m3 is 2 or more, a plurality of R3 may be the same or different from each other.
    公开号:BE1026753B1
    申请号:E20195797
    申请日:2019-11-15
    公开日:2020-10-12
    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 which contains this salt as well as a method for producing a resist pattern using the resist composition. BACKGROUND OF THE INVENTION
    [0002] [0002] Patent document 1 mentions a resist composition including 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.
    [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] [0004] An object of the present invention is to provide a salt capable of producing a resist pattern having a CD (CDU) uniformity better than that of a resist pattern formed from a resist composition comprising the resin. comprising the salts mentioned above.
    [0005] [0005] The present invention includes the following inventions.
    [1] [1] A salt represented by formula (I): Gum S, 7O + SO, © (RS) ma (R2) m2 where, in formula (I), R *, R2 and R each independently represent a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 12 carbon atoms, and -CH> - included in the hydrocarbon group may be replaced by -O- or - CO-,
    [2] [2] A deactivation agent comprising a salt according to [1].
    [3] [3] A resist composition comprising the 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 having an acid labile group is a resin including at least one resin 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):; | nn The RS The RS | << mrs Fo | Ho: 81 82 ue {ot el St SZ bre {at-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 bond to -CO-, R ° * and R °° each independently represent a d atom 'hydrogen 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 a an integer from 0 to 14, n1 represents an integer from 0 to 10, and n1 'represents an integer from 0 to 3.
    [5] [5] The resist composition according to [4], wherein the resin comprising a structural unit having an acid labile group comprises a structural unit represented by the formula (a2-A): | Ho A aso> {a2-À} a (RP> nb where, in the formula (a2-A), R250 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms having optionally a halogen atom, R °°! represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group, A2 ° 0 represents a single bond or * -X °° 1- (a252-x252) 5; and * represents a binding site to 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.
    [6] [6] The composition of resist according to any one of [3] to [5], where the acid generator includes a salt represented by the formula (B1): at z OS (BI)
    [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 of drying the applied composition to form a composition layer, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and (5) a step of developing the heated composition layer.
    [0006] [0006] It is possible to produce a resist pattern with satisfactory CD uniformity (CDU) by using a resist composition containing a salt of the present invention. Mode for implementing the invention
    [0007] [0007] As used herein, the term "(meth) acrylate" each 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] [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 reacting a salt represented by formula (Ia) with silver oxide in a solvent: (Rm GU G AgO , AT
    [0011] [0011] The salt represented by the formula (Ia) can be produced by reacting a compound represented by the formula (Ib) with a compound represented by the formula (Ic) in the presence of phosphorus pentoxide and methanesulfonic acid in a solvent, which is followed by bringing into contact with sodium iodide: Rent Q Rom P2O5 Nal AS -; CO: H + A CH3SO3H 3 u (RÈ) my COH; (R2} m2 (R °) m3 (R2) m2 (I-b) (I-c) (I-a) where all the symbols are identical to those defined above.
    [0012] Salt (I) can also be obtained by mixing a salt represented by formula (Id) in the presence of a basic catalyst in a solvent: Ra (R ') ma COH _ - Ss O3S-CF3z _ = CO , + (RS) m3 GO (Ra; ”(R °) m2 (Id) (I) where all symbols are the same as defined above. Examples of the base include triethylamine 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.
    [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 (Irc) in the presence = of trifluoromethanesulfonic acid and trifluoroacetic anhydride in a solvent: (Rm: 0 (R ') m CF3SO3H cu _ S —— Ss O2S — CF3 GO Cs 2 (or OH Al Ie (R °) ms (Ib) (Ic) (Ia) where all the symbols are identical to those defined above Examples of the solvent include chloroform, acetonitrile and the like The reaction is usually carried out at a temperature in a range of 0 to 60 ° C for 0.5 to 24 hours.
    [0014] [0014] The salt (I) can also be obtained by mixing a salt represented by the formula (Ie) in the presence of a basic catalyst in a solvent: R) m (Rm A. _ A - $ O3S-CFz3 —____ CO, (Rò) ms 3 (RZ) (R °) m3 (R ) M2 (Ie) (I) where all symbols are the same as defined above. Examples of the base include sodium hydroxide and the like Examples of the solvent include chloroform and the like.
    [0015] The salt represented by the formula (Ie) can be obtained by reacting a compound represented by the formula (Ib) with a compound represented by the formula (If) in the presence = of trifluoromethanesulfonic acid and trifluoroacetic anhydride in a solvent: R "m1 1 R n1 CF3SO3H À. 7 Ya (Fos CO2Me EA, De (RÈ) m2 (Ib) (If) (Ie) where all the symbols are identical to those defined above.
    [0016] <Deactivating agent, "Quencher"> The deactivating agent or quencher of the present invention comprises a salt (I). The quencher can comprise one salt (I) or two or more salts (I).
    [0017] [0017] <Resist composition> The resist composition of the present invention comprises a deactivating agent containing 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 called“ 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).
    [0018] [0018] The salt content (T) 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 amount of the solid component of a resist composition.
    [0019] <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 a 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 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 non-leaving hydrocarbon group mentioned later (hereinafter sometimes referred to as "structural unit (a5))) and other structural units derived from monomers known in the art.
    [0020] [0020] <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)").
    [0021] [0021] 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. .
    [0022] Examples of the hydrocarbon group for R2, R ° 2 and R33 include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and groups obtained by combining these groups.
