RESIST COMPOSITION AND RESIST PATTERN PRODUCTION METHOD

专利摘要:
Disclosed is a resist composition comprising a compound represented by formula (I) as defined in claim 1, a resin having an acid labile group and an acid generator, the resin having an acid labile group acid including at least one structural unit selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2) as defined in claim 1, wherein L1 represents a single bond or an alkanediyl group; R1 represents an acid labile group; R2 represents *-L1-OH, etc.; X1 represents a single bond, an alkanediyl group, etc.; m2 represents 0 to 3, m3 represents an integer of 0 to 5, wherein 0≤m2 + m3≤5, R3 represents a halogen atom, etc.; La1 and La2 represent -O-, etc.; Ra4 and Ra5 represent a hydrogen atom or a methyl group; Ra6 and Ra7 represent an alkyl group, an alicyclic hydrocarbon group, etc.; m1 represents 0 to 14, n1 represents 0 to 10 and n1' represents an integer from 0 to 3.
公开号:BE1028139B1
申请号:E20215209
申请日:2021-03-19
公开日:2022-02-18
发明作者:Nobuhiko Nishitani；Yuji Kita；Koji Ichikawa
申请人:Sumitomo Chemical Co；
IPC主号:

专利说明:

[0001] The present invention relates to a resist composition, and a method for producing a resist pattern using the resist composition. Description of the state of the art
[0002] [0002] JP 2002-258483 mentions a resist composition including a compound of the following structural formula, a resin having the following structural formula and an acid generator. age HS Fa OH TA SUMMARY OF THE INVENTION
[0003] The present invention proposes to provide a resist composition capable of producing a resist pattern with a line edge roughness (LER) which is better than that of a resist pattern formed from a resist composition.
[0004] The present invention includes the following.
[1] [1] A resist composition comprising a compound represented by formula (I), a resin having an acid labile group and an acid generator, the resin having an acid labile group includes at least one group 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):
[2] [2] The resist composition according to [1], wherein L is a single bond or an alkanediyl group having 1 to 4 carbon atoms which may have a halogen atom.
[3] [3] The resist composition according to [1] or [2], wherein R* is a group represented by formula (1a) or a group represented by formula (2a): 1 Raaí AL} (1a) naa Raa3 wherein, in formula (1a), R°*, R°2 and R223 each independently represent an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent , an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or R* and R°°° are bonded to each other another to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms with carbon atoms to which R* and R222 are bonded, naa represents 0 or 1, and
[4] [4] The resist composition according to [3], wherein R* is a group represented by the formula (1a).
[5] [5] The resist composition according to [3], wherein R* is a group represented by the formula (2a).
[6] [6] The resist composition according to [5], in which R22 and R* are linked together to form a heterocyclic group having 3 to 8 carbon atoms with -C-X - in which R22 and R22 are linked.
[7] [7] The resist composition according to any of [1] to [6], wherein m2 is 1.
[8] [8] The resist composition according to any one of [1] to [7], wherein R is *-L*-OH,
[9] [9] The resist composition according to any of [1] to [7], wherein R is *-L!-O-R!.
[10] [10] The resist composition according to any one of [1] to [7], wherein R° is *-X*-Ph-L!-O-R},
[11] [11] The resist composition according to any of [1] to [10], wherein m3 is 1 or 2, and 5 R3 is a halogen atom.
[12] [12] The resist composition according to [1] to [11], wherein the resin having an acid labile group includes a structural unit represented by the formula (a2-A): [ie A { A (a2-A) | + OH (RE where, in the formula (a2-A), R°59 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, R ®1 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group, A20 represents a single bond or * -X°°1- (A852-X252) p-, and * represents a bonding site at carbon atoms to which -R° is bonded, A22 represents an alkanediyl group having 1 to 6 carbon atoms, x°°1 and X252 each independently represent - O-, -CO-O- or -O-CO-, nb represents 0 or 1, and mb represents an integer from 0 to 4, and when mb is an integer from 2 or more, a plurality ity of R2! can be the same or different from each other.
[13] [13] The resist composition according to any one of [1] to [12], wherein the acid generator includes a salt represented by the formula (B1): Q 1 + 'O,S Lb1 2 OS | AIA (B) the where, in the 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 divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom included in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, Y represents a methyl group which may have a substituent, or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CHz- included in the group alicyclic hydrocarbon can be replaced by -O-, -S (O)2- or -CO-, and Z' represents an organic cation.
[14] [14] The resist composition according to any one of [1] to [13], further comprising an acid generating salt having an acidity lower than that of an acid generated from the acid generator.
[15] [15] A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to any one of [1] to [14] onto a substrate, (2) a step drying the applied composition to form a composition layer, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and
[0005] [0005] It is possible to provide a resist pattern with satisfactory line edge roughness (LER) by using a resist composition of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0006] [0006] In the present description, “(meth)acrylic monomer” means at least one selected from the group consisting of a monomer having a structure of “CH:=CH-CO-" and a monomer “CH:=C(CH ;)-CO-". Similarly, “(meth)acrylate” and “(meth)acrylic acid” each mean “at least one selected from the group consisting of acrylate and methacrylate” and “at least one selected from the group consisting of acrylic acid and methacrylic acid". When a structural unit having “CH2=C(CH3)-CO-” or “CH:=CH-CO-” is exemplified, a structural unit having both groups shall be similarly exemplified. In the groups mentioned in the present description, the groups capable of having a linear structure and a branched structure, may have the linear structure or the branched structure. “Combined group” means a group in which two or more exemplified groups are bonded, and the valences of these groups can be changed appropriately depending on a form of bonding.
[0007] [0007] In the following, "solids content of the resist composition" means the total content of the constituents of the resist composition in which the solvent (E) mentioned later is removed.
[0008] <Resist composition> The resist composition of the present invention includes a compound represented by formula (I) (hereinafter sometimes referred to as "compound (I)"), a resin having an acid-labile group which includes at least one structural unit selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2) (hereinafter sometimes referred to as "resin (A )”) and an acid generator (hereinafter sometimes referred to as “acid generator (B)”). “Acid labile group” means a group having a leaving group which is removed by contact with an acid, thereby converting to a constitutional unit having a hydrophilic group (e.g. a hydroxy group or a carboxy group).
[0009] <Compound (I)> The resist composition of the present invention includes a compound (D: R1 δ | N (I) | "au (R>) m3 where, in formula (IT), all symbols are the same as those defined above.
[0010] [0010] Examples of the alkanediyl group in L! 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- 1,6-diyl; and 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 -2,4-diyl, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4 group -diyl. The number of carbon atoms of the alkanediyl group is preferably 1 to 4, and more preferably 1 to 3.
[0011] [0011] The second acid-labile group as for R° means a group in which a group represented by R3 is removed to form a hydroxy acid when contacted with an acid (eg, p-toluenesulfonic acid).
[0012] [0012] Examples of the alkyl group as for R°*, R@° and R°° include methyl group, ethyl group, propyl group, n-butyl group, n-pentyl group, n- hexyl, n-heptyl, n-octyl and the like. The number of carbon atoms of the alkyl group as for R°%*, R°°° and R22 is preferably 1 to 6, and more preferably 1 to 3.
[0013] [0013] Examples of the substituent of the alkyl group having 1 to 8 carbon atoms which may have a substituent include an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms and an aromatic hydrocarbon group. having 6 to 18 carbon atoms. Examples of the substituent of the alkenyl group having 2 to 8 carbon atoms which may have a substituent include an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms atoms. Examples of the substituent of the alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of the substituent of the aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms and an alicyclic hydrocarbon group having 3 to 20 carbon atoms. More specifically, examples thereof include groups obtained by combining an alkyl group and an alicyclic hydrocarbon group (alkylcycloalkyl groups or cycloalkylalkyl groups such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group and norbornylethyl group), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having an alkyl group (a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (a p-cyclohexylphenyl group, a p- adamantylphenyl, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group and the like. naa is preferably 1.
[0014] [0014] When R®*! and Ra are bonded to each other to form an alicyclic hydrocarbon group, examples of the group
[0015] [0015] Examples of the group represented by the formula (1a) include a 1,1-dialkylalkoxycarbonyl group (a group in which R°*, R222 and R223 are an alkyl group, and preferably a tert-butoxycarbonyl group in the formula (1a)), a 2-alkyladamantan-2-yloxycarbonyl group (a group in which R°*, R222 and carbon atoms to which R°°* and R222 are attached form an adamantyl group, and R°°* is a alkyl group of formula (1a)) and a 1-(adamantan-1-yl)-1-alkylalkoxycarbonyl group (a group in which R°* and R222 are an alkyl group, and R®3 is an adamantyl group in the formula (1a)).
[0016] [0016] Examples of the hydrocarbon group such as for R@*, R@° and R223' include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and groups obtained by combining these groups.
[0017] [0017] Specific examples of the acid labile group (1a) - include the following groups. *represents a binding site. DTO Or (I-R1-1-1) (I-R1-1-2) (I-R1-1-3) (1-R'-1-4) (I-R'-1-5) ( LR1-1-6) (I-R1.1-7) (I-R'-1-8) (1-R!-1-9) (1-R'-1-10) (1-R' -1-11) (1-R'-4-12) (1-R'-1-13) (1-R'-1-14) (I-R2-1-15) (1-R - 1-16) Tb Yb 16 OL po (-R2-1-17) (1-R2-1-18) (1-R2.1-19) (1-R -1-20) (1-R2. 1-21) (I-R2-1-22) (-R1-1-23)
[0018] [0018] Specific examples of the acid-labile group (2a) include the following groups. * represents a binding site. * * RAS * * (I-R1-2-1) (L-R1-2-2) (I-R1-2-3) (-R1-2-4) (LR1-2-5) (I- R1-2-6) (IR*-2-7) (I-R1-2-8) Tan (I-R1-2-10) (I-R1-2-11) (1-R'-2- 12) (I-R1-2-13) (I-R1-2-14) (IR*-2-15) (I-R1-2-16) (I-R1-2-17) (IR'- 2-18) (I-R1-2-19) When R* and R2 combine to form a group having an acetal ring structure, the compounds represented by the following formulas are exemplified.
