RESIN, PHOTORESIST COMPOSITION AND METHOD FOR PRODUCING PHOTORESIST PATTERN AND COMPOUND

专利摘要:
An object of the present invention is to provide a resin capable of producing a resist pattern with satisfactory line edge roughness (LER), and a resist composition comprising the resin. Disclosed is a resin comprising the structural unit represented by the formula (I), and a structural unit represented by the formula (a1-1) and/or a structural unit represented by the formula (a1-2), such as defined in claim 1 and a resist composition comprising this resin, wherein, in the formula (I), the formula (a1-1) and the formula (a1-2), wherein R1, Ra4 and Ra5 each represent an atom of hydrogen or a methyl group, X1 represents a single bond or -CO-O-*, X2 represents -CO-O-*, -O-* or the like, Ar1 and Ar2 each represent an aromatic hydrocarbon group which may have a substituent, R2 each represents a hydrogen atom, an acid labile group and the like, n represents an integer of 1 to 3, La1 and La2 each represent -O- or * -O-(CH2)k1-CO-O-, k1 represents an integer of 1 to 7, Ra6 and Ra7 each represent an alkyl group, an alicyclic hydrocarbon group, a group obtained by combining these groups or the like, m1 represents an integer from 0 to 14, n1 represents an integer from 0 to 10, and n1' represents an integer from 0 to 3.
公开号:BE1027801B1
申请号:E20205941
申请日:2020-12-16
公开日:2022-02-07
发明作者:Yuji Kita；Koji Ichikawa
申请人:Sumitomo Chemical Co；
IPC主号:

专利说明:

[0001] The present invention relates to a resin, a resist composition and a method for producing a resist pattern using the resist composition, and a compound. BACKGROUND OF THE INVENTION
[0002] [0002] Patent document 1 mentions a resin including the following structural units. H H CHs toch, +CH, +CH;
[0003] [0003] Patent document 1: JP 10-186642 A Description of the invention Problems to be solved by the invention
[0004] An object of the present invention is to provide a resin which forms a resist pattern having a line edge roughness (LER "Line Edge Roughness") better than that of a resist pattern formed from a resist composition comprising the aforementioned resin. Ways to solve problems
[0005] The present invention includes the following inventions.
[1] [1] A resin comprising a structural unit represented by formula (I), and 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): R1 test X' (|) | 1 Ar The | Ar--o-r ) n where, in formula (I), R* represents a hydrogen atom or a methyl group, xt represents a single bond or -CO-O-* (* represents a bond site to Ar*), X represents -CO-O-*, -O-*, -O-CO-*, -O-CO-(CH>)mm-O-* or -O-(CHz)nn-CO-O-* (* represents a binding site to Ar”), mm and nn represent 0 or 1, Art and Ar” each independently represent an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, R2 each independently represents a carbon atom hydrogen or an acid-labile group, or when there are two or more R*, two
[2] [2] The resin according to [1], in which X* is a single bond.
[3] [3] The resin according to [1] or [2], in which X is -CO-O-* or -O-* (* represents an Art binding site).
[4] [4] The resin according to any one of [1] to [3], wherein n is 1 or
[5] [5] The resin according to any one of [1] to [4], wherein the acid labile group in R is a group represented by formula (1a) or a group represented by formula (2a):
[6] [6] The resin according to any one of [1] to [5], wherein R° is a hydrogen atom, or n is 2 or more and two R* combine to form a group having an acetal structure cyclic.
[7] [7] The resin according to any one of [1] to [6], further comprising a structural unit represented by the formula (a2-A):
[8] [8] A resist composition comprising the resin according to any one of [1] to [7] and an acid generator.
[9] [9] The resist composition according to [8], wherein the acid generator comprises a salt represented by the formula (B1):
[10] [10] The resist composition according to [8] or [9], further comprising an acid-generating salt having an acidity lower than that of an acid generated by the acid generator.
[11] [11] A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to any one of [8] to [10] onto a substrate, (2) a step drying the applied composition to form a layer of composition, (3) a step of exposing the layer of composition, (4) a step of heating the exposed layer of composition, and (5) a step of developing the heated composition layer.
[12] [12] A compound represented by formula (IA):
[13] [13] The compound according to [12], wherein X* is a single bond.
[14] [14] The compound according to [12] or [13], wherein X is -CO-O-* or -O-* (* represents a benzene ring binding site).
[15] [15] A compound according to any one of [12] to [14], wherein n° is 0.
[16] [16] A compound according to any one of [12] to [15], wherein R* and R° are hydrogen atom, or R3 and R* combine together to form a group having a cyclic acetal structure.
[17] [17] A resin comprising a structural unit derived from the compound according to any one of [12] to [16]. Effects of the invention
[0006] It is possible to produce a resist pattern with satisfactory line edge roughness (LER) by using a resist composition in which a resin including a structural unit of the present invention is used.