    [0023] [0023] Examples of group (1) include the following groups.
    [0024] [0024] Specific examples of group (2) include the following groups. * represents a bond. A. O. 0 0 ° A A ”TD ro Ao APPD A ee * NO NOR * AL * Oo
    [0025] [0025] Monomer (a1) 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.
    [0026] 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 a hydrocarbon-alicyclic group is used in a resist composition, it is possible to improve the resolution of a resist pattern.
    [0027] The structural unit derived from a (meth) acrylic monomer having a group (1) is preferably a structural unit represented by the formula (a1-0) (hereinafter sometimes referred to as structural unit (a1- 0) ), a structural unit represented by formula (a1-1) (hereinafter sometimes called structural unit (a1-1)) or a structural unit represented by formula (a1-2) (hereinafter sometimes called structural unit ( a1-2)). These structural units can be used alone, or two or more structural units can be used in combination. The Ra01 - + ras + Ra5 C = C = Cc El
    [0028] [0028] R20! R ° * and R °° are preferably a methyl group.
    [0029] [0029] 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). Hs Hs Hs CH3 H Hs Ho Joe en Ho (a1-0-1) (a1-0-2) (a1-0-3) X $ 5 (a1-0-4) (a1-05) (6106) Hs Hs CH CHs H Ha HR OS Jo to to EE PE (107) (a1-0-8) (2105) (@ 1-0-10) (a1-0-11) (a1-0-12)
    [0030] [0030] 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 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.
    [0031] [0031] Examples of structural unit (a1-2) include a structural unit represented by any one of the formula (a1-2-1) to the formula (a1-2-6) and a structural unit in which a methyl group corresponding to R® in the structural unit (a1-2) is substituted with a hydrogen atom, and the structural units represented by the formula (a1-2-2), the formula (a1-2-5 ) and formula (a1-2-6) are preferred.
    [0032] When the resin (A) includes a structural unit (a1-0) and / or a structural unit (a1-1) and / or a structural unit (a1-2), their total content is usually 10 to 95% by moles, preferably 15 to 90% by moles, more preferably 20 to 85% by moles, more preferably 25 to 70%, and more preferably 30 to 70% by moles based on all structural units of the resin (A).
    [0033] In structural unit (a1), examples of 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 ) "):
    [0034] 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.
    [0035] [0035] 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 atoms carbon or an alicyclic hydrocarbon group, and more preferably a methyl group or an ethyl group.
    [0036] [0036] -OC (R23%) (R235) -0-R2% in structural unit (a1-4) is removed by contacting with an acid (eg p-toluenesulfonic acid) to form a hydroxy group.
    [0037] [0037] 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 formula (a1-4-12) and a structural unit in which a hydrogen atom corresponding to R °° is substituted with a methyl group, and more preferably the structural units represented by formula (a1-4 -1) to formula (a1-4-5) and formula (a1-4-10). AH, ï CH: de - CH - CH,: on, H - OH & do. Vd DOC) 00 POG dn Ie (at-4-2) (84-403) aaa CT am 5 KV; Wies) {a1-4-8; "'He + HW H y 3 La ® Le CH SF SCH, ©“ Ott oen, do, z 6 À Sa Oe MARS OR ANT {at-4-83 {a1-4- 9} {at-4-10) {pf-4-111 a 4 sa
    [0038] 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).
    [0039] [0039] 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) ").
    [0040] [0040] 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.
    [0041] [0041] 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.
    [0042] 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).
    [0043] [0043] The structural unit (a1) also includes the following structural units. Tel Lu FO # 0 SO FO Fo% 05H D DD KR © (at-3-1) (a1-3-2) (a1-3-3) (a1-3-4) (a1-3-5) ( a1-3-6) (a1-3-7)
    [0044] 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 most preferably 20 to 60 mole%, based on all the structural units of the resin (A).
    [0045] [0045] <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.
    [0046] [0046] <Structural unit (a2)> The hydroxy group possessed by the structural unit (a2) may be 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 where high energy rays such as a KrF (248nm) excimer laser are used as the exposure source, electron beam or extreme ultraviolet light (UVE), it is preferred to use a structural unit (a2) having a phenolic hydroxy group as the structural unit (a2). When using an ArF (193nm) excimer laser or the like, a structural unit (a2) having an alcoholic hydroxy group is preferably used as the structural unit (a2), and more preferably a structural unit (a2- 1) mentioned later. The structural unit (a2) can be included alone, or two or more structural units can be included.
    [0047] In structural unit (a2), examples of 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
    [0048] Examples of the halogen atom in R ° ® include a fluorine atom, a chlorine atom and a bromine atom.
    [0049] [0049] 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-O-A92-CO-0- or * -0-A-52-CO-O- are preferred.
    [0050] Examples of alkanediyl group include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane group -1,5- divle, hexane-1,6-diyl group, butane-1,3-diyl group, group
    [0051] [0051] 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-.
    [0052] [0052] mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.
    [0053] Examples of structural unit (a2-A) include structural units derived from monomers mentioned in JP 2010-204634 A and JP 2012-12577 A.
    [0054] 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.
    [0055] [0055] 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)” ).
    [0056] 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.
    [0057] [0057] 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. [4 pre | 1H = | [8 pr] IE: + rs Bt
    [0058] [0058] 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 the structural units of the resin (A).
    [0059] <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. Preferably, an γ-butyrolactone ring, an adamantanelactone ring or a bridged ring including a γ-butyrolactone ring structure (eg, a structural unit represented by the following formula (a3-2)) is exemplified.