[0019] [0019] Examples of the alkanediyl group in X* include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane group -1,5-diyl and a hexane-1,6-diyl group; and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane -2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4 group -diyl. The number of carbon atoms of the alkanediyl group is preferably 1 to 4, and more preferably 1 to 3.
[0020] [0020] Examples of the substituent which may belong to Ph such as R* include a halogen atom, a hydroxy group, a cyano group, a carboxy group, an alkyl group having 1 to 12 carbon atoms, a fluoride group of alkyl having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a group obtained by combining two or more of these groups.
[0021] [0021] Examples of halogen atom as for R* include fluorine atom, chlorine atom, bromine atom and iodine atom.
[0022] [0022] Examples of the compound (I) include the compounds represented by the following formulas. oo Aon oo oo (1-1) (1-2) (3) (1-4) oo An oo oo CFaT]CF3 CF3 F3 CF3 F3 CF3 F3 Fa ee CF: CF; [CF CF5 1 CFs on Tr pepe) OH (1-5) (1-6) (1-7) (1-8) es Dn A Qu (1-9) I A Goes Or
[0023] [0023] _ $ 5 6 0 H OD 117) OH (1.48) (19) (1-20) O1 0 UD A1 (1-21) (1-22) (1-23) (1-24) OD E F F F F F
[0024] [0024] MoN LT LT > | © IX © | I VL OL “00 ÔH H (1-41) (1-42) (1-43) (1-44) on oo 1 a © | Û © 0 NO 0 NA (1-45) (1-46) (1-47) (1-48) SOUND & LE oo D I | I A
[0025] [0025] The content of compound (I) is usually 0.001 to 20% by mass, preferably 0.005 to 15% by mass, and more preferably 0.01 to 10% by mass, based on the content. in solids of the resist composition.
[0026] <Resin (A)> Resin (A) includes a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)") and includes at least one member selected from the group consisting of into the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2) mentioned later It is preferred 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 the structural unit (a1) and the structural unit (s) (e.g. a structural unit having a halogen atom mentioned later (hereinafter sometimes referred to as “structural unit (a4)"), a structural unit having a non-leaving hydrocarbon group mentioned later (hereinafter sometimes referred to as "structural unit (a5)")) and other structural units derived from monomers known in the art.
[0027] <Structural unit (a1)> The structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter sometimes referred to as “monomer (a1)”). The acid-labile group contained in the resin (A) is preferably a group represented by formula (1) (hereinafter also referred to as group (1)) and/or a group represented by formula (2) (in the sequence also called group (2)):
[0028] [0028] Examples of the alkyl group for R2%, R22 and R°° include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group and analogues.
[0029] [0029] Examples of the hydrocarbon group in RŸ, R° and R include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and groups formed by combining these groups.
[0030] [0030] Examples of group (1) include the following groups.
[0031] [0031] Specific examples of group (2) include the following groups. * represents ve pose bond. Lo oo 0 „0 AR AM AR A DO To
[0032] The monomer (al) is preferably a monomer having an acid-labile group and an ethylenically unsaturated bond, and more preferably a (meth)acrylic monomer having an acid-labile group.
[0033] Among the (meth)acrylic monomers having an acid-labile group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferably cited by way of example. When a resin (A) including a structural unit derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in a resist composition, it is possible to improve the resolution of a resist pattern.
[0034] [0034] 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 referred to as structural unit (a1-0), a structural unit represented by formula (a1-1) (hereinafter sometimes referred to as structural unit (a1-1)) or a structural unit represented by formula (a1-2) (hereinafter sometimes referred to as structural unit (a1-2) )).
[0035] [0035] RO R°* and R°° are preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
[0036] The structural unit (a1-0) includes, for example, a structural unit represented by any one of formula (a1-0-1) to formula (a1-0-18) and a structural unit wherein a methyl group corresponding to R*° in the structural unit (a1-0) is substituted by a hydrogen atom and is preferably a structural unit represented by any one of the formula (a1-0-1 ) to the formula (a1-0-10), the formula (a1-0-13) and the formula (a1-0-14).
[0037] [0037] The structural unit (a1-1) includes, for example, structural units derived from the monomers mentioned in JP 2010-204646 A. Among these structural units, a structural unit represented by any one of the formula (a1-1-1) to the formula (a1-1-7) and a structural unit in which a methyl group corresponding to R°* in the structural unit (a1-1) is substituted by a hydrogen atom are preferred, and a structural unit represented by any one of formula (a1-1-1) to formula (a1-1-4) is more preferred. F H NOT
[0038] [0038] Examples of structural unit (a1-2) include a structural unit represented by any one of formula (a1-2-1) to formula (a1-2-12) and a structural unit in which a methyl group corresponding to R® in the structural unit (a1-2) is substituted by a hydrogen atom and a structural unit represented by any one of formula (a1-2-2), formula (a1-2 -5), formula (a1-2-6) and formula (a1-2-10) to formula (a1-2-12) is preferable.
[0039] [0039] When the resin (A) comprises a structural unit (a1-0), its content is generally from 5 to 80 mol%, preferably from 5 to 75 mol%, and more preferably from 10 to 70 mol%, on the base of all the structural units of the resin (A). When the resin (A) comprises a structural unit (a1-1) and/or a structural unit (a1-2), its total content is usually 10 to 90 mol%, preferably 15 to 85 mol%, of more preferably 20 to 80 mol%, more preferably 20 to 75 mol%, and more preferably 20 to 70 mol%, based on all structural units of the resin (A).
[0040] [0040] In the structural unit (a1), examples of the structural unit having a group (2) include a structural unit represented by the formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1- 4)»): 32 | Ho F° | 7th (a1-4) R334 oR23 (RE), ass where in the formula (a1-4), R23 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, R233 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group, A23 represents a single bond or * -X2*- (A2-x252) ne", and * represents a bonding site at carbon atoms to which - R° is bonded, A22 represents an alkanediyl group having 1 to 6 carbon atoms, x°31 and X each independently represent -O-, -CO-O- or -O-CO-, nc represents 0 or 1, the represents an integer of 0 to 4, and when la is 2 or more, a plurality of R°° may be the same or different from each other the others, and R23% and R°° each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R836 represents a hydrocarbon group having 1 to 20 carbon atoms, or R°° and R° ° are bonded with each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with -C- O- to which R33 and R°° are bonded, and -CH>- included in the hydrocarbon group and the divalent hydrocarbon group can be replaced by -O- or -S-.
[0041] [0041] Examples of halogen atom in R232 and R233 include fluorine atom, chlorine atom and bromine atom.
[0042] [0042] Examples of *-X°*-(a2%2-X232),e- include *-O-, *-CO-O-, *-O-CO-, *-CO-0-A332- CO-0-, *-0-CO-A332-0-, *-0-A332-CO-0-, *-CO-0-A%32-0-CO- and *-0-CO-A% 32-0-CO-. Of these, *-CO-0-, *-CO-0-A332-CO-0- or *-O-A3*2_-CO-O- are preferred.
[0043] Examples of the aforementioned alkanediyl group include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane -1,5-diyl, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group , a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
[0044] [0044] A is preferably a single bond, *-CO-O- or *-CO-O- A232-CO-O-, more preferably a single bond, *-CO-O- or *-CO- — O-CH--CO-O-, and more preferably a single bond or *-CO-O-.
[0045] la is preferably 0, 1 or 2, more preferably 0 or 1, and more preferably 0.
[0046] [0046] R33* is preferably a hydrogen atom.
[0047] [0047] The structural unit (a1-4) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646 A. The structural unit preferably includes the structural units represented by the formula (a1-4- 1) to the formula (a1-4-18) and a structural unit in which a hydrogen atom corresponding to R23 is substituted with a methyl group, and more preferably structural units represented by the formula (a1-4-1 ) to the formula (a1-4-5), the formula (a1-4-10), the formula (a1-4-13) and the formula (a1-4-14).
[0048] When the resin (A) includes the structural unit (a1-4), the content is preferably 3 to 80 mol%, more preferably 5 to 75 mol%, more preferably 7 to 70 mol%, of more preferably 7 to 65 mol%, and more preferably 10 to 60 mol% based on the total of all structural units of the resin (A).
[0049] [0049] 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) ").
[0050] [0050] The halogen atom includes a fluorine atom and a chlorine atom and is preferably a fluorine atom.
[0051] [0051] Examples of the structural unit (a1-5) include structural units derived from the monomers mentioned in JP 2010-61117 A. Among these structural units, the structural units represented by the formula (a1-5-1) to formula (a1-5-4) are preferred, and structural units represented by formula (a1-5-1) or formula (a1-5-2) are more preferred.
[0052] [0052] When the resin (A) includes the structural unit (a1-5), the content is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, more preferably 5 to 40 mol%, and more preferably 5 to 30 mol%, based on all structural units of resin (A).
[0053] The structural unit (a1) also includes the following structural units. #9 Fo FO SO 0 FO FO ZO bd DD Da Q (a1-3-1) (a1-3-2) (a1-3-3) (a1-3-4) (a1-3-5) (a1 -3-6) (a1-3-7)
[0054] [0054] When the resin (A) includes the structural units mentioned above such as (a1-3-1) to (a1-3-7), the content is preferably 10 to 95 mol%, more preferably 15 to 90 mol% mol%, more preferably 20 to 85 mol%, more preferably 20 to 70 mol%, and more preferably 20 to 60 mol%, based on all structural units of the resin (A ).