[0007] As used herein, "(meth)acrylic monomer" means at least one monomer selected from the group consisting of a monomer having a structure of "CH>=CH-CO-" and a monomer having a structure of "CHz=C(CH3)-CO-". Similarly, "(meth)acrylate" and "(meth)acrylic acid" mean "at least one selected from the group consisting of an acrylate and a methacrylate" and "at least one selected from the group consisting of acrylic acid and methacrylic acid", respectively. When a structural unit having "CH2=C(CH3)-CO-" or "CH;=CH-CO-" is cited as for example, a structural unit having both groups should be exemplified in a similar manner.In the groups mentioned in the present description, concerning the groups capable of having both a linear structure and a branched structure, they may have either a linear structure or a branched structure "A combined group" means a group obtained by linking two or more their exemplified groups, the valence number of which may suitably vary depending on the bond state. The term "derived" or "induced", as used herein, means that a polymerizable C=C bond included in the molecule becomes a -C-C- group upon polymerization. When stereoisomers exist, all stereoisomers are included.
[0008] [Resin] The resin of the present invention is a resin (hereinafter sometimes referred to as "resin (A)") including a structural unit represented by formula (I) (hereinafter sometimes referred to as structural unit (I) ), and at least one structural unit unit selected from the group consisting of a structural unit represented by formula (a1-1) (hereinafter sometimes referred to as structural unit (a1-1)) and a structural unit represented by formula ( a1-2) (hereinafter sometimes referred to as structural unit (a1-2)).
[0009] [0009] <Structural unit (I)> The structural unit (I) is represented by the following formula: /# mi —} | A () j elo ) n where, in formula (I), R* represents a hydrogen atom or a methyl group, xt represents a single bond or -CO-O-* (* represents a binding site at Ar ”), X represents -CO-O-*, -O-*, -O-CO-*, -O-CO-(CH>)mm-O-* or -O-(CH>)nn-CO-O-* ( * represents a binding site to Ar”), mm and nn represent 0 or 1, Art and Ar“ each independently represent an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, R each independently represent a hydrogen atom or an acid-labile group, or when two or more R* exist, two R* may combine to form a group having a cyclic acetal structure,
[0010] [0010] Examples of the divalent aromatic hydrocarbon group for Art and Ar include benzenediyl group, naphthalenediyl group, anthracenediyl group and the like.
[0011] The substituent is preferably a halogen atom, an alkyl fluoride group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group having 1 to 11 carbon atoms, an alkoxycarbonyl group having 2 to 11 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyloxy group having 2 to 11 carbon atoms, more preferably a halogen atom, a fluoride group d alkyl having 1 to 6 carbon atoms, a hydroxy group, an alkoxy group having 1 to 11 carbon atoms, an alkoxycarbonyl group having 2 to 11 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyloxy group having 2 to 11 carbon atoms, and more preferably a halogen atom, a hydroxy group, an alkyl fluoride group having 1 to 6 carbon atoms or an alkoxy group having 1 to 11 carbon atoms.
[0012] [0012] The acid-labile group for R means a group in which a group represented by R is eliminated by contact with an acid (for example, p-toluenesulfonic acid) to form a hydroxy group. When R° of the structural unit (I) used in the production of resin (A) is an acid-labile group, in resin (A), R2 can be eliminated (R is converted into an atom of hydrogen) by contact with an acid, and the removal rate is preferably 40% to 100%, more preferably 60% to 100% and more preferably 100%. Examples of the acid-labile group include a group represented by formula (1a) (hereinafter sometimes referred to as "acid-labile group (1a)"), a group represented by formula (2a) (hereinafter sometimes referred to as "acid-labile group (2a)") and the like: O Raa1 Aj Pee (13) naa Raa3 where, in formula (la), R°*, R22 and R®* 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 that can have a substituent, or R* and R22 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 R222 are bonded, naa represents 0 or 1, and * represents a bond: Raat * er (2 a) paaz where in the formula (2a), R°* and R® each independently represents 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 R°°* and R223 may be bonded together the other to form a heterocyclic group having 3 to 20 carbon atoms with -CX°- in which R22 and R°5 are bonded, and -CHz- included in the hydrocarbon group and the heterocyclic group can be replaced by -O- or -S-, X represents an oxygen atom or a sulfur atom, * represents a bonding position.
[0013] [0013] Examples of the alkyl group for R°*, R°°2 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 for R@*, R°°2 and R°°° is preferably 1 to 6, and more preferably 1 to 3.
[0014] [0014] 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, groups obtained by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, alkylcycloalkyl groups or cycloalkylalkyl groups such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl 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, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (an p-cyclohexylphenyl, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group and the like.
[0015] When R°°* and Ra 2 are bonded to each other to form an alicyclic hydrocarbon group, examples of the -C(R22)(R222)(R223) moiety include the following groups. The number of carbon atoms of the alicyclic hydrocarbon group is preferably from 3 to 16 and more preferably from 3 to 12. * represents a bonding position to -O- DH ie ©; paas D 0 , paas , paas ; Raa3; Raa3 “paah, paah; Raa3
[0016] [0016]
[0017] [0017] Examples of the hydrocarbon group in R°°", R@2 and R223 include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and groups obtained by combining these groups.
[0018] [0018] Specific examples of the acid-labile group (1a) include the following groups. * represents a bond. 565065 (I-R2-1-1) (I-R2-1-2) (I-R2-1-3) (I-R2-1-4) (I-R2-1-5) (1-R2 .1-6) % YO 1H YO Yo D (I-R2-1-7) (I-R2-1-8) (I-R2-1-9) (I-R2-1-10) (I- R2-1-11) (I-R2-1-12)
[0019] [0019] Specific examples of the acid-labile group (2a) include the following groups. * represents a bond.