    [0060] [0060] 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: pate rats ses fe Font} Lork + roof ter + 20 de Le Va (RE) pa HT Be @ pr O O
    [0061] [0061] 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.
    [0062] In formula (a3-1) with formula (a3-3), preferably, L ° * to L °° are each independently -O- or a group in which k3 is an integer of 1 to 4 in * -O- (CH2) es-CO-O-, more preferably -O- and * -O- CH2-CO-O-, and more preferably an oxygen atom, R818 at R °! 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.
    [0063] In the formula (a3-4), R ** is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or a group ethyl, and more preferably a hydrogen atom or a methyl group, R22 is preferably a carboxy group, a cyano group or a methyl group, 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) ':
    [0064] [0064] Examples of structural unit (a3) include structural units derived from the monomers mentioned in JP 2010-204646 A, from the monomers mentioned in JP 2000-122294 A and from the monomers mentioned in JP 2012-41274 A. The unit structural (a3) is preferably a structural unit represented by any of the formula (a3-1-1), the formula (a3-1-2), the formula (a3-2-1), the formula ( a3- 2-2), formula (a3-3-1), formula (a3-3-2) and formula (a3-4-1) to formula (a3-4-12), and the units in which the methyl groups corresponding to R ° * $, RP, R220 and R2 * in the formula (a3-1) in the formula (a3-4) are substituted with hydrogen atoms in the structural units below above.
    [0065] [0065] CH3 H3 Hs CH3 Hs Hz Hz Hz HS} rer Dr tt tnt} TH
    [0066] [0066] 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).
    [0067] [0067] <Structural unit (a4)> Examples of structural unit (a4) include the following structural units: Lt R41
    [0068] [0068] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group. , a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; and polycyclic alicyclic saturated hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* represents a bond).
    [0069] Examples of structural unit (a4) include a structural unit represented by at least one chosen from the group consisting of formula (a4-0), formula (a4-1), formula (a4-2), the formula (a4-3) and the formula (a4-4): R ° ton + (a4-0) O
    [0070] 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.
    [0071] [0071] L “is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
    [0072] [0072] 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: 1 EN: tr Lu - fa © & © + k dre 06 (a4-0-1) (a4-0-2) (a4-0-3) (a4-0-4) PEPE Pet Pp Et Fs 2Fs FC Sr ad Fa F3 F2 8F17 @ + 07) (040-8) (a4-0-9) (eso 0) (a4-0-11) (a4-0-12) ter tet A WET cs CaFs 2F5 FÂ FF: sF13
    [0073] [0073] H, Ra41 Le ST
    [0074] [0074] 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.
    [0075] Examples of a substituent optionally 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:
    [0076] Examples of a saturated hydrocarbon group in A® ** ° include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a 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 a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* represents a binding site): Examples of a group formed by combination include a group obtained by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, and include an alkanediyl group-alicyclic hydrocarbon group, an alicyclic hydrocarbon group-alkyl group, an alkanediyl group-alicyclic hydrocarbon group-alkyl group and the like.
    [0077] [0077] 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).
    [0078] [0078] 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— (a44 _ — _ pa47 (a-g2 ) where in the 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 halogen atom,
    [0079] The number of carbon atoms of the saturated hydrocarbon group for A ° * ° is preferably 1 to 6, and more preferably 1 to 3.
    [0080] The preferred structure of the group represented by the formula (a-g2) is the following structure (* is a binding site to a carbonyl group).
    [0081] [0081] 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.
    [0082] Examples of divalent saturated hydrocarbon group represented by A3% 2, A and A ** in the group represented by the formula
    [0083] [0083] 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, 2e ee pe es x, OL, Oo Le AP se Ah TY Fr Ar ”T _ | O
    [0084] [0084] 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.
    [0085] [0085]
    [0086] Examples of structural unit represented by formula (a4-1) include a structural unit represented by formula (a4-2) and a structural unit represented by formula (a4-3): Hz RS 0 O ( a4-2) The
    [0087] [0087] 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.
    [0088] 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).
    [0089] [0089] Examples of the structural unit (a4) include a structural unit represented by the formula (a4-3): HR "
    [0090] [0090] 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.
    [0091] In formula (a4-3), L ° is preferably an ethylene group.
    [0092] 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).
    [0093] It is also possible to cite by way of example, as structural unit (a4), a structural unit represented by the formula (a4-4): bei SC (a4-4) pa ”where, in the formula ( a4-4), Rf ! represents a hydrogen atom or a methyl group, AR! represents - (CH2) j1-, - (CH2) j2-O- (CH2); 3- or - (CH2); 4-CO-O- (CH2) j5-, j1 to j5 each independently represent an integer of 1 to 6, and R22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom.
    [0094] [0094] Examples of the saturated hydrocarbon group for R * include those which are the same as the saturated hydrocarbon group represented by R2 * 2. R ° 22 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and more preferably an alkyl group having 1 to 6 carbon atoms having a fluorine atom.
    [0095] In the formula (a4-4), A! is preferably - (CHz); 1-, more preferably an ethylene group or a methylene group, and more preferably a methylene group.
    [0096] 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
    [0097] 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).
    [0098] <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. The structural unit (a5) includes, for example, a structural unit represented by the formula (a5-1): 51 Ho 55 / R52 where, in the formula (a5-1), R “! represents a hydrogen atom or a methyl group,
    [0099] The alicyclic hydrocarbon group in R ° 2 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.