[0055] The structural unit (a1) also includes the following structural units. LE Hz | Hs > | The = | Lu From DL) 2 3 DD) ) (a1-6-1) (a1-6-2) (a1-6-3)
[0056] <Structural Unit(s)> The structural unit(s) derives from a monomer having no acid-labile group (hereinafter referred to as "monomer(s)"). It is possible to use as the monomer from which the structural unit(s) derives, a monomer having no acid-labile group known in the resist field. The structural unit(s) preferably has a hydroxy group or a lactone ring. When a resin comprising a structural unit having a hydroxy group and not having an acid-labile group (hereinafter sometimes referred to as "structural unit (a2)") and/or a structural unit having a lactone ring and does not having no acid-labile group (hereinafter sometimes referred to as "structural unit (a3)") is used in the resist composition of the present invention, it is possible to improve the resolution of a resist pattern and the adhesion to a substrate.
[0057] <Structural Unit (a2)> The hydroxy group belonging to the structural unit (a2) may be either an alcoholic hydroxy group or a phenolic hydroxy group. When a resist pattern is produced from the resist composition of the present invention, in the case of using, as an exposure source, high energy rays such as a KrF (248 nm) excimer laser , electron beam or extreme ultraviolet (EUV) light, the structural unit (a2) having a phenolic hydroxy group is preferably used as the structural unit (a2), and it is more preferable to use the unit structure (a2-A) mentioned below. When using an ArF excimer laser (193 nm) or the like, a structural unit (a2) having an alcoholic hydroxy group is preferably used as the structural unit (a2), and it is more preferred to use the structural unit (a2-1) mentioned later. The structural unit (a2) can be included alone, or two or more structural units can be included.
[0058] In the structural unit (a2), examples of the structural unit having a phenolic hydroxy group include a structural unit represented by the formula (a2-A) (hereinafter sometimes referred to as "structural unit (a2-A )»): R250
[0059] [0059] Examples of the halogen atom in R°° and R°* include a fluorine atom, a chlorine atom and a bromine atom.
[0060] [0060] Examples of *-X2*!-(a252-X°52)p- include *-O-, *-CO-O-, *-0-CO-, *-CO-O-A3 - CO-O-, *-O-CO-A3 -O-, *-OA°* -CO-O-, *-CO-0-A°**-0- CO- and *-O-CO -A®%*-0-CO-. Of these, *-CO-O-, *-CO-O-A®%*-CO-0- or *-O-A®*-CO-O- is preferred.
[0061] [0061]
[0062] A2°0 is preferably a single bond, *-CO-O- or *-CO-O-A3*-CO-O-, more preferably a single bond, *-CO-O- or *- CO-O-CHz>-CO-O-, and more preferably a single bond or *-CO-O-.
[0063] [0063] mb is preferably 0, 1 or 2, more preferably 0 or 1, and more preferably 0.
[0064] Examples of structural unit (a2-A) include structural units derived from monomers mentioned in JP 2010-204634 A and JP 2012-12577 A.
[0065] [0065] 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. The structural unit (a2-A) can be included in a resin (A) by treatment with an acid such as p-toluenesulfonic acid after polymerization, for example, with a structural unit (a1-4). The structural unit (a2-A) can also be included in the resin (A) by treatment with an alkaline substance such as tetramethylammonium hydroxide after polymerization with acetoxystyrene.
[0066] [0066] Examples of the structural unit having an alcoholic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)" ).H, a14 Pf
[0067] In the formula (a2-1), L°* is preferably -O- or -O-(CH2); -CO- O- (fl represents an integer from 1 to 4), and more preferably - O-, R31* is preferably a methyl group, R2!5 is preferably a hydrogen atom, RS is preferably a hydrogen atom or a hydroxy group, and ol is preferably an integer from 0 to 3, and more preferably 0 or 1.
[0068] [0068] 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-
[0069] [0069] When the resin (A) includes the structural unit (a2-1), the content is usually 1 to 45 mol%, preferably 1 to 40 mol%, more preferably 1 to 35 mol%, more preferably 1 to 20 mol% and more preferably 1 to 10 mol%, based on all structural units of resin (A).
[0070] [0070] <Structural unit (a3)> The lactone ring belonging to the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring or a β-valerolactone ring, or a condensed ring one monocyclic lactone ring and the other ring. Preferably, a γ-butyrolactone ring, an adamantanelactone ring or a bridged ring including a γ-butyrolactone ring structure (eg, a structural unit represented by the following formula (a3-2)) is exemplified.
[0071] The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3) or the formula (a3-4). These structural units may be included alone, or two or more structural units may be included:
[0072] [0072] Examples of the aliphatic hydrocarbon group in R°*, R222, R223 and R°°° include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec -butyl and a tert-butyl group.
[0073] [0073] Examples of alkanediyl group in L® and L® include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4 -diyl, pentane-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane group - 1,2-diyl, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
[0074] In formula (a3-1) to formula (a3-3), preferably, L°* to L°° are each independently -O- or a group in which k3 is an integer from 1 to 4 in *-O-(CH2)(3-CO-O-, more preferably -O- and *-O-CH2-CO-O-, and more preferably an oxygen atom, RAS at R°2! are preferably a methyl group, preferably, R°° and R223 are each independently a carboxy group, a cyano group or a methyl group, and preferably, p1, q1 and r1 are each independently an integer from 0 to 2, and preferably still 0 or 1.
[0075] 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): 1 ter =! a7 (a3-4)'
[0076] Examples of structural unit (a3) include structural units derived from monomers mentioned in JP 2010-204646 A, monomers mentioned in JP 2000-122294 A and monomers mentioned in JP 2012-41274 A. structure (a3) is preferably a structural unit represented by any one of formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula ( a3- 2-2), the formula (a3-3-1), the formula (a3-3-2) and the formula (a3-4-1) to the formula (a3-4-12), and the units structural groups in which the methyl groups corresponding to R°1$, R°1°, R220 and R°°* in the formula (a3-1) to the formula (a3-4) are substituted with hydrogen atoms in the structural units above.
[0077] [0077] Hs Hs Hs Hs Hs Hs Hs Hz tet © rat en, 0 Jen 4} Jon ST teen} Oo 45 HA As RA Voen TO ER (e3-1-1) (a3-2-1) Le) & ( e3-3-1) TI 4- (a3-2-2) (a3-2x-2) © (a3-1-2) (a3-3-2) H CH H2 CH Na CH, H2 CH, a H Az Hs C 3 C 3 CC Het Eu SA EN PR Oo De ï © GO © 9 De) À 0 Ô (a3-4-1) d & 2 AQ (a3-4-6) (a3-4-2) ( a3-4-3) (a3-4-4) & (a3-4-5) © Ha HH Hz Ha Hz CH: c*_LH3 c2 CH3 + CL Ha c CH TT + + TT TR D ° a. ) 0.0.
[0078] When the resin (A) includes the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, and more preferably 10 to 60 mol%, based on all the structural units of the resin (A). Each content of structural unit (a3-1), structural unit (a3-2), structural unit (a3-3) or structural unit (a3-4) is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and more preferably 10 to 50 mol%, based on all the structural units of the resin (A).
[0079] [0079] <Structural unit (a4)> Examples of structural unit (a4) include the following structural units: 1 H, PR“
[0080] [0080] Examples of the chain saturated hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group.
[0081] [0081] Examples of the structural unit (a4) include a structural unit represented by the formula (a4-0), a structural unit represented by the formula (a4-1), and a structural unit represented by the formula (a4-4 ):
[0082] [0082] Examples of the alkanediyl group in L* include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group and butane-1,4-diyl group; and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl.
[0083] [0083] Examples of perfluoroalkanediyl group in L“ include difluoromethylene group, perfluoroethylene group, perfluoroethylfluoromethylene group, perfluoropropane-1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane-2 group, 2-diyl, a perfluorobutane-1,4-diyl group, a perfluorobutane-2,2-diyl group, a perfluorobutane-1,2-diyl group, a perfluoropentane-1,5-diyl group, a perfluoropentane-2 group, 2-diyl, a perfluoropentane-3,3-diyl group, a perfluorohexane-1,6-diyl group, a perfluoro-hexane-2,2-diyl group, a perfluorohexane-3,3-diyl group, a perfluoroheptane- 1,7-diyl, a perfluoroheptane-2,2-diyl group, a perfluoroheptane-3,4-diyl group, a perfluoroheptane-4,4-diyl group,
[0084] [0084] L is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
[0085] [0085] Examples of the structural unit (a4-0) include the following structural units, and the structural units in which a methyl group corresponding to R°* in the structural unit (a4-0) is substituted with a hydrogen in the following structural units: H H H H H H
[0086] [0086] — Ra41
[0087] [0087]
[0088] [0088] 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.
[0089] [0089] Examples of the substituent belonging to R°* include at least one selected from the group consisting of a halogen atom and a group represented by the formula (a-g3). Examples of halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom, and fluorine atom is preferred: + —X243— A 245 (a-g3) where , in the formula (a-g3),
[0090] [0090] Examples of the saturated hydrocarbon group in A include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group; monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* represents a bonding site). OD -6D -GH-CH-EBD Examples of the 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.
[0091] [0091] 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).