[0020] When two R* combine to form a group having a cyclic acetal structure, examples of *-(R2)2 include a group represented by formula (3a) (hereinafter sometimes referred to as "group (3a)") ): *x. (3a); Rab2 where, in formula (3a), R®! and R® each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or RP! and PR can 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, and -CH>- included in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O- or -CO-, and * represents a bond to an oxygen atom. Examples of the alkyl group and the alicyclic hydrocarbon group include the same groups as mentioned for R®@*, pae2 and pes
[0021] The acid labile group in R* is preferably an acid labile group (2a). R2 is preferably a hydrogen atom or a group represented by formula (2a), or two R* preferably combine together to form a group having a cyclic acetal structure, and R2 is more preferably a hydrogen atom , or two R* more preferably combine to form a group having a cyclic acetal structure.
[0022] [0022] Examples of the structural unit (I) include the structural units mentioned below. The structural unit (I) is preferably a structural unit (I-1) to a structural unit (I-14), a structural unit (I-17) to a structural unit (I-20), a structural unit ( I- 25) to a structural unit (I-28), a structural unit (I- 33) to a structural unit (I-58) or a structural unit (I-67) to a structural unit (1-92), and more preferably a structural unit (I-1) to a structural unit (I-8), a structural unit (I-13), a structural unit (1-14), a structural unit (I-17) to a structural unit (I-20), structural unit (I-25) to structural unit (I-28), structural unit (I-33) to structural unit (I-58), structural unit (I- 67), a structural unit (I-68), a structural unit (I-71), a structural unit (I-72), a structural unit (I-81) or a structural unit (1-82).
[0023] [0023]
[0024] [0024] H CHs H CH, rat Pt Hat ft
[0025] [0025]
[0026] [0026] H CH H CH3 rét ER PET PET OO 9 O 9 ô, OO Q 9 O [ - 57 es + DO + (-47) (aa FF (-49) (1-50) 0 25 2% 6 À 0 © of el AA Oo o + Q, + Q,
[0027] [0027] HH
[0028] [0028] Cc H CH Pnt St te TST
[0029] [0029] H CHs H CHs gt and gt rt 0.0 9 9 9 os % OL 9 hee 9 X > Len Oo — O (1-85) (1-86) (1-87) (1-88) H CHs H CH FT TSF TE} TST
[0030] It is also possible to cite by way of example, as structural unit (I), structural units in which a hydrogen atom corresponding to R! in structural units each represented by formula (I-1), formula (1-3), formula (I-5), formula (I-7), formula (I-9), formula ( I-11), Formula (I-13), Formula (I-15), Formula (1-17), Formula (1-19), Formula (I-21), Formula (I- 23), Formula (I-25), Formula (I-27), Formula (I-29), Formula (I-31), Formula (I-33), Formula (I-35) , Formula (I-37), Formula (I-39), Formula (I-41), Formula (I-43), Formula (I-45), Formula (I-47), formula (I-49), formula (I-51), formula (I-53), formula (1-55) to formula (I-70), formula (I-71), formula ( I-73), formula (I-75), formula (I-77), formula (I-79), formula (1-81), formula (I-83), formula (I- 85), Formula (I-87), Formula (I-89) and Formula (1-91) is substituted with a methyl group, and structural units in which a methyl group corresponding to R* in structural units each represented by the formula ( I-2), Formula (1-4), Formula (I-6), Formula (I-8), Formula (I-10), Formula (1-12), Formula (1- 14), Formula (1-16), Formula (1-18), Formula (1-20), Formula (1-22), Formula (1-24), Formula (1-26) , Formula (1-28), Formula (1-30), Formula (1-32), Formula (1-34), Formula (1-36), Formula (1-38), formula (1-40), formula (1-42), formula (1-44), formula (1-46), formula (1-48), formula (1-50), formula ( 1-52), formula (1-54), formula (1-72), formula (1-74), formula (1-76), formula (1-78), formula (1- 80), formula (1-82), formula (1-84), formula (1-86), formula (1-88), formula (1-90) and formula (1-92) is substituted by a hydrogen atom.
[0031] The content of structural unit (I) in the resin (A) is preferably from 3 to 80 mol%, more preferably from 5 to 60 mol%, more preferably from 5 to 55 mol%, and more preferably still 5 to 50 mol%, based on all structural units.
[0032] [0032] <Structural unit (A1-1) and structural unit (A1-2)> A structural unit (a1-1) and a structural unit (a1-2) are represented by the following formulas: an Ra4 ar Ra5 C = CEl
[0033] [0033] R* and R°° are preferably a methyl group.
[0034] [0034] Examples of the structural unit (a1-1) include structural units derived from the monomers mentioned in JP 2010-204646 A. Of these, 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 preferable, and a structural unit represented by any one of formula (a1-1-1) to formula (a1-1-4) is more preferable.
[0035] The content of the structural unit (a1-1) in the resin (A) is preferably 1 to 60 mol%, more preferably 1 to 55 mol%, more preferably 2 to 55 mol%. , and more preferably 2 to 50 mol%, based on all structural units.
[0036] [0036] 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.
[0037] [0037] The content of the structural unit (a1-2) in the resin (A) is preferably 5 to 70 mol%, more preferably 10 to 65 mol%, more preferably 15 to 65 mol® %, and more preferably 15 to 60 mole %, based on all structural units.