    [0100] [0100] 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) in the formula (L1-4). In the following formulas, * and ** each represent a binding site, and * represents a binding site to an oxygen atom. A pa VE A er ”pW nn (L1-1) (L1-2) (L1-3) (L1-4) ° In the formula (L1-1), X represents * -O-CO- or * -CO -O- (* represents a binding site to L *), Lt represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms, L ** represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 atoms of carbon, and the total number of carbon atoms of L and L1 is 16 or less. In formula (L1-2), LS represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms, L ** represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms, and the number total carbon atoms of L3 and DL is 17 or less. In formula (L1-3), L $ represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms, L * and L each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms , and the total number of carbon atoms of L * °, L $ and LV is 15 or less. In the formula (L1-4),
    [0101] [0101] 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.
    [0102] [0102] The group represented by the formula (L1-1) includes, for example, the following divalent groups. "Na url AL‚ Ak ‚Ag Ay
    [0103] [0103]
    [0104] [0104] The group represented by the formula (L1-2) includes, for example, the following divalent groups. ON Do DY CH3 CH3 CHs „Oo Aho” Aho ”Aho Ah O"
    [0105] [0105] The group represented by the formula (L1-3) includes, for example, the following divalent groups. CHs © Q. DOES DA NO sis OY = “A CHs
    [0106] [0106] The group represented by the formula (L1-4) includes, for example, the following divalent groups.
    [0107] [0107] L ° ”is preferably a single bond or a group represented by the formula (L1-1).
    [0108] [0108] 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.
    [0109] [0109]
    [0110] [0110] <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.
    [0111] [0111] 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 "):
    [0112] [0112] Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
    [0113] [0113] 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.
    [0114] [0114] Examples of the organic cation of ZA * include an organic onium cation, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation and an organic phosphonium cation. Among these organic cations, an organic sulfonium cation and an organic iodonium cation are preferred, and an arylsulfonium cation is more preferred. Specific examples thereof include a cation represented by any one of formula (b2-1) to formula (b2-4) (hereinafter sometimes referred to as "cation (b2-1)" depending on the number. the formula).
    [0115] [0115] N Re (R ”) m2 (R °%) n2 69 9 R $ BC 2st-CH-C — RP12 Rb6 À 4 RP10 pb11 (b2-1) (b2-2) (b2-3) (RP13) 2 (D) sa + £ LA FA s + (b2-4)
    [0116] [0116] The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.
    [0117] [0117] 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.
    [0118] [0118] Examples of an aromatic hydrocarbon group include aryl groups such as phenyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group.
    [0119] [0119] 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.
    [0120] 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 ring containing a sulfur atom 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. LA A A AT LAN
    [0121] [0121] The cycle formed by combining RP and RPI 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.
    [0122] [0122] Among the cation (b2-1) to the cation (b2-4), a cation (b2-1) is preferred.
    [0123] [0123] Examples of cation (b2-1) include the following cations and the like. CHs CaHs pe tCaHe | | D N Os 7 © Or Les Os Or O5 ae; s Ô 3 € (62: 0-1) {b2-c-2) {b2-c-3) (b2-c-4) (b2-c-5) (b2-c-6) Ges Cathz CH3 CHg CHs © © © Le (Ms (ss iel Vet hel Vs (3e 7 =) Si a CHa (b2-c-7) (62-6-8) (b2-c-9) (b2-c-10) ( 02-6-17)
    [0124] [0124] © GO OH t-CaH9 (b2-c-14) (b2-0-15) (b2-c-12) (b2-c-13)> © Ö Ç OG 041 | 0 GT Og © F (b2-c-16) (b2-c-17) (b2-c-18) (b2-c-19) (b2-c-20)
    [0125] [0125]; D Oo, A (b2-c-21) (b2-c-22) (b2-c-23) (b2-c-24) (b2025) (b2-c-26) (b2-c-27)
    [0126] [0126] Examples of cation (b2-2) include the following cations and the like. + + +
    [0127] [0127] Examples of cation (b2-3) include the following cations and the like.
    [0128] [0128] Examples of cation (b2-4) include the following cations and the like. ©. (2 2 4) = ADS pc HS DS Cao (2 D ©) (b2-c-35) (b2-c-36) (b2-c-37) Hs Hs Hs> @ (2
    [0129] [0129] The structural unit represented by the formula (II-2-A ") is preferably a structural unit represented by the formula (II-2-A): RS
    [0130] [0130] The structural unit represented by the formula (II-2-A) is preferably a structural unit represented by the formula (II-2-A-1):
    [0131] [0131] 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
    [0132] [0132] 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.
    [0133] [0133] The structural unit having a sulfonio group and an organic anion in a side chain is preferably a structural unit represented by the formula (II-1-1): R114 Len ai (11-1-1) OO - All Rts “RIl2
    [0134] [0134] Examples of structural unit including a cation in formula (II-1-1) include the following structural units and structural units in which a group corresponding to R "* is substituted by a hydrogen atom, an atom. of fluorine, a trifluoromethyl group or the like Hs CH3 Hs Hs CHs CH3 E Pet Pt st TS HS} © © © SL IC OO ane © 0 SC CHs CHs CH CH CH oi PST ton, el ett 0 ons CH3
    [0135] [0135] 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).