[0092] When R°* is a saturated hydrocarbon group having the group represented by formula (a-g3), R°° is more preferably a group represented by formula (a-g2): + —A246— a44__ Aa47 (a-g2) where, in the formula (a-g2), A°*° represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, X21* represents **-O-CO - or **-CO-O- (** represents a binding site to A2), A represents a saturated hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, the total number of carbon atoms of A°°, A and X°** is 18 or less, and at least one of A *® and A37 has at least one halogen atom, and * represents a carbonyl group binding site.
[0093] [0093] The number of carbon atoms of the saturated hydrocarbon group of A3' is preferably 1 to 6, and more preferably 1 to 3.
[0094] [0094] The preferred structure of the group represented by formula (a-g2) is the following structure (* represents a bonding site to a carbonyl group).
[0095] Examples of alkanediyl group in A°* include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane- 1,5-diyl and a hexane-1,6-diyl group; and branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
[0096] [0096] Examples of the divalent saturated hydrocarbon group represented by A22 A°° and A ** in the group represented by formula (a-g1) include a linear or branched alkanediyl group and a monocyclic divalent alicyclic saturated hydrocarbon group, and divalent saturated hydrocarbon groups formed by combining an alkanediyl group and a divalent alicyclic saturated hydrocarbon group. Specific examples thereof include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1- methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like.
[0097] In the group represented by the formula (a-g1), examples of the group in which X** is -O-, -CO-, -CO-O- or -O-CO- include the following groups. In the following examples, * and ** each represent a binding site, and ** represents a binding site at -O-CO-R°*, + do + Tex * % * ex O O O O O O Ô O Ö Ö Ö П AL П X AA
[0098] [0098] Examples of the structural unit represented by the formula (a4-1) include the following structural units, and the structural units in which a methyl group corresponding to A°* in the structural unit represented by the formula (a4- 1) in the following structural units is substituted with a hydrogen atom.
[0099] [0099] H H H H H Hs PP PE ff “B
[0100] [0100] Examples of the structural unit represented by the formula (a4-1) include a structural unit represented by the formula (a4-2) and a structural unit represented by the formula (a4-3): Ha RS
[0101] [0101] Examples of the alkanediyl group having 1 to 6 carbon atoms of L'* include the same groups as those mentioned for A34 Examples of the saturated hydrocarbon group of R include the same groups as those mentioned of R*, The alkanediyl group in L* is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.
[0102] [0102] The structural unit represented by the formula (a4-2) includes, for example, the structural units represented by the formula (a4-1-1) to the formula (a4-1-11). A structural unit in which a methyl group corresponding to RË in the structural unit (a4-2) is substituted with a hydrogen atom is also exemplified as a structural unit represented by (a4-2):
[0103] [0103] Ha OR"
[0104] [0104] Examples of the alkanediyl group in L° include those which are the same as those mentioned in the alkanediyl group of A°**,
[0105] The divalent saturated hydrocarbon group optionally having a fluorine atom in A is preferably a divalent chain saturated hydrocarbon group optionally having a fluorine atom and a divalent saturated alicyclic hydrocarbon group optionally having a fluorine atom, and more preferably a perfluoroalkanediyl group. Examples of the divalent saturated chain hydrocarbon group optionally having a fluorine atom include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group; and perfluoroalkanediyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group. The divalent alicyclic saturated hydrocarbon group optionally having a fluorine atom may be monocyclic or polycyclic. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic group include adamantanediyl group, norbornanediyl group, perfluoroadamantanediyl group and the like.
[0106] [0106] Examples of saturated hydrocarbon group and saturated hydrocarbon group optionally having a fluorine atom for AF* include the same groups as mentioned for R°#2. Preferred among these groups are fluorinated alkyl groups such as trifluoromethyl group , difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3 group ,3,3-pentafluoropropyl, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3 group ,3,4,4,5,5,5-nonafluoropentyl, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorooctyl group; a cyclopropylmethyl group, a cyclopropyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group, a perfluorocyclohexyl group, an adamantyl group, an adamantylmethyl group, an adamantyldimethyl group, a norbornyl group, a norbornylmethyl group, a perfluoroadamantyl group, a perfluoroadamantylmethyl and the like.
[0107] [0107] In the formula (a4-3), L° is preferably an ethylene group. The divalent saturated hydrocarbon group of Af is preferably a group including a divalent chain saturated hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a divalent chain saturated hydrocarbon group having 2 to 3 carbon atoms.
[0108] [0108] The structural unit represented by the formula (a4-3) includes, for example, structural units represented by the formula (a4-1"-1) to the formula (a4-1'-11). structural unit in which a methyl group corresponding to R7 in a structural unit (a4-3) is substituted with a hydrogen atom is also exemplified as a structural unit represented by (a4-3).
[0109] It is also possible to cite by way of example, as structural unit (a4), a structural unit represented by the formula (a4-4): Ls Re
[0110] [0110] Examples of the saturated hydrocarbon group of R2* include those which are the same as the saturated hydrocarbon group represented by R°*2, RP2 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and more preferably an alkyl group having 1 to 6 atoms carbon having a fluorine atom.
[0111] In the formula (a4-4), A ! is preferably -(CH>)j1-, more preferably an ethylene group or a methylene group, and more preferably a methylene group.
[0112] 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 (a44) is substituted with a hydrogen atom in the structural units represented by the following formulas.
[0113] [0113] 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).
[0114] <Structural unit (a5)> Examples of the non-leaving hydrocarbon group belonging to the structural unit (a5) include groups having a linear, branched or cyclic hydrocarbon group. Of these, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. The structural unit (a5) includes, for example, a structural unit represented by the formula (a5-1): H, 51 —— St (a5-1) 55 / R52 where, in the formula (a5-1) , R° represents a hydrogen atom or a methyl group, R° represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom included in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and L°° represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CHz- included in the saturated hydrocarbon group may be replaced by -O- or -CO-.
[0115] [0115] The alicyclic hydrocarbon group in R° can be monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon group includes, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group. The polycyclic alicyclic hydrocarbon group includes, for example, an adamantyl group and a norbornyl group.
[0116] [0116] Examples of the divalent saturated hydrocarbon group in L” include a divalent chain saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and a divalent chain saturated hydrocarbon group is preferred.
[0117] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by L°° is replaced by -O- or -CO- includes, for example, groups represented by formula (L1-1) at formula (L1-%). In the following formulas, * and ** each represent a binding site, and * represents a binding site to an oxygen atom. ee ST SUB OS Set SC (L1-1) (L1-2) (L1-3) ° (L1-4)
[0118] [0118] Lt is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
[0119] The group represented by the formula (L1-1) includes, for example, the following divalent groups.
[0120] The group represented by formula (L1-2) includes, for example, the following divalent groups. ne py +: 4 3 3 LE Über ber te ber
[0121] The group represented by formula (L1-3) includes, for example, the following divalent groups. Hs 0 9 ml mr A DAT A „DO OA
[0122] The group represented by the formula (L1-4) includes, for example, the following divalent groups. î À ek À" SI en DO 0” „SIT N SS DISS D OS.
[0123] L°° is preferably a single bond or a group represented by the formula (L1-1).
[0124] [0124] Examples of the structural unit (a5-1) include the following structural units and the structural units in which a methyl group corresponding to R° in the structural unit (a5-1) is substituted with a hydrogen atom in the following structural units.
[0125] [0125]
[0126] <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.
[0127] [0127] The structural unit having a sulfonate group or a carboxylate group and an organic cation in a side chain is preferably a structural unit represented by the formula (II-2-A"):
[0128] [0128] Examples of the halogen atom represented by RS include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0129] [0129] Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X!B include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, or a combination thereof.
[0130] [0130] Those in which -CHz- included in the saturated hydrocarbon group are replaced by -O-, -S- or -CO- include, for example, divalent groups represented by formula (X1) to formula (X53) .
[0132] [0132] Examples of the organic cation represented by ZA' include organic onium cation, organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation and organic phosphonium cation. Among these organic cations, an organic sulfonium cation and an organic iodonium cation are preferred, and an arylsulfonium cation is more preferred. Specific examples thereof include a cation represented by any one of the formula (b2-1) to the above-mentioned formula (b2-4) (hereinafter sometimes referred to as "cation (b2-1)" according to formula number).
[0133] The structural unit represented by the formula (II-2-A") is preferably a structural unit represented by the formula (II-2-A): RIIS
[0134] [0134] Examples of a perfluoroalkyl group having 1 to 6 carbon atoms represented by RI, RI! Q and Q include those which are the same as the perfluoroalkyl group having 1 to 6 carbon atoms represented by Q” mentioned later.
[0135] The structural unit represented by the formula (II-2-A) is preferably a structural unit represented by the formula (II-2-A-1): R!!!3 NH
[0136] [0136] Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by RS include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec -butyl, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group.
[0137] The structural unit represented by the formula (II-2-A-1) is preferably a structural unit represented by the formula (II-2-A-2):
[0138] [0138] The structural unit represented by the formula (II-2-A") includes, for example, the following structural units, the structural units in which a group corresponding to the methyl group of RIB is substituted by an alkyl group having 1 to 6 carbon atoms optionally having a hydrogen atom, a halogen atom (for example, a fluorine atom) or a halogen atom (for example, a trifluoromethyl group, etc.) and the structural units mentioned in WO 2012/050015 A. ZA” represents an organic cation.
[0139] [0139] The structural unit having a cation having a sulfonio group and an organic anion in a side chain is preferably a structural unit represented by the formula (II-1-1): R!!4 er RIS (II-1 -1)
[0140] [0140] Examples of the structural unit including a cation in the formula (II-1-1) include the following structural units, the structural units in which a group corresponding to the methyl group of R"* is substituted by an atom of hydrogen, a halogen atom (for example, a fluorine atom) or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom (for example, a trifluoromethyl group etc.).