[0038] The resin (A) of the present invention may be a polymer comprising one or more structural units other than the structural unit (I), the structural unit (a1-1) and the structural unit (a1-2 ). Examples of the structural unit other than the structural unit (I), the structural unit (a1-1) and the structural unit (a1-2) include a structural unit having an acid labile group other than l 'structural unit (I), structural unit (a1-1) and structural unit (a1-2) (hereinafter sometimes referred to as "structural unit (a1)"), a structural unit which is a structural unit other that the structural unit having an acid-labile group and has a halogen atom (hereinafter sometimes referred to as “structural unit (a4)>), a structural unit having no acid-labile group other than l structural unit (I) (hereinafter sometimes referred to as "structural unit(s)"), A structural unit having a non-leaving hydrocarbon group (hereinafter sometimes referred to as "structural unit (a5)") and the like. "Acid labile group" means a group having a leaving group which is removed by contact with an acid, thereby forming a hydrophilic group (e.g. a hydroxy group or a carboxy group).
[0039] <Structural Unit (a1)> The structural unit (a1) is derived from a monomer comprising an acid-labile group (hereinafter sometimes referred to as "monomer (a1)").
[0040] [0040] Examples of the alkyl group for R°*, R22 and R include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group and the like. .
[0041] [0041] Examples of the hydrocarbon group in R2!, R2 and R33 include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and groups obtained by combining these groups.
[0042] Examples of group (1) include the following groups.
[0043] [0043] Specific examples of group (2) include the following groups. * represents a binding position.
[0044] 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.
[0045] 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.
[0046] The structural unit derived from a (meth)acrylic monomer having a group (1) is preferably a structural unit represented by the formula (a1-0) (hereinafter sometimes referred to as structural unit (a1-0) These structural units can be used alone, or two or more structural units can be used in combination:
[0047] R°°1 is preferably a methyl group.
[0048] [0048] Examples of the structural unit (a1-0) include, for example, a structural unit represented by any one of the formula (a1-0-1) to the formula (a1-0-18) and a structural unit in which a methyl group corresponding to R2° in the structural unit (a1-0) is substituted with a hydrogen atom and a structural unit represented by any one of the formula (a1-0-1) to formula (a1-0-10), formula (a1-0-13) and formula (a1-0-14) are preferable.
[0049] [0049] When the resin (A) includes the structural unit (a1-0), its content is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 40 mol%, based on all the structural units of the resin (A).
[0050] [0050] Examples of the structural unit having a group (2) in the structural unit (a1) include a structural unit represented by the formula (a1-4) (hereinafter sometimes referred to as “structural unit (a1-4 )")): R332 R333 | 5 a34 (97-8); ne Ra35 where, in the formula (a1-4),
[0051] Examples of halogen atom for R23 and R233 include fluorine atom, chlorine atom and bromine atom.
[0052] [0052] Examples of *-X°*-(a2%2-X232),e- include *-O-, *-CO-O-, *-O-CO-, *-CO-0-A332- CO-0-, *-0-CO-A332-0-, *-OA°° -CO-0-, *-CO-0-A3*2-0-
[0053] [0053] Examples of the alkanediyl group in A include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2- diyl, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
[0054] [0054] A is preferably a single bond, *-CO-O- or *-CO-O- A232-CO-O-, more preferably a single bond, *-CO-O- or *-CO-O -CHz-CO-O-, and more preferably a single bond or *-CO-O-.
[0055] La is preferably 0, 1 or 2, more preferably 0 or 1, and more preferably 0.
[0056] [0056] R33* is preferably a hydrogen atom.
[0057] [0057] 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 R° in the structural unit (a1-4) is substituted with a methyl group, and more preferably units structures each represented by formula (a1-4-1) to formula (a1-4-5), formula (a1-4-10), formula (a1-4-13) and formula (a1-4 -14). PET PETPETPET rg rdt OO. OO N°0 be 970 OO (a1-4-1) (a1-4-2) (a1-4-3) JL OO ag À et ve P&L P&L PET TPE CHs3 OCHs3 Hs OCHs L Bot or oro TO Dd tn ( a1-4-8) (a1-4-9) (a1-4-10) (a1-4-11) (a1-4-12) Ve NET
[0058] [0058] When the resin (A) includes the structural unit (a1-4), the content is preferably 1 to 60 mol%, more preferably 2 to 50 mol%, more preferably 3 to 40 mol%, on the base of the total of all the structural units of the resin (A).
[0059] [0059] Examples of the structural unit having a group (2) derived from a (meth)acrylic monomer also includes a structural unit represented by the formula (a1-5) (hereinafter sometimes referred to as “structural unit (a1 -5)”). The Re “Et St Na Pme (a1-5)
[0060] [0060] Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferred.
[0061] [0061] 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 a structural unit represented by formula (a1-5-1) or formula (a1-5-2) is more preferred.
[0062] 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).
[0063] [0063] Examples of the structural unit (a1) also include the following structural units. qq EE € x © 0 59H95 (a1-3-1) (a1-3-2) (a1-3-3) (a1-3-4) (a1-3-5) (a1-3-6) ( a1-3-7)
[0064] [0064] When the resin (A) comprises the aforementioned structural units, the content is preferably 5 to 60 mol%, preferably 5 to 50 mol%, and more preferably 10 to 40 mol%, based on all the structural units of the resin (A).