    [0136] [0136] Examples of the sulfonylimide anion represented by A include the following. CFs Fa FzC-CF2 F Oa CF O2 Fz O257CF2 O, S —— CF, os, | | 'N | N [7 O3S-CF3 O2S-CF3 O2S-CF3 | —CF | - CF, FC-CF2 928 CF2 02870F2 CF3 (l-b-1) (l-b-2) (I-b-3) (I-b-4) (I-b-5)
    [0137] [0137] Examples of sulfonylmethide anion include the following.
    [0138] [0138] Examples of the carboxylic acid anion include the following. from ie AL in, od. KA Me CHs 9 Ö De ID TO OX or) 0 FFF re _ HG - AL EC HAS Ao pk “0 LK on FETT FF
    [0139] [0139] Examples of structural unit represented by formula (II-1-1) include structural units represented by the following formulas.
    [0140] [0140] 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).
    [0141] [0141] 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.
    [0142] 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).
    [0143] [0143] <Resin other than resin (A)> The resist composition of the present invention may include a resin other than resin (A), in addition to resin (A). The resin other than resin (A) ) includes, for example, a resin including a structural unit (a4) or a structural unit (a5) (hereinafter sometimes called resin (X)).
    [0144] [0144] 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, particularly preferred 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass, based on 100 parts by mass of the resin (A).
    [0145] [0145] 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. In the present description, "solid component of the resist composition" means the total amount of components obtained by removing a solvent (E) mentioned later from the total amount of the resist composition. The solid component of the resist composition and the Resin content can be measured by a known analytical means such as liquid chromatography or gas chromatography.
    [0146] [0146] <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.
    [0147] [0147] 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) "): Qh z1 * OS | LN (B1)
    [0148] [0148] Examples of the perfluoroalkyl group represented by Q% and QP include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group and a perfluorohexyl group.
    [0149] [0149] 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.
    [0150] [0150] The group in which -CH> - 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 the formula (b1 -1) to the formula (b1-3). In groups represented by formula (b1-1) with formula (b1-3) and groups represented by formula (b1-4) with formula (b1-11) which are specific examples thereof, * and ** represent a binding site, and * represents a binding to -Y.
    [0151] [0151] mm 9 b3 xk Oo [LS * x 0 ek No So x DS, ba T * | b6 „197
    [0152] 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.
    [0153] [0153] LP is preferably a single bond.
    [0154] [0154] 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).
    [0155] [0155] Examples of the group represented by the formula (b1-1) include the groups represented by the formula (b1-4) to the formula (b1-8).
    [0156] [0156] LP3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
    [0157] [0157] Examples of the group represented by formula (b1-3) include groups represented by formula (b1-9) to formula (b1-11). mt LL x AE OS a x oe
    [0158] [0158] 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.
    [0159] [0159] Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.
    [0160] [0160] Examples of the group represented by the formula (b1-4) include the following:
    [0161] [0161] Examples of the group represented by the formula (b1-5) include the following:
    [0162] [0162] Examples of the group represented by the formula (b1-6) include the following: A, SH Ah PA To 5 + DE PA ae ae; ij; 1 0 Ao Auto Kto Auto Athos oO # Ad A7
    [0163] [0163] Examples of the group represented by the formula (b1-7) include the following:
    [0164] [0164] Examples of the group represented by the formula (b1-8) include the following: x O ** x se sk To Dr PO La O O
    [0165] [0165] Examples of the group represented by the formula (b1-2) include the following: to “, Oo
    [0166] [0166] Examples of the group represented by the formula (b1-9) include the following:
    [0167] [0167] Examples of the group represented by the formula (b1-10) include the following:
    [0168] [0168] Examples of a group represented by the formula (b1-11) include the following: Hs 9 Ö ok Het F; F F X F © F F Hz F F3 F F3 zr AAN ho LA ALA re CH3
    [0169] [0169] 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).
    [0170] [0170]> 000-045-0574 2500 (Y1) (2) (13) (4) (Y5) (Ye) 7 (v8) (Y9) (Y10) (Y11) Os, OS Oo STADS R Hed
    [0171] [0171] 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) ja-CO-OR®! or a group - (CH2); - O-CO-RE (where RP represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or groups obtained by combining these groups, -CHz- included in an alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, - S (O) 2- or -CO-, an atom of hydrogen 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 ja represents an integer of 0 to 4) and the like.
    [0172] [0172] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
    [0173] [0173] Examples of Y include the following. CHa CHs H3C4, CH3 a0cAA 09 => 0% OH
    [0174] [0174]
    [0175] [0175] 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 -CH> - constituting the alicyclic hydrocarbon group or the adamantyl group can 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.
    [0176] [0176] The anion in the salt represented by formula (B1) is preferably an anion represented by formula (B1-A-1) to formula (B1-A-55) [hereinafter sometimes referred to as "anion (B1-A-1) "according to the number of the formula], and more preferably an anion represented by any one of the formula (B1-A-1) to the formula (B1-A-4), the formula (B1- A-9), formula (B1-A- 10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40) and formula (B1-A-47) to formula (B1-A-55).