[0141] [0141] 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 examples of the sulfonic acid anion include those which are the same as an anion represented by the above-mentioned formula (B1).
[0142] [0142] Examples of the sulfonylimide anion represented by A include the following. F2 frs Fact —CF4 E 028-CF3 028-CF2 028-CF2 0.S—CF, 0.5—C. LL LL J Dz O;S-CF3 0282 025<F2 bone F, 0.4, F3 F,C-C-CF3 F2
[0143] [0143] Examples of the sulfonylmethide anion include the following.
[0144] [0144] Examples of the carboxylic acid anion include the following. nt he Lo Horn À wok, Jer 7 Os CHs Ô H
[0145] [0145] Examples of the structural unit represented by formula (II-1-1) include structural units represented by the following formulas.
[0146] [0146] When the structural unit (IT) is included in the resin (A), the content of the structural unit (IT) is preferably 1 to 20 mol%, more preferably 2 to 15 mol®%, and more preferably 3 to 10 mol%, based on all structural units of resin (A).
[0147] The resin (A) may include structural units other than the aforementioned structural units, and examples of the structural units include the structural units well known in the art.
[0148] The resin (A) is preferably a resin composed of a structural unit (a1) (including at least one element selected from the group consisting of the structural unit (a1-1) and the structural unit ( a1-2)) and a structural unit (s), i.e. a copolymer of a monomer (a1) and a monomer (s).
[0149] The respective structural units constituting the resin (A) may be used singly, or two or more structural units may be used in combination. By using a monomer from which these structural units are derived, it is possible to produce these structural units by a known polymerization process (eg, a radical polymerization process). The content of respective structural units included in the resin (A) can be adjusted depending on the amount of monomer used in the polymerization.
[0150] <Resin other than resin (A)> The resist composition of the present invention may include the resin other than resin (A).
[0151] The resin (X) is preferably a resin including a structural unit (a4), in particular.
[0152] [0152] The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less. , based on the solid component of the resist composition. When including resins other than resin (A), the total content of resin (A) and resins other than resin (A) is preferably 80% by mass or more and 99% by mass or less, and more preferably 90 mass% or more and 99 mass% or less, based on the solid component of the resist composition. The solid component of the resist composition and the content of the resin can be measured by a known analytical means such as liquid chromatography or gas chromatography.
[0153] [0153] <Acid Generator (B)> A non-ionic or ionic acid generator can be used as the acid generator (B). Examples of nonionic acid generator include sulfonate esters (eg, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (eg, disulfone, ketosulfone, sulfonyldiazomethane) and the like. Typical examples of the ionic acid generator include onium salts containing an onium cation (eg, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the onium salt anion include sulfonic acid anion, sulfonylimide anion, sulfonylmethide anion and the like.
[0154] [0154]
[0155] The acid generator (B) is preferably an acid generator containing fluorine, and more preferably a salt represented by the formula (B1) (hereinafter sometimes called “acid generator (B1) "): Qh + -0.S [61 21 OS AS, (B) des where, in the formula (B1), QPt and Q° each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms , LP! represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CHz- included in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom included in the hydrocarbon group divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CH>- included in the alicyclic hydrocarbon group may be replaced by -O-, -S(0)z- or -CO-, and Z1* represents a cat organic ion.
[0156] [0156] Examples of the perfluoroalkyl group represented by Q” and Q® include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl and a perfluorohexyl group.
[0157] [0157] Examples of divalent saturated hydrocarbon group in LP include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, or the divalent saturated hydrocarbon group may be a group formed by combining two or more of these groups in combination.
[0158] [0158] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by L” is replaced by -O- or -CO- includes, for example, a group represented by any one of the formula (b1- 1) to formula (b1-3). In the groups represented by formula (b1-1) to formula (b1-3) and the groups represented by formula (b1-4) to formula (b1-11) which are specific examples thereof, * and ** represent a binding site, and * represents a -Y binding site.
[0159] [0159] xx N b3 *% OA + O DD No A , DS, b4 T * DS, be 87
[0160] [0160] In the groups represented by formula (b1-1) to formula (b1-3), when -CHz- included in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of atoms of carbon before replacement is taken as the number of carbon atoms of the saturated hydrocarbon group.
[0161] [0161]
[0162] [0162] Examples of the group represented by the formula (b1-3) include the groups represented by the formula (b1-9) to the formula (b1-11). ANSE NET OS ns N DES
[0163] [0163]
[0164] [0164] Examples of the group represented by the formula (b1-4) include the following: oe Aon Js 3 2 No DONS uk LEO ON CH3
[0165] [0165] Examples of the group represented by the formula (b1-5) include the following: Q 9 O Q ANS, As N A At
[0166] [0166] Examples of the group represented by the formula (b1-6) include the following:
[0167] [0167] Examples of the group represented by the formula (b1-7) include the following: Hs O ae -
[0168] [0168] Examples of the group represented by the formula (b1-8) include the following: 0 Hr SO M Do © Do” 0 To O O O
[0169] [0169] Examples of the group represented by the formula (b1-2) include the following: 2 9 Ng + HA, _ x OO TB a Te HA | A Hot, Oo F Oo F AA AA HA HA A. A CH3
[0170] [0170] Examples of the group represented by the formula (b1-9) include the following:
[0171] [0171] Examples of the group represented by the formula (b1-10) include the following: DS MAA a AS ONE of Ö O #3 Ha 4x Hs es x & Ad } Ads “ dm * 4% PS “* FH xx FE mu H Hs F F3 F Fo bf PE Ff Fa € A
[0172] [0172] Examples of the group represented by the formula (b1-11) include the following:
[0173] [0173] Examples of the alicyclic hydrocarbon group represented by Y include groups represented by formula (Y1) to formula (Y11) and by formula (Y36) to formula (Y38).
[0174] [0174] 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, an glycidyloxy, a -(CHz);,-CO-OR®* group or a -(CH2);a-O-CO-RP! (where RP represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups, and -CH>- included in an alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SOz- or -CO-, a hydrogen atom included in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted by a hydroxy group or a fluorine atom, and j represents an integer from 0 to 4).
[0175] [0175] Examples of halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom. Examples of the alicyclic hydrocarbon group include cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group and the like. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples of these include a methylcyclohexyl group, a dimethylcyclohexyl group and the like. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 12, and more preferably 3 to 10. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group , a biphenyl group and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples thereof include an aromatic hydrocarbon group which has a chain hydrocarbon group having 1 to 18 carbon atoms (a tolyl group, a xylyl, cumenyl group, mesityl group, p-methylphenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group etc.) , and an aromatic hydrocarbon group which has an alicyclic hydrocarbon group, having 3 to 18 carbon atoms, , p-adamantylphenyl group, p-cyclohexylphenyl group, etc.). The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 14, and more preferably 6 to 10.
[0176] [0176] Examples of Y include the following.
[0177] [0177] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, more preferably a hydrocarbon group alicyclic 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 (0)z- or -CO-. Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or groups represented by formula (Y42) and formula (Y100) to formula (Y114).
[0178] [0178] The anion in the salt represented by the formula (B1) is preferably an anion represented by the formula (B1-A-1) to the formula (B1-A-59) [hereinafter sometimes called "anion (B1-A-1)" according to the number of the formula], and more preferably an anion represented by any one of the formula (B1-A-1) to the formula (B1-A-4), the formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40) and formula (B1-A-47) to formula (B1-A-59).
[0179] [0179] OH 0 b1 92 we have a SoL Sd 70 SP Sp OS bone LAM bone T >LA41 3
[0180] [0180] O O
[0181] [0181]
[0182] [0182]
[0183] [0183]
[0184] [0184] O
[0185] [0185] R to RU each independently represent, for example, an alkyl group having 1 to 4 carbon atoms, and preferably a methyl group or an ethyl group. R® is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms or a group formed by combining these groups, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. LA is a single bond or an alkanediyl group having 1 to 4 carbon atoms. QP! and QP2 are the same as those defined above.
[0186] [0186] The anion in the salt represented by the formula (B1) preferably includes anions represented by the formula (B1a-1) to the formula (B1a-38).
[0187] [0187]
[0188] [0188] Be A Me, oe Ge - F 7 _ F O3 OS 035
[0189] Of these, an anion represented by any one of formula (B1a-1) to formula (B1a-3) and formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula (B1a-19) and formula (B1a-22) to formula (B1a-38) is preferred.
[0190] [0190] Examples of organic cation of Z1* include organic onium cation, organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation and organic phosphonium cation. Of these, an organic sulfonium cation and an organic iodonium cation are preferred, and an arylsulfonium cation is more preferred. Specific examples thereof include a cation represented by any one of formula (b2-1) to formula (b2-4) (hereinafter sometimes referred to as "cation (b2-1)" depending on the number of the formula).
[0191] The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.
[0192] [0192] Examples of an alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include methylcyclohexyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyladamantan-2- 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.
[0193] [0193] Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, biphenyl group, naphthyl group and phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples thereof include an aromatic hydrocarbon group having a chain hydrocarbon group (a tolyl group, a xylyl group, a cumenyl group, a mesityl group, p-methylphenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group etc.), and an aromatic hydrocarbon group having a hydrocarbon group alicyclic (a p-cyclohexylphenyl group, a p-adamantylphenyl group etc.).
[0194] Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
[0195] The ring formed by linking RP* and RP5 together, with the sulfur atoms to which RP and RP are linked, can be a monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated ring. This ring includes a ring having 3 to 18 carbon atoms and is preferably a ring having 4 to 18 carbon atoms. The sulfur atom-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. * 1. *; * * * * & SS & & & & X + N
[0196] [0196] The cycle formed by combining RP and RE 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 (a tetrahydrothiophenium ring), a thian-1-ium ring, a 1,4-oxathian-4-ium ring and the like. The cycle formed by combining RP!! and PR 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 oxocycloheptane ring, oxocyclohexane ring, oxonorbornane ring, oxoadamantane ring and the like.