[0065] [0065] Examples of structural unit (al) also include the following structural units. Hz CH Le = | The = | LE ++ d G D, Lu Dr DL)
[0066] [0066] <Structural Unit(s)> The structural unit(s) is derived from a monomer having no acid-labile group (hereinafter referred to as "monomer(s)"). The monomer from which the structural unit(s) is derived, has no known acid-labile group in the resist field.
[0067] [0067] <Structural Unit (a2)>
[0068] 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 )»): H, RS + A250 (a2-A) Don (RS) where, in the formula (a2-A), R250 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms possibly having a halogen atom, R°°! represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an 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 *-X2**-(a252- X252) 5", and * represents a bonding site at the carbon atoms to which -R°° is bonded, A represents an alkanediyl group having 1 to 6 carbon atoms, x°°!1 and X each independently represent - O-, -CO-O- or -O-CO-, nb represents 0 or 1, and mb represents an integer of 0 to 4, and when mb is an integer of 2 or more, a plurality of R°* may be same or different from each other.
[0069] [0069] Examples of the halogen atom in R® and R°* include a fluorine atom, a chlorine atom and a bromine atom. Examples of an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom in R2°° include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2 group, 2,3,3,4,4-octafluorobutyl, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group and a perfluorohexyl group. R°50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom or a methyl group. Examples of the alkyl group in R°* include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and more preferably a methyl group.
[0070] [0070] Examples of *-X°°*-(A252-X252) p- include *-O-, *-CO-O-, *-O-CO-, *-CO-O-A3 -CO -O-, *-0-CO-A352-0-, *-OA°° -CO-O-, *-CO-0-A°* -0- CO- and *-0-CO-A %2-0-CO-. Of these, *-CO-O-, *-CO-O-A°**-CO-O- or *-O-A352-CO-O- is preferred.
[0071] [0071] Examples of the alkanediyl group in A22 include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2 group -diyl, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
[0072] A°° is preferably a single bond, *-CO-O- or *-CO-OA°*2-CO-O-, more preferably a single bond, *-CO-O- or *- CO-O-CH>-CO-O-, and more preferably a single bond or *-CO-O-.
[0073] mb is preferably 0, 1 or 2, more preferably 0 or 1, and more preferably 0.
[0074] Examples of structural unit (a2-A) include structural units derived from monomers mentioned in JP 2010-204634 A and JP 2012-12577 A.
[0075] [0075] Examples of the structural unit (a2-A) include the structural units represented by the formula (a2-2-1) to the formula (a2-2-16), and a structural unit in which a corresponding methyl group at
[0076] [0076] When the structural unit (a2-A) is included in the resin (A), the content of the structural unit (a2-A) is preferably 1 to 80 mol%, more preferably 3 to 70 mol. %, more preferably 5 to 60 mol%, and more preferably 10 to 50 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.
[0077] [0077] 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)” ).
[0078] In the formula (a2-1), L®3 is preferably -O- or -O-(CH»)-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, R°16 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.
[0079] [0079] The structural unit (a2-1) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646 A. A structural unit represented by any one of the formula (a2-1-1) to the formula (a2-1-6) is preferred, a structural unit represented by any one of the formula (a2-1-1) to the formula (a2-1-4) is more preferred, and a structural unit represented by formula (a2-1-1) or formula (a2-1-3) is more preferred.
[0080] [0080] 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 the resin (A).
[0081] <Structural unit (a3)> The lactone ring belonging to the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring or an α-valerolactone ring, or a condensed ring. one monocyclic lactone ring and the other ring. Preferably, a γ-butyrolactone ring, an adamantanelactone ring or a bridged ring including a γ-butyrolactone ring structure (eg, a structural unit represented by the following formula (a3-2)) is exemplified.
[0082] 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: Ra18 rats ie f | | CHz=-C CH 4 CHC CHz-C tzt tet Tet tzt ha Ls Xa 16 a7 (Rp (R222) 1 (re, Sn Oo OD O
[0083] [0083] Examples of the aliphatic hydrocarbon group in R°*, R222, R223 and R22° include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and a tert-butyl group.
[0084] [0084] 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.
[0085] In formula (a3-1) to formula (a3-3), preferably, L* to Lê° are each independently -O- or a group in which k3 is an enter of 1 to 4 in *- O-(CH2)es-CO-O-, more preferably -O- and *-O- CH2-CO-O-, and more preferably an oxygen atom, RAS at R°2! are preferably methyl, preferably R°° and R223 are each independently a carboxy group, a cyano group or a methyl group, and preferably p1, q1 and r1 are each independently an integer from 0 to 2, and more preferably 0 or 1.
[0086] 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 an ethyl group, 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°°-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)" 7 Tt 7
[0087] 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 units in which the methyl groups corresponding to R#8, RS, R220 and R°2* in the formula (a3-1) to the formula (a3-4) are substituted with hydrogen atoms in the structural units shown above.
[0088] [0088]
[0089] [0089] When the resin (A) includes the structural unit (a3), the total content is usually 1 to 70 mol%, preferably 3 to 65 mol%, and more preferably 5 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 1 to 60 mol%, more preferably 3 to 50 mol%, and more preferably 5 to 50 mol%, based on all the structural units of the resin (A).
[0090] [0090] <Structural unit (a4)> Examples of structural unit (a4) include the following structural units:
[0091] [0091] 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.