    [0177] [0177] OH Oo OH a! Qb _ af! cu a! a2 _ On, A4 038 Lad -o sp OS O3S O ° O 9 (B1-A-1) (B1-A-2) (B1-A-3) ab! ‚Ol all Lab R2 Qt ab 7 On A4 ”028 On A4 7 OX A4 O3S 3 O3S L
    [0178] [0178] 0 OH QP1 gold OP a2 7 Sg c os or! Lab ve (B1-A-13) (B1-A-14) O ° (B1-A-15) OH 0 X OH a a2 oO ob! QP2 OH _ _ O o „en La AN of! „Ob oO O oe A 0 ro ok O 3 FT NF 6 (B1-A-16) (B1-A-18) (B1-A-17) | X
    [0179] [0179] QE Q »2 O CHs3 ed a“ 9 CHs - | A4 Ces o os o O> 9 5 ©) O (B1-A-25) (B1-A-26)
    [0180] [0180] oo Onis 9 ar! Qt R7 ob d ede _ =, A4 _ LA4 _ LA4 O3S L O3S So ”So O3S No Ô Qb2 È Qb2 (B1-A-33) (B1-A-34) (B1-A-35) F F F H
    [0181] [0181] 9 O O O = L_ 9, b y b1 b2 [SF 9 Q A O bl Ab2 b1 ab2
    [0182] [0182] Preferred anions in the salt represented by formula (B1) are anions represented by formula (B1a-1) to formula (B1a-34).
    [0183] [0183] O
    [0184] [0184] 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-30) is preferable.
    [0185] [0185] 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 formula represented by the formula (II-2-A "). Among them, an organic sulfonium cation and an organic iodonium cation are preferable, and an arylsulfonium cation is more preferable.
    [0186] [0186] The acid generator (B) is a combination of the above-mentioned anions and the above-mentioned organic cations, and these can optionally be combined. Examples of the acid generator (B) are preferably combinations of an anion represented by any one of formula (B1a-1) with formula (B1a-3) and formula (B1a-7) to formula (B1a-16), formula (Bla 18), formula (B1a-19) and from formula (B1a-22) to formula (B1a-34) with a cation (b2-1) or a cation (b2-3).
    [0187] [0187] Examples of the acid generator (B) are preferably those represented by the formula (B1-1) to the 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.
    [0188] [0188] or our TS (B1-13) (B1-14) (B1-15). Q @ AOF Se A 9 oon: JK} ST PA SE “1 Das (B1-16) Ö ae (B1-19) (B1-20) (B121)
    [0189] [0189] 0 © X D PK Oo pre (B1-22) 0 ei + = 3 € (B1-23) OO (B1-24) Q ©
    [0190] [0190] Oo LF F 0 () 1 © F 0. Oft eed Of chek
    [0191] [0191]
    [0192] [0192] In the resist composition of the present invention, the content of acid generator is 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.
    [0193] [0193] <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.
    [0194] [0194] <"Quencher" quencher (C)> Examples of the quencher (C) include a basic organic compound containing nitrogen and an acid-generating salt having an acidity lower than that of a acid generated by an acid generator (B) (excluding a salt represented by formula (D). When the resist composition includes the deactivating agent (C) the content of the deactivating agent (C) is preferably about 0.01 to 5 wt%, and more preferably 0.01 to 3 wt% based on the amount of the solid component of the resist composition.
    [0195] [0195] 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, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldildicycloldicylamine, methyldyldicycloldohexylamine, methyldildicldicyclohexylamine, methyldildicycloldoldohexylamine, methyldildicycloldoldicylamine, methyldildicycloldoldohexylamine, methyldildicycloldoldohexylamine, methyldildicycloldoldohexylamine. ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, la = tris [2- (2- (2- methoxyethoxy) eth yl] 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.
    [0196] [0196] Examples of the ammonium salt include tetramethylammonium hydroxide,: tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide , 3- (trifluoromethyl) phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate and choline.
    [0197] [0197] The acidity in an acid generating salt having an acidity lower than that of an acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). Regarding the acid generating salt having lower acidity than an acid generated from the acid generator (B), the acid dissociation constant of an acid generated from the salt usually responds to the inequality following: -3 <pKa, preferably -1 <pKa <7, and more preferably 0 <pKa <5.
    [0198] [0198] Examples of the weak acid internal salt (D) include the following salts. coo ”“ 00 + 99 dio ”940“ 0-0 040 oo 007 oo 00 00 do 5-0 070 65 6- Br CI _ oo oo COO AS Ho Ho Hoo HD EO 5 00 00 © coo SF > HO SO SAR
    [0199] [0199] <Other components> The resist composition of the present invention may also include components other than the components mentioned above (hereinafter sometimes referred to as "other components (F)"). The other components (F) do not are not particularly limited and it is possible to use various additives known in the resist field, for example sensitizers, dissolution inhibitors, surfactants, stabilizers and dyes.
    [0200] [0200] <Preparation of resist composition> The resist composition of the present invention can be prepared by mixing a quencher containing the 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, an appropriate temperature of
    [0201] [0201] <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.
    [0202] The resist composition can usually be applied to a substrate by means of an apparatus used conventionally, such as a centrifugal applicator ("spin coater"). Examples of the substrate include inorganic substrates such as a silicon wafer. Before application of the resist composition, the substrate can be washed, and an organic anti-reflective film can be formed on the substrate.
    [0203] [0203] The solvent is removed by drying the applied composition to form a composition layer. The drying is carried out by evaporating the solvent by means of a heating device such as a hotplate (called "precooking") or a decompression device. The heating temperature is preferably 50 to 200 ° C and the heating time is preferably 10 to 180 seconds. The pressure during drying under reduced pressure is preferably about 1 to 1.0 x 10 ° Pa.