[0197] 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. © CaHs € a CeH13 CgH17 of 7878 ‘of 578 of of (b2-c-1) (b2-c-2) (b2-c-3) (b2-c-4) | (b2-c-5) (b2-c6) (b2-c-7) (b2-c-8) H3 H3 H3 -C4Hg -C‚Hg © © Ce O CG (2 HA -C,H (b2- c-14) (b2-c-9) (b2-c-10) (b2-c-11) (b2-c-12) (b2-c-13)
[0198] [0198]
[0199] [0199] Examples of cation (b2-2) include the following cations. + + + DD O0 JOO DQ (b2-c-28) (b2-c-29) (b2-c-30) (b2-c-50)
[0200] [0200] Examples of cation (b2-3) include the following cations. © 145 AO (b2-c-31) (b2-c-32) (b2-c-33) (b2-c-34)
[0201] [0201] Examples of cation (b2-4) include the following cations. Hz Q Q Q © (b2-c-35) (b2-c-36) (b2-c-37) (b2-c-38) Ha Ha Hs Ha © 2 Q Q
[0202] [0202] The acid generator (B) is a combination of the aforementioned anion and the aforementioned organic cation, and these may be optionally combined. The acid generator (B) preferably includes a combination of an anion represented by any one of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (Bla-16), formula (B1a-18), formula (B1a-19) and from formula (B1a-22) to formula (B1a-38) with a cation (b2-1), a cation (b2-3), a cation (b2-4).
[0203] [0203] The acid generator (B) preferably includes those represented by the formula (B1-1) to the formula (B1-56). Among these acid generators, those containing an arylsulfonium cation are preferred, and those represented by formula (B1-1) to formula (B1-3), formula (B1-5) to formula (B1-7) , formula (B1-11) to formula (B1-14), formula (B1-20) to formula (B1-26), formula (B1-29) and formula (B1-31) to formula (B1-56) are particularly preferred.
[0204] [0204] VE TR VA ne SA (B1-13) (B1-14) (B1-15) sage Ol re OR Ca Ö Ô (B1-17) (2 (B1-18) (B1-16) (©
[0205] [0205] 0 EA h 0 5 PA Lx of Ô (B1-23) © (B1-24)
[0206] [0206] | 0 © A OTT ( of ooo
[0207] [0207]
[0208] [0208]
[0209] In the composition of the present invention, the total content of the acid generator is preferably 1 mass part or more and 45 mass parts or less, preferably 3 mass parts or more and 40 mass parts. or less, and more preferably 10 parts by mass or more and 40 parts by mass or less based on 100 parts by mass of the resin (A) mentioned below.
[0210] [0210] <Solvent (E)> The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more and 99% by mass or less. The content of the solvent (E) can be measured, for example, by a means of analysis known as liquid chromatography or gas chromatography. Examples of solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; and cyclic esters such as γ-butyrolactone. Solvent (E) can be used alone, or two or more solvents can be used.
[0211] [0211] <Deactivating agent (C) ("Quencher (C)")> Examples of deactivating agent (C) include an organic compound containing basic nitrogen, and an acid-generating salt having a lower acidity. to that of an acid generated from an acid generator (B). When the resist composition includes the quenching agent, the content of the quenching agent (C) is preferably about 0.01 to 15% by weight, more preferably about 0.01 to 10% by weight. , more preferably about 0.01 to 5% by weight, and more preferably about 0.01 to 3% by weight, based on the amount of the solid component of the resist composition. Examples of the basic nitrogen-containing organic compound include an amine and an ammonium salt. Examples of amine include aliphatic amine and aromatic amine. Examples of aliphatic amine include primary amine, secondary amine and tertiary amine. Examples of amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline , diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine , ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, la = tris[2-(2-methoxyethoxy)ethyl]amin e, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4"-diamino-1,2-diphenylethane, 4,4"-diamino-3,3"-dimethyldiphenylmethane, 4,4" diamino-3,3"-diethyldiphenylmethane, 2,2'-methylenebisaniline, limedazole, 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.
[0212] The acidity in an acid-generating salt having a lower acidity than an acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). Regarding the acid-generating salt having a lower acidity than an acid generated from the acid generator (B), the acid dissociation constant of an acid generated from the salt usually satisfies the inequality following: -3 < pKa, preferably -1 < pKa < 7, and more preferably 0 < pKa < 5.
[0213] [0213] Examples of the weak acid inner salt (D) include the following salts. coo 00 + 00 oo do 000 0 40 007 oo” coo coo 007 coo” OO Gi Dodo
[0214] <Other components> The resist composition of the present invention may also include components other than the above-mentioned components (hereinafter sometimes referred to as "other components (F)"), 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 colorants.
[0215] <Preparation of the resist composition> The resist composition of the present invention can be prepared by mixing a salt (I), a resin (A) and an acid generator (B). , resins other than the resin (A) to be used, a solvent (E), a deactivating agent (C) and other components (F). The mixing order of these components is any order and it is not particularly limited. It is possible to select, as the temperature during mixing, an appropriate temperature of 10 to 40°C, depending on the kind of the resin, the solvent solubility (E) of the resin and the like. It is possible to choose, as mixing time, an appropriate time of 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited and it is possible to use mixing with agitation. After mixing the respective components, the mixture is preferably filtered through a filter having a pore diameter of about 0.003 to 0.2 µm.
[0216] [0216] (Method for producing a resist pattern) The method for producing a resist pattern of the present invention includes: (1) a step of applying the resist composition of the present invention to a substrate, (2) a step of drying the applied composition to form a layer of composition, (3) a step of exposing the layer of composition, (4) a step of heating the exposed layer of composition, and (5) a step of development of the heated composition layer. The resist composition can typically be applied to a substrate by means of conventionally used apparatus, such as a spinner. Examples of substrate include inorganic substrates such as a silicon wafer. Prior to application of the resist composition, the substrate may be washed, and an organic antireflection film may be formed on the substrate.
[0217] [0217] (Application) The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) or resist composition for UVE exposure, in particular an electron beam (EB) resist composition or resist composition for UVE exposure, and the composition of resist is useful for fine processing of semiconductors.
[0218] The present invention will be described more specifically by means of examples. The percentages and the parts expressing the contents or the amounts used in the examples are by weight unless otherwise indicated.
[0219] [0219] 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”,
[0220] Synthesis Example 1: Synthesis of the compound represented by the formula (K-1) he “a, LA 0, H To (I-1-a) (l-1-b) (1-1) We have mixed 5 parts of a compound represented by formula (I-1-a), 230 parts of ethyl acetate and 12.88 parts of a compound represented by formula (I-1-b), which was followed by stirring at 23°C for 30 minutes and further cooling to 5°C. To the mixture thus obtained, 23.48 parts of diisopropylethylamine were added dropwise, followed by raising the temperature to 70°C, stirring at 70°C for 2 hours and further cooling to 23°C. To the thus obtained mixture, 120 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 120 parts of a 5% oxalic acid aqueous solution was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 120 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was carried out five times. The organic layer thus obtained was concentrated, then the concentrated mass was isolated using a column (silica gel 60 N (spherical, neutral) 100-210 µm; manufactured by Kanto Chemical Co., Inc., development solvent: n-heptane/ethyl acetate = 10/1) to obtain 7.24 parts of a compound represented by formula (I-1). MASS (mass spectrometry): 227.1 [M+H]"
[0221] Synthesis Example 2: Synthesis of the salt represented by the formula (I-5) 0 CF3 pH AL do A CF$ OH N cr 3 CF Do — 3 9 CE, F3 (I-5-a) (l- 1-b) (1-5) Cr 8 parts of a compound represented by formula (I-5-a), 100 parts of ethyl acetate and 15.72 parts of a compound represented by Formula (I-1-b) followed by stirring at 23°C for 30 minutes and further cooling to 5°C. To the mixture thus obtained, 10.59 parts of diisopropylethylamine were added dropwise, followed by raising the temperature to 70°C, stirring at 70°C for 4 hours and further cooling to 23°C. To the mixture thus obtained, 100 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 50 parts of a 5% oxalic acid aqueous solution was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 50 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was carried out five times. The organic layer thus obtained was concentrated, then the concentrated mass was isolated using a column (silica gel 60 N (spherical, neutral) 100-210 µm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane/ethyl acetate = 10/1) to obtain 7.15 parts of a compound represented by formula (I-5). MASS (mass spectrometry): 527.1 [M+H]"
[0222] Synthesis Example 3: Synthesis of Compound by Formula (I-9) | A AT Os on LG + (1-9-a) (I-1-b) (1-9) 6.50 parts of a compound represented by the formula (I-9-a), 160 parts of ethyl acetate and 15.19 parts of a compound represented by formula (I-1-b), which was followed by stirring at 23°C for 30 minutes and further cooling to 5 °C. To the mixture thus obtained, 18.05 parts of diisopropylethylamine were added dropwise, followed by raising the temperature to 70°C, stirring at 70°C for 4 hours and further cooling to 23°C. To the mixture thus obtained, 160 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 80 parts of a 5% oxalic acid aqueous solution was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 80 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was carried out five times. The organic layer thus obtained was concentrated, then the concentrated mass was isolated using a column (silica gel 60 N (spherical, neutral) 100-210 µm; manufactured by Kanto Chemical Co., Inc., development solvent: n-heptane/ethyl acetate = 10/1) to obtain 5.80 parts of a compound represented by formula (I-9). MASS (mass spectrometry):319.2 [M+H]"