[0092] [0092] Examples of the structural unit (a4) include a structural unit represented by the formula (a4-0), a structural unit represented by the formula (a4-1), and a structural unit represented by the formula (a4-4 ): R54 good (a4-0) O
[0093] [0093] 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.
[0094] 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,
[0095] [0095] L® is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
[0096] [0096] 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:
[0097] [0097] Ra41Hz VS
[0098] [0098] Examples of the saturated hydrocarbon group in R°* include a chain hydrocarbon group and a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and the groups formed by combining these groups.
[0099] [0099] 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.
[0100] [0100] 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 the halogen atom is preferably fluorine atom: + ——Xa43— a a45 (a-g3) where, in the formula (a-g3), X represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-0-, A: represents a saturated hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, and * represents a binding site at R2*2.
[0101] [0101] 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).
[0102] [0102] 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).
[0103] [0103] 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 (ag 2) where, in the formula (a-g2),
[0104] The number of carbon atoms of the saturated hydrocarbon group for A°*° is preferably 1 to 6, and more preferably 1 to 3.
[0105] [0105] The preferred structure of the group represented by the formula (a-g2) is the following structure (* is a bonding site to a carbonyl group).
[0106] [0106] 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.
[0107] [0107] Examples of the divalent saturated hydrocarbon group represented by A, A3 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 a group divalent saturated hydrocarbon 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.
[0108] In a group represented by formula (a-g1), examples of the group in which X** is -O-, -CO-, -CO-O- or -O-CO- include the following groups. In the following examples, * and ** each represent a binding site, and ** is a -O-CO-R®** binding site, YT _ AT Le A ï 0 O O O
[0109] [0109] 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 R** in the structural unit represented by the formula (a4- 1) in the following structural units is substituted with a hydrogen atom.
[0110] [0110] Hs Hs Hz Hs Hg Hg iron Jon er: er: er: “jen
[0111] [0111] 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): Ho RS
[0112] [0112] Examples of the alkanediyl group having 1 to 6 carbon atoms for L*% include the same groups as those mentioned for
[0113] Examples of the structural unit represented by formula (a4-2) include structural units each of which is represented by formula (a4-1-1) to formula (a4-1-11). It is also possible to exemplify as a structural unit represented by the formula (a4-2), a structural unit in which a methyl group corresponding to R® in a structural unit (a4-2) is substituted with an atom of hydrogen.
[0114] [0114] HzRP
[0115] [0115] Examples of the alkanediyl group in L° include those which are the same as those mentioned for A *.
[0116] [0116] The divalent saturated hydrocarbon group optionally having a fluorine atom in Afl is preferably a divalent chain saturated hydrocarbon group optionally having a fluorine atom and a divalent alicyclic saturated hydrocarbon group optionally having a fluorine atom, and more preferably a perfluoroalkanediyl group.
[0117] [0117] 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. Of these groups, preferred are fluorinated alkyl groups such as a 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; cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantylmethyl group and the like.
[0118] [0118] In the formula (a4-3), L° is preferably an ethylene group.
[0119] Examples of the structural unit represented by formula (a4-3) include structural units each of which is represented by formula (a4-1-1) to formula (a4-1"-11). It is also possible to exemplify as the structural unit represented by the formula (a4-3), a structural unit in which a methyl group corresponding to R in a structural unit (a4-3) is substituted with an atom of hydrogen.
[0120] [0120] Examples of the structural unit (a4) include a structural unit represented by the formula (a4-4): eu ° Ao SU (a4-4) pa” where, in the formula (a4-4), R2 ! represents a hydrogen atom or a methyl group,
[0121] [0121] Examples of saturated hydrocarbon group for R include those which are the same as the saturated hydrocarbon group represented by R°*2, Rf is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and more preferably an alkyl group having 1 to 6 carbon atoms having a fluorine atom.
[0122] [0122] In the formula (a4-4), A”! is preferably -(CHz)1-, more preferably an ethylene group or a methylene group, and more preferably a methylene group.
[0123] [0123] The structural unit represented by the formula (a4-4) includes, for example, the following structural units and the structural units in which a methyl group corresponding to R* in the structural unit (a4-4) is substituted with a hydrogen atom in the structural units represented by the following formulas.
[0124] [0124] 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).
[0125] <Structural unit (a5)> Examples of the non-leaving hydrocarbon group belonging to the structural unit (a5) include groups having a linear, branched or cyclic hydrocarbon group. Of these, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. The structural unit (a5) includes, for example, a structural unit represented by the formula (a5-1): 51 H2 (a5-1) 55
[0126] [0126] 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.
[0127] [0127] 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.
[0128] [0128] Examples of the group in which -CH>- included in the divalent saturated hydrocarbon group represented by L°° is replaced by -O- or -CO- include the groups represented by the formula (L1-1) to the formula (L1-4). In the following formulas, * and ** each represent a binding site, and * represents a binding site to an oxygen atom.
[0129] [0129] L* is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
[0130] The group represented by the formula (L1-1) includes, for example, the following divalent groups. + xx * 2 dx #13 xp Ÿ C4 +k AN * 8 ek H CH Hs O ok Ö N + 07 A Ô 2 Hs CHs
[0131] The group represented by the formula (L1-2) includes, for example, the following divalent groups. OA of HT Hs Hz 3 Do Aho” Aho” Aho” Aho”
[0132] The group represented by the formula (L1-3) includes, for example, the following divalent groups.