    [0204] [0204] The layer of composition thus obtained is usually exposed by means of an alignment device. The alignment device may be a liquid immersion alignment device. Different exposure sources can be used as an exposure source, for example exposure sources capable of emitting a laser beam in an ultraviolet region such as an excimer laser at KrF (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm) and an Fz excimer laser (wavelength 157 nm), an exposure source capable of emitting a harmonic laser beam in a far ultraviolet region or a vacuum ultraviolet region by laser beam wavelength conversion from a solid state laser source (YAG or semiconductor laser), an exposure source capable of emitting an electron beam or UVE and the like. In the present specification, such radiation exposure is sometimes collectively referred to as “exposure”. Exposure is usually conducted through a mask corresponding to a required pattern. When an electron beam is used as the exposure source, the exposure can be conducted by direct writing without using a mask.
    [0205] [0205] The exposed composition layer is subjected to a heat treatment (called “post-exposure curing”) to promote the deprotection reaction in a labile group in an acid medium. The heating temperature is usually about 50 to 200 ° C, and preferably about 70 to 150 ° C.
    [0206] [0206] The heated composition layer is usually developed with a developing solution by means of a developing apparatus. Examples of the development process include an immersion process, a paddle process, a spray process, a dynamic dispensing process and the like. The development temperature is preferably, for example, 5 to 60 ° C and the development time is preferably, for example, 5 to 300 seconds. It is possible to produce a positive resist pattern or a negative resist pattern by choosing the type of developing solution as follows.
    [0207] [0207] When the positive resist pattern is produced from the resist composition of the present invention, an alkaline developing solution is used as the developing solution. The alkaline developing solution can be various aqueous alkaline solutions used in this field. Examples of these include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly known as choline). The surfactant may be contained in the alkaline developing solution.
    [0208] [0208] When the negative resist pattern is produced from the resist composition of the present invention, a developing solution containing an organic solvent (hereinafter sometimes referred to as "organic developing solution") is used as a developing solution. .
    [0209] [0209] The developed resist pattern is preferably washed with a rinse solution. The rinsing solution is not particularly limited as long as it does not dissolve the resist pattern, and it is possible to use a solution containing an ordinary organic solvent which is preferably an alcoholic solvent or an ester solvent. After washing, the rinse solution which remains on the substrate and the pattern is preferably removed.
    [0210] [0210] <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 a KrF excimer laser. electron beam (FE) or a resist composition for exposure to extreme ultraviolet (UVE), and more suitable as a resist composition for exposure to an electron beam (FE) or as a resist composition for exposure to UVE and the Resist composition is useful for fine processing of semiconductors.
    [0211] [0211] 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.
    [0212] [0212] The structures of the compounds were confirmed by measuring a molecular ion peak by mass spectrometry (liquid chromatography: Model 1100, manufactured by Agilent Technologies, Inc, mass spectrometry: Model LC / MSD, manufactured by Agilent Technologies, Inc.). The value of this molecular ion peak in the following examples is indicated by “MASS”.
    [0213] [0213] Example 1: synthesis of the salt represented by formula (1-3)
    [0214] [0214] Example 2: synthesis of the salt represented by formula (I-12)
    [0215] [0215] Example 3: synthesis of the salt represented by formula (I-13)
    [0216] [0216] Example 4: synthesis of the salt represented by formula (I-14)
    [0217] [0217] Synthesis of Resin The compounds (monomers) used in the synthesis of the resin (A) are indicated below. Hereinafter, these compounds are called "monomer (a1-1-3)" depending on the number of formulas. ox CH = O O
    [0218] [0218] Synthesis Example 1 [Synthesis of Resin A1] A monomer (a1-4-2), a monomer (a1-1-3) and a monomer (a1-2-6) were used as monomers , these monomers were mixed in a molar ratio of 38:24:38 [monomer (a1-4-2): monomer (a1-1-3): monomer (a1-2-6)], and methyl isobutyl ketone a was added to this mixture of monomers in an amount equal to 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile as an initiator was added in an amount of 7 by mol% based on the total molar number of all the monomers, which was followed by polymerization with heating to 83 ° C for about 5 hours. To the polymerization reaction mixture thus obtained an aqueous solution of p-toluenesulfonic acid was added. After stirring for 6 hours, an organic layer was isolated by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A1 resin (copolymer) having a weight average molecular weight of about 5.3 x 10 ° with a yield of 78%. This Al resin includes the following structural units.
    [0219] [0219] <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] ableau 1 nu Generator Salt (I) Composition Agent Deactivated PB / PEB resist resin Composition | A1 = B1-43 = FE 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 = summer |) 110 ° C / 3 10 parts | 3.4 parts 0.7 part 120 ° C Composition | A1 = B1-43 = ee IT 110 ° C / 4 10 parts | 3.4 parts 0.7 part 120 ° C 5 10 parts | 3.4 parts 0.7 part 120 ° C Composition | A1 = B1-43 = IX-1 = 110 ° C / Comparative | 10 games | 3.4 parts 0.7 part 120 ° C 1 Composition | A1 = B1-43 = IX-2 = 110 ° C / Comparative | 10 games | 3.4 parts 0.7 parts 120 ° C 2
    [0221] [0221] <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
    [0222] [0222] (Evaluation of 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 is then 0.04 μm. The coated silicon wafer was precooked on the direct hot plate at the temperature shown in the "PB" column of Table 1 for 60 seconds to form a composition layer. Using a direct electron beam writing system (“ELS-F125 125 keV”, manufactured by ELIONIX INC.), Contact hole patterns (40 nm hole spacing / 17 mm hole diameter nm) were written directly onto the composition layer formed on the wafer while the exposure dose was changed in stages. After exposure, a post-exposure baking was performed on the hotplate at the temperature shown in the "PEB" column of Table 1 for 60 seconds, which was followed by paddle development with an aqueous solution of d. 2.38 wt% tetramethylammonium hydroxide for 60 seconds to obtain a resist pattern.