[0223] [0223] Synthesis Example 4: Synthesis of the compound represented by the formula (1-39)° OD, OMe (I1-39-c) Q,
[0224] [0224] Synthesis Example 5: Synthesis of the compound represented by the formula (1-37) ue os -
[0225] Synthesis Example 6: Synthesis of Compound Represented by Formula (1-4)
[0226] Synthesis Example 7: Synthesis of the Compound Represented by Formula (I-41) Ah pod LAN È OC | H | To (|-41-a) (l-1-b) (1-41)
[0227] [0227] Synthesis Example 8: Synthesis of the compound represented by the formula (1-45) - MA LM n > Û DO — — —(— O HO So A (1-45-a) (l-1-b) (1-45)
[0228] Synthesis Example 9: Synthesis of Compound Represented by Formula (1-55) 49 SE 4 AT De TE LA (1-55-a) (1-1-b) (1-55) 10 parts of a compound represented by formula (1-55-a), 75 parts of ethyl acetate and 26.85 parts of diisopropylethylamine, followed by stirring at 23°C for 30 minutes and further by cooling to 5°C. To the mixture thus obtained, 15.11 parts of a compound represented by the formula (I-1-b) were added dropwise, followed by raising the temperature to 23°C and further stirring at 23°C for 18 hours. To the mixture thus obtained, 75 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 30 parts of a 5% oxalic acid aqueous solution was added, and after stirring at 23°C for 30 minutes, the 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, the organic layer was isolated by separation. This water washing operation was carried out five times. The organic layer thus obtained was concentrated, then the concentrated mass was isolated using a column (silica gel 60 N (spherical, neutral) 100-210 µm; manufactured by Kanto Chemical Co., Inc., development solvent: n-heptane/ethyl acetate = 10/1) to obtain 12.32 parts of a compound represented by formula (I-55). MASS (mass spectrometry): 367.1 [M+H]"
[0228] [0228] Synthesis Example 10: Synthesis of a compound represented by the formula (I-60) ue OQ 3 + 0A LG, Oo Or DAO (I-60-a) (I-60-b) (1-60 ) 10 parts of a compound represented by formula (I-60-a), 0.55 part of a compound represented by formula (I-39-c), 100 parts of ethyl acetate were mixed and 10 parts tetrahydrofuran, followed by stirring at 23°C for 30 minutes and further cooling to 10°C. To the thus obtained mixed solution, 2.76 parts of a compound represented by the formula (I-60-b) were added dropwise at 10°C, followed by a temperature rise to 23° C and further by stirring at 23° C. for 2 hours. To the thus obtained mixture, 70 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was repeated five times. The organic layer thus obtained was concentrated, then the concentrated mass was isolated using a column (silica gel 60 N (spherical, neutral) 100-210 µm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane/ethyl acetate = 10/1) to obtain 9.15 parts of a compound represented by formula (1-60). MASS (mass spectrometry): 481.3 [M+H]"
[0229] Synthesis Example 11: Synthesis of a Compound Represented by Formula (I-65) Ah SG re == H Do! (I-1-b) ' (1-65-a) (1-65) 5 parts of a compound represented by the formula (I-65-a), 20 parts of ethyl acetate and 7.14 parts diisopropylethylamine, followed by stirring at 23°C for 30 minutes and further cooling to 5°C. To the mixture thus obtained, 3.92 parts of a compound represented by formula (I-1-b) was added dropwise, followed by stirring at 23°C for 18 hours. To the mixture thus obtained, 20 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 10 parts of a 5% oxalic acid aqueous solution was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 10 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was carried out five times. The organic layer thus obtained was concentrated, then the concentrated mass was isolated using a column (silica gel 60 N (spherical, neutral) 100-210 µm; manufactured by Kanto Chemical Co., Inc., development solvent: n-heptane/ethyl acetate = 10/1) to obtain 2.48 parts of a compound represented by formula (I-65). MASS (mass spectrometry): 478.9 [M+H]"
[0230] [0230] Synthesis Example 12: Synthesis of a Compound Represented by Formula (I-71) AA
[0231] [0231] Synthesis Example 13: Synthesis of a Compound Represented by Formula (1-75)
[0232] [0232] Synthesis Example 14: Synthesis of a compound represented by formula (I-76)
[0233] Synthesis Example 15: Synthesis of Compound Represented by Formula (1-79)
[0234] [0234] Synthesis Example 16: Synthesis of Compound Represented by Formula (I-80)
[0235] Synthesis Example 17: Synthesis of Compound by Formula (IX-1) eu Re TEA Os H + __, y PO (IX-1-a) (IX-1-b) (IX-1) We have mixed 25.7 parts of a compound represented by formula (IX-1-a), 120 parts of acetone and 48.58 parts of triethylamine, followed by stirring at 23°C for 30 minutes and further by cooling to 5°C. To the mixture thus obtained, 36.91 parts of a compound represented by the formula (XI-1-b) were added, followed by raising the temperature to 23°C and further stirring at 23 °C for 6 hours. To the mixture thus obtained, 120 parts of tert-butyl methyl ether and 80 parts of ion-exchanged water were added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 60 parts of a saturated aqueous solution of ammonium chloride was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. To the organic layer thus obtained, 60 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. This water washing operation was carried out five times. The organic layer thus obtained was concentrated and then the concentrated mass was isolated using a column (silica gel 60 N (spherical, neutral) 100-210 µm; manufactured by Kanto Chemical Co., Inc., solvent development: n-heptane/ethyl acetate = 5/1) to obtain 27.18 parts of a compound represented by formula (IX-1).
[0236] [0236] Resin synthesis
[0237] Synthesis Example 18 [Synthesis of Resin A1] A monomer (a1-1-3) and a monomer (a1-2-6), a monomer (a2-1-3), a monomer ( a3-4-2) and a monomer (a1-4-2) as monomers, these monomers were mixed in a molar ratio of 20:35:3:15:27 [monomer (a1-1-3):monomer ( a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators in the amount of 1.2 mol% and 3.6 mol% based on the molar number total of all monomers, followed by heating at 73°C for about 5 hours. To the polymerization reaction solution thus obtained, an aqueous solution of p-toluenesulfonic acid (2.5% by mass) was added in an amount of 2.0 times the total mass of all monomers, thereby was followed by stirring for 12 hours and further isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and recovery to obtain resin A1 (copolymer) having a mass-average molecular weight of about 5.3 x 10° with a yield of 63%. This A1 resin has the following structural units.
[0238] Synthesis Example 19 [Synthesis of Resin A2] A monomer (a1-1-3), a monomer (a1-2-6), a monomer (a2-1-3), a monomer ( a3-4-2) and a monomer (a1-4-13) as monomers, these monomers were mixed in a molar ratio of 20:35:3:15:27 [monomer (a1-1-3): monomer ( a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-13)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the molar number total of all monomers, followed by heating at 73°C for about 5 hours. To the polymerization reaction solution thus obtained, an aqueous solution of p-toluenesulfonic acid (2.5% by mass) was added in an amount of 2.0 times the total mass of all monomers, thereby was followed by stirring for 12 hours and further isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and collection to obtain resin A2 having a weight-average molecular weight of about 5. 1 x 103 with a yield of 61%. This A2 resin has the following structural units. Hz Hz Hs Hz H tone to tou to ch
[0239] [0239] Synthesis Example 20 [Synthesis of Resin A3]
[0240] Synthesis Example 21 [Synthesis of Resin A4] Monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2), and monomer (a1-2-6) were used. a1-4-13) as monomers, these monomers were mixed in a molar ratio of 53:3:12:32 [monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4 -2): monomer (a1-4-13)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitria and azobis (2,4 dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the total molar number of all monomers, followed by heating at 73°C for about 5 hours. To the polymerization reaction solution thus obtained, an aqueous solution of p-toluenesulfonic acid (2.5% by mass) was added in an amount of 2.0 times the total mass of all monomers, thereby was followed by stirring for 12 hours and further isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and collection to obtain an A4 resin having a weight-average molecular weight of about 5. 1 x 103 with a yield of 79%. This A4 resin has the following structural units. Hs Hs Hs tr dou dot fon O d 0 0 L- ô. A4 HOH H Ö
[0241] [0241] Synthesis Example 22 [Synthesis of Resin AX1] 100 parts of polyvinylphenol (VP-15000; manufactured by Nippon Soda Co., Ltd.), 400 parts of methyl isobutyl ketone and 0.004 part of p-toluenesulfonic acid dihydrate were charged, which was followed by concentration until the total amount of this mixed solution became 273 parts. After concentration, 8.01 parts of ethyl vinyl ether was added dropwise to the resin solution, and then reaction was carried out by stirring for 2.5 hours. Then, to this reaction solution, 58.2 parts of ion-exchanged water and 0.005 part of triethylamine were added, followed by stirring and further isolation by separation. Then, the operation of adding 60 parts of ion-exchanged water to the organic layer, followed by isolation by separation, was performed four times. After the washing was completed, the organic layer was concentrated to obtain an AX1 resin having a mass average molecular weight of about 1.6 x 10% with a yield of 88%. A ratio of an ethoxyethyl group introduced into all structural units of the AX1 resin was 30.1 mol%. AX1 resin has the following structural units.