[0133] The group represented by formula (L1-4) includes, for example, the following divalent groups. xx O ait * Oase AO „IT A A Q xx À Va * Q xx SO ts A}
[0134] [0134] L° is preferably a single bond or a group represented by the formula (L1-1).
[0135] [0135] 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.
[0136] [0136]
[0137] <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.
[0138] [0138] 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"):
[0139] [0139] Examples of the halogen atom represented by RS include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0140] [0140] 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.
[0141] [0141] 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) . Before replacing -CHz- included in the saturated hydrocarbon group with -O-, -S- or -CO-, the number of carbon atoms is 17 or less. In the following formulas, * and ** represent a binding site, and * represents an A' binding site.
[0142] [0142] X represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms.
[0143] [0143] 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. 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) mentioned later.
[0144] The structural unit represented by the formula (II-2-A") is preferably a structural unit represented by the formula (II-2-A): RIIS
[0145] [0145] Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by R', RI Q and Q include those which are the same as the perfluoroalkyl group having 1 to 6 carbon atoms represented by QP: mentioned later.
[0146] The structural unit represented by formula (II-2-A) is preferably a structural unit represented by formula (II-2-A-1): RS
[0147] [0147] Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by RŸ include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec -butyl, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. Examples of the divalent saturated hydrocarbon group represented by Xl include those which are the same as the divalent saturated hydrocarbon group represented by XE,
[0148] The structural unit represented by the formula (II-2-A-1) is preferably a structural unit represented by the formula (II-2-A-2): RIIS
[0149] [0149] Examples of the structural unit represented by the formula (II-2-A") include the following structural units, the structural units in which a group corresponding to the methyl group of R1 is substituted by a hydrogen atom, a halogen atom (for example, a fluorine atom) or an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom (for example, a trifluoromethyl group, etc.) and the structural units mentioned in WO 2012/050015 A. ZA” represents an organic cation.
[0150] [0150] The structural unit having a cation having a sulfonio group and an organic anion in a side chain is preferably a structural unit represented by the formula (II-1-1): R'14 ett pis (II-1- 1) OO—A1-RNÆS7
[0151] [0151] Examples of the structural unit including a cation in the formula (IL-1-1) include the following structural units and the structural units in which a group corresponding to the methyl group for R!!* is substituted by a 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.). =S TC E PS TE tene} OC OO OO Q &
[0152] [0152] Examples of the organic anion represented by A include a sulfonic acid anion, a sulfonylimide anion, a sulfonyl methide anion and a carboxylic acid anion. The organic anion represented by A is preferably a sulfonic acid anion, and examples of the sulfonic acid anion include those which are the same as an anion represented by the formula (B1).
[0153] [0153] Examples of the sulfonylimide anion represented by A include the following.
[0154] [0154] Examples of the sulfonyl methide anion include the following. CF3 F,C—CF3 O,S—CF; O2S-CF, o,s-CF, Os _ Fo O2 | F4C. F O2 | F,C—s — F,C—C—s 1 F2C-C-S 1 Os —CF4 O2S-GF > O2S-GF > LF, F,b-CF;
[0155] [0155] Examples of the carboxylic acid anion include the following. ne Ho A Hz ALL mo, DD ‘ Oe CHs 0 De ‘ C ON H 7° Le 6 À O4 2 O4 3 ne A, Ao EU KG do “b D ç OH ee ee © FFF 9
[0156] [0156] Examples of the structural unit represented by the formula (II-1-1) include the following structural units.
[0157] [0157] 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).
[0158] The resin (A) may include a structural unit other than the aforementioned structural units, and examples of the structural units include the structural units well known in the art.
[0159] The resin (A) is preferably a resin composed of a structural unit (I), a structural unit (a1-1) and a structural unit (a1-2), a resin composed of a structural unit (T) and a structural unit (a1-1), a resin composed of a structural unit (T) and a structural unit (a1-2), a resin composed of a structural unit ( I), a structural unit (a1-1), a structural unit (a1-2) and a structural unit (s), a resin composed of a structural unit (I), a structural unit structure (a1-1), a structure unit (a1-2), a structure unit (a1) and structure unit (s), a resin composed of a structure unit (I), a structure unit (a1-1) and a structural unit (s), a resin composed of a structural unit (I), a structural unit (a1-2) and a structural unit (s), a resin composed a structural unit (I), a structural unit (a1-
[0160] The structural unit (a1) is preferably an a(1-4) structural unit. The structural unit (s) is preferably at least one unit selected from the group consisting of a structural unit (a2) and a structural unit (a3). The structural unit (a2) is preferably one selected from the group consisting of the structural unit (a2-1) and a structural unit (a2-A). The structural unit (a3) is preferably at least one unit selected from the group consisting of a structural unit represented by the formula (a3-1), a structural unit represented by the formula (a3-2) and a structural unit represented by the formula (a3-4).
[0161] 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.
[0162] <Compound (IA)> The compound of the present invention is a compound represented by formula (IA) (hereinafter sometimes referred to as "compound (IA)"): R1 onl | | (a) IRS]tee) GOLD
[0163] [0163] Compound (IA) is a compound in which Ar is a greater number trivalent or multivalent benzene ring, n = 2, and each -O-R is bonded to each other in formula (I). Such a compound (IA) is, for example, a monomer from which the aforementioned structural units represented by formula (I-13) to formula (I-16), formula (1-19) to formula (I -24) ), formula (1-27) to formula (I-66) and formula (I-71) to formula (I-92) are derived.