    [0223] [0223] In the resist pattern formed after development, the effective sensitivity was expressed as the exposure dose at which a hole diameter of 17 nm of a formed pattern was obtained.
    [0224] [0224] <Evaluation of CD Uniformity (CDU)> In the effective sensitivity, the hole diameter of 17 nm was determined by measuring 24 times a same hole and the average of the measured values was taken as the average diameter the hole. The standard deviation was determined under the conditions where the average diameter of 400 holes around patterns formed at a hole diameter of 17 nm in the same wafer was considered a population. The results are shown in Table 2. The numerical value in the table represents the standard deviation (nm).
    [0225] [0225] [Table 2] Example 5 Composition 1 Example 6 Composition 2 Example 7 Composition 3 Example 8 Composition 4 Example 9 Composition 5 Composition Comparative Example 1 2.89 Comparative 1 29 Composition Comparative Example 2 2.85 Comparative 2,285 Compared to Comparative Compositions 1 and 2 , Compositions 1 to 5 exhibit a low standard deviation, leading to a satisfactory assessment of CD uniformity (CDU).
    [0226] [0226] Since resist patterns with satisfactory CD uniformity (CDU) can be obtained, a resist composition comprising a lath (1) of the present invention is useful for fine processing of semiconductors and is very. industrially useful.
    权利要求:
    Claims (13)
    [1]
    1. A salt represented by the formula (I): (R ') rnA 3 TO
    CIZ (R ’) mz where in formula (I), R *, R2 and R each independently represent a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 12 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 furthermore, a plurarity of R2 may be the same or different from each other, and m3 represents an integer of 0 to 4, and when m3 is 2 or more, a plurality of R * may be the same or different from each other.
    [2]
    2. The salt according to claim 1, wherein R * represents a fluorine atom, a trifluoromethyl group or an alkyl group having 1 to 6 carbon atoms, and -CH; - included in the alkyl group can be replaced by -O - or -CO-.
    [3]
    3. The salt according to one of claims 1 or 2, wherein R and R3 each independently represent a fluorine atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and -CH:> - included in the alkyl group and the group Alicyclic hydrocarbon can be replaced by -O- or -CO-.
    [4]
    4. The salt of any one of claims 1 to 3, wherein m1 represents an integer of 0 to 3.
    [5]
    5. The salt of any one of claims 1 to 4, wherein m2 and m3 each independently represent an integer of 0 to 2.
    [6]
    6. The salt according to any one of claims 1 to 5, wherein the salt is represented by any one of the salts of formula (I-1) to formula (I-20):
    “0 Co Us Ds Ds
    HZ SQ SQ DE (1-1) (1-2) (1-3) (1-4) Oo Be Ge Des
    SQ AQ SQ SQ ° (1-5) ° (1-6) CO (1-7) e (1-8) - - - 0 Os Os Os Dy
    SQ SQ SQ AR (1-9) (1-10) (1-11) (1-12) -> o> ° “0 2 AO Le seu Oe WO 1 80 1 8Q 1 80 1 80 (1-13) (1-14) (1-15) (1-16)>> o>> HO HO - D Ds sou Os Os | SQ | SO SQ SQ
    FO (1-17); (1-18) i (1-19) (1-20)
    [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 comprising a structural unit having an acid labile group is a resin including at least one resin selected from the group consisting of a structural unit represented by the formula (al- 1) and a structural unit represented by the formula (a1-2): © H, A Ho RS | + If ST (5 ° 1 82 9. NE, YTS Ra [JOH RT, ms df Vint {at-4} {a1-2} 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 of 1 to 7, and * represents a bond to -CO-, R ° * and R °° each independently represent a hydrogen atom or a methyl group, R °° and R each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group obtained by combining these groups, m1 represents an integer of 0 to 14, nl represents an integer of 0 to 10, and nl 'represents an integer of 0 to 3.
    [10]
    10. The resist composition of claim 9, wherein the resin comprising a structural unit having an acid labile group comprises a structural unit represented by the formula (a2-A): Ho RSS
    HA Joen A | {a2-A} Ve er (R® ") mb where, in the formula (a2-A), R250 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, R °°! represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group, A2 ° 0 represents a single bond or * -X °° 1- (a252-x252) 5; and * represents a site bond to the carbon atom to which -R2 ° is bonded, 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):
    Qt 2 OS LAS, {B1) i where, in formula (B1), QP! and Q ° each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, LP represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CH> - included in the saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH> - included in the alicyclic hydrocarbon group can be replaced by -O-, -S (O)> - or -CO-, and Z * represents an organic cation.
    [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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    同族专利:
    公开号 | 公开日
    TW202028184A|2020-08-01|
    JP2020083880A|2020-06-04|
    US20200159116A1|2020-05-21|
    BE1026753A1|2020-05-28|
    KR20200059166A|2020-05-28|
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    法律状态:
    2020-10-28| FG| Patent granted|Effective date: 20201012 |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2018217064|2018-11-20|
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