[0242] [0242] <Preparation of Resist Composition> As shown in Table 1, the following components were mixed and the mixture thus obtained was filtered through a fluororesin filter having a pore diameter of 0.2 µm to prepare resist compositions. Table 1 Composition of | Resin Gene- | Compound |Agent of | PB/ resistor | (I) deactivation | PEB of acid on (C B1-43 = a Al= I-1 = C1 = 100°C/ Composition 1140 parts A part | 0.7 part |100°C parts B1-43 = in A2 = I-1 = C1 = 100°C/ 10 parts parts 0.2 parts 0.7 parts |100°C B1-43 = a Al= I-5 = C1 = 100°C/ 10 parts parts 0.2 parts 0.7 parts | 100°C B1-43 = we A2 = I-5 = C1 = 100°C/ 10 parts parts 0.2 part 0.7 part |100°C B1-43 = a Al= I-9 = C1 = 100° C/ Composition 5 10 parts Se part 0.7 part |100°C parts B1-43 = a A2 = I-9 = C1 = 100°C/ Composition 6 140 parts Se part |0.7 part |100°C parts B1-43 = a A1 = I-4 = C1 = 100°C/ Composition 7140 parts BA part | 0.7 part | 100°C parts B1-43 = en A2 = I4= C1 = 100°C/ Composition 8140 parts BA part |0.7 part |100°C
[0243] [0243] <Resin> A1, A2, A3, A4, AX1: Resin A1, Resin A2, Resin A3, Resin A4, Resin AX1 <Acid generator> B1-43: Salt represented by the formula (B1-43) (synthesized according to the examples of JP 2016-47815 A) + O, 3, OTA
[0244] [0244] (Evaluation of the exposure of a resist composition to an electron beam: development with butyl acetate)
[0245] [0245] Evaluation of line edge roughness (LER): The trench width of irregularities on the surface of the side wall of the resist pattern produced at the effective sensitivity was measured by a scanning electron microscope to determine the roughness. line edge. The results are shown in Table 2.
[0246] [0246] Priority is claimed of Japanese Application No. 2020-050973 filed March 23, 2020 and Japanese Application No. 2020-171045 filed October 9, 2020, the contents of which are incorporated herein by reference.

权利要求:
Claims (18)
[1]
1. A resist composition comprising a compound represented by formula (I), a resin having a first acid labile group and an acid generator, the resin having a first acid labile group includes at least one group selected in the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2):
R
Ö | N(I) | a (RÈ)m3 where, in the formula (I), L* represents a single bond or an alkanediyl group having 1 to 6 carbon atoms which may have a substituent, said substituent includes a halogen atom, a hydroxy group, a cyano group, a carboxy group, an alkyl group having 1 to 12 carbon atoms, an alkyl fluoride group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms and a group obtained by combining two or more of these groups, R* represents an acid labile group, R2 represents *-L'-OH, *-L*-OR*, *-X!-Ph-L'-OH or *-X*-Ph -L*- OR}, * represents a benzene ring bonding site, and Ri and R* may combine to form a group having an acetal ring structure, xt represents a single bond, an alkanediyl group having 1 to 6 carbon atoms carbon, -O-, -S-, -SO- or -SO--, Ph represents a phenylene group which may have a substituent, m2 represents an integer from 0 to 3, and when m2 is equal to or greater than 2, several R may be the same or different from each other, R3 represents a halogen atom, a hydroxy group, an alkyl fluoride group having 1 to 6 carbon atoms or an alkyl group having
1 to 12 carbon atoms, and -CHz- included in the alkyl group may be replaced by -O- or -CO-, and m3 represents an integer of 0 to 5, and when m3 is equal to or greater than 2, a plurality of R* can be the same or different from each other, in which 0 < m2 + M3 < 5: Le RM Le Ra5 = | = | La1 La2 u [or 13060, nt" (a1-1) (a1-2) where, in formula (a1-1) and formula (a1-2): Lt and L22 each independently represent -O- or *- O- (CH>):-CO-O-, and k1 represents an integer from 1 to 7, * represents a bonding site to -CO-, R°* and R® each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, R°° and R each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups, m1 represents an integer of 0 to 14, nl represents an integer from 0 to 10, and nl' represents an integer from 0 to 3.
[2]
2. The resist composition according to claim 1, wherein L* is a single bond or an alkanediyl group having 1 to 4 carbon atoms which may have a halogen atom.
[3]
3. A resist composition according to claim 1 or 2, wherein R* is a group represented by formula (1a) or a group represented by formula (2a):
CG ) Raa1 + —O aa2 (1a) as Raa3 where, in formula (1a), R°*, R°2 and R223 each independently represent an alkyl group having 1 to 8 carbon atoms which may have a substituent, a group alkenyl having 2 to 8 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or R°* and R222 may be bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms with carbon atoms to which R* and R°°° are bonded, naa represents 0 or 1, and * represents a bond: paat' + — RS (2a) Raa2' Where, in formula (2a), R®** and R®7 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R®* represents a hydrocarbon group having 1 to 20 carbon atoms, or R22 and R223 can be linked together to form a heterocyclic group having 3 to 20 carbon atoms with -C-X°- in which R22 and R°* are bonded, and -CH:- included in the hydrocarbon group and the heterocyclic group may be replaced by -O- or -S-, X* represents an oxygen atom or a sulfur atom, and * represents a binding site.
[4]
4. A resist composition according to claim 3, wherein R* is a group represented by formula (1a).
[5]
5. A resist composition according to claim 3, wherein R* is a group represented by formula (2a).
[6]
6. A resist composition according to claim 5, wherein R22 and R223 are linked to each other to form a heterocyclic group having 3 to 8 carbon atoms with -C-X°- in which R22 and R°* are linked.
[7]
7. A resist composition according to any one of claims 1 to 6, wherein m2 is 1.
[8]
8. A resist composition according to any one of claims 1 to 7, wherein m2 is 1 or 2 and R* is *-L*-OH.
[9]
9. A resist composition of any one of claims 1 to 7, wherein m2 is 1 or 2 and R* is *-L*-O-R*,
[10]
10. A resist composition according to any one of claims 1 to 7, wherein m2 is 1 or 2 and R* is *-X!-Ph-L!-O-R*,
[11]
11. A resist composition according to any one of claims 1 to 10, wherein m3 is 1 or 2, and R3 is a halogen atom.
[12]
12. A resist composition according to any one of claims 1 to 11, wherein the resin having an acid labile group further includes a structural unit represented by the formula (a2-A): a50
HE A250 (a2-A) in (R°) where, in the formula (a2-A), R°59 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, R®1 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group, A20 represents a single bond or * -X°°- (a82-x252) 5", and * represents a site for bonding to carbon atoms to which -R°* is bonded, A2 represents an alkanediyl group having 1 to 6 carbon atoms, x° °!1 and X252 each independently represents -O-, -CO-O- or -O-CO-, nb represents 0 or 1, and mb represents an integer from 0 to 4, and when mb is an integer from 2 or pl us, a plurality of R2! can be the same or different from each other.
[13]
13. The resist composition according to any one of claims 1 to 12, wherein the acid generator includes a salt represented by the ol * O3S LA Z* 03 > xy (BIJ) formula (B1): a” where , in the 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, -CH:- included in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom included in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, Y represents a methyl group which may have a substituent, or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CHz- included in the group alicyclic hydrocarbon can be replaced by -O-, -S (O)2- or -CO-, and Z' represents an organic cation.
[14]
14. The resist composition according to any one of claims 1 to 13, further comprising an acid generating salt having a lower acidity than an acid generated from the acid generator.
[15]
15. The resist composition according to any one of claims 1 to 14, wherein L! represents a single bond.
[16]
16. The resist composition according to any one of claims 1 to 14 wherein L! represents —(CF3)2C-.
[17]
17. The resist composition according to claim 1, wherein the compound represented by formula (T) is represented by any one of the following formulas:
4 5 £ © (1-1) (1-2) (1-3) (1-4) oo SN oo oo CFaT]CF3 CF3 F3 CF3 F3 CF3 F3 CF3|CFs CF3 F3 CF3 F3 CF3 F3 an 21° AD OH (1-5) (1-6) (1-7) (1-8) © ons A “oo ( LA, as (1-9) 7
S (1-13) (1-14) Do OD, ï (1-16)
00 HO LO (1-17) OH (1-18) (1-19) (1-20) O © Ç © (1-21) (1-22) (1-23) 9 (1-24) MoN Do” Do” in
FFFFFFFFFFF 7 F on OH " (1-25) (1-26) (1-27) (26) A VON Vo Vo CF3 3 Fs F3 OO on N OH (1-29) (1-30) (1-31 ) (1-32) SE nos t SA (1-33) (1-34) (1-35) (1-36) OS H on
H
O
O O (1-37) (1-38) (1-39) (1-40)
VON | go oo | go | | © XX © xx _ 00 NO 0 OH H (-41) (1-42) (1-43) (1-44) VON oo 1 a L | 9 © © NO 0 NA (1-45) (1-46) (1-47) (1-48) AN oo oo oo ST & LA (1-49) (1-50) (1-51) in 8 8
S (L53) (1-54) of Ne > (1-55) on ee (1-56) "
S
ODD DAT CAD
OLDO-ONDO
S QUE, LTD, (-61) (1-62) OH WHAT, - (1-64)
A oo oo oo | 9 | x v Lx | | “OO os H OH (1-65) (1-66) (1-67) (1-68)
OH oO go y DE | ) IN © > 'NA | on Oo (1-69) (1-70) (1-71) (1-72) AO bo 0 DD A | | | | | | | | © T° OT OO O0 (1-73) (1-74) on Or he | OH LL OH | | | | | | H C 10 OH OO (1-77) (1-78) (1-79) om
[18]
18. A process for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to any one of claims 1 to 17 on a substrate, (2) a step of drying the composition applied to form a composition layer, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and (5) a step of developing the composition layer heated.

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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JP2020050973|2020-03-23|

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JP2020171045|2020-10-09|

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