[0164] [0164] Examples of the aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent for Ar* include the same exemplified groups as the aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent for Ar*. placeholder for Art in formula (D).
[0165] [0165] Examples of the acid labile group for R3 and R* include the same exemplified groups as the acid labile group for R* in formula (I) (acid labile group (1a) or acid-labile group (2a), etc.).
[0166] [0166] When R and R* combine to form a group having a cyclic acetal structure, examples of such a group include the same groups exemplified when two R* combine with each other to form a group having a cyclic acetal structure in formula (I) (group (3a), etc.).
[0167] [0167] Examples of the halogen atom, the alkyl fluoride group having 1 to 6 carbon atoms or the alkyl group having 1 to 12 carbon atoms (-CH>- included in the alkyl group and the group alkyl fluoride can be replaced by -O- or -CO-) for R° include the same groups as the substituent for Ar in formula (1). n' is preferably an integer from 0 to 2, more preferably 0 or 1, and more preferably 0.
[0168] [0168] Examples of the compound (IA) include the following. 4 oh 4 cn
[0169] [0169] H
[0170] [0170]
[0171] [0171] HCH H Hs CH, CH; CH; ct Pa 5 > O do & /— O > A Oo > ( [> > RS (IA-85) (IA-86) (IA-87) (IA-88)
[0172] It is also possible to cite by way of example, as compound (IA), a compound in which a hydrogen atom corresponding to R* in compounds each represented by the formula (IA-13), the formula (IA-15), formula (IA-19), formula (IA-21), formula (IA-23), formula (IA-27), formula (IA-29), formula ( IA-31), Formula (IA-33), Formula (IA-35), Formula (IA-37), Formula (IA-39), Formula (IA-41), Formula (IA- 43), the formula (IA-45), the formula
[0173] [0173] <Production method of compound (IA)> A compound (IA) can be obtained by reacting a compound represented by the formula (Ia) with a compound represented by the formula (Ib) in the presence of a catalyst in a solvent: R! R! cH=4 c | HQ | x} X!
[0174] [0174] [Resist composition] The resist composition of the present invention preferably includes a resin (A) and an acid generator known in the field of resists (hereinafter sometimes referred to as "acid generator (B)"). "). The resist composition of the present invention may further include a resin other than resin (A).
[0175] [0175] <Resin other than resin (A)> The resin other than resin (A) may be a resin which does not include at least one selected from the group consisting of a structural unit (I) or a structural unit (a1-1) and a structural unit (a1-2). Examples of such a resin include a resin in which a structural unit (T) is removed from the resin (A) (hereinafter sometimes referred to as "resin (AY)"), a resin in which at least one structural unit selected in the group consisting of the structural unit (a1-1) and the structural unit (a1-2) is removed from the resin (A) (hereinafter sometimes referred to as "resin (AZ)"), a resin composed only of a structural unit (a4) and a structural unit (a5) (hereinafter sometimes referred to as resin (X)) and the like.
[0176] The resin (X) is preferably a resin including a structural unit (a4).
[0177] In the resist composition of the present invention, the resin (A) can be used in combination with the resin other than the resin (A), and when used in combination with the resin other than the resin (A ), the resin (A) is preferably used in combination with a resin including a structural unit having an acid labile group and/or a resin including a structural unit having a fluorine atom, and more preferably used in combination with resin (AY), resin (AZ) and/or resin (X).
[0178] [0178] <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.
[0179] [0179] Specific examples of the acid generator (B) include compounds generating acid upon exposure to radiation mentioned in JP 63-26653 A, JP 55-164824 A, JP 62-69263 A, JP 63-146038 A , JP 63-163452 A, JP 62-153853 A, JP 63-146029 A, US Patent No.
[0180] The acid generator (B) is preferably an acid generator containing fluorine, and more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as “acid generator (B1) "): Qh + -0.S [61 zi' 038 | ALA, (BIJ) La where, in the formula (B1),
[0181] [0181] Examples of the perfluoroalkyl group represented by QPt and QP include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluorohexyl group.
[0182] [0182] 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 using two or more of these groups in combination.
[0183] [0183] The group in which -CH>- included in the divalent saturated hydrocarbon group represented by L” is replaced by -O- or -CO- includes, for example, a group represented by any one of the formula (b1 -1) to formula (b1-3). In the groups represented by formula (b1-1) to formula (b1-3) and the groups represented by formula (b1-4) to formula (b1-11) which are specific examples thereof, * and ** represent a bond, and * represents a bond to -Y.
[0184] [0184] ax X b3 *% OL + „Oo DD SA | b4 T*DS, be b7
[0185] [0185] In the groups represented by the formula (b1-1) to the formula (b1-3), when -CHz- included in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of atoms of carbon before replacement is taken as the number of carbon atoms of the saturated hydrocarbon group.
[0186] [0186] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by L! is replaced by -O- or -CO- is preferably a group represented by formula (b1-1) or formula (b1-3). Examples of the group represented by the formula (b1-1) include the groups represented by the formula (b1-4) to the formula (b1-8): 9 O î b11 1 b12 Ao tE, TT” RE (b1-4 ) (b1-5) (b1-6) 9 X b16 Oo Ao AR mb AN DS, b187* 2 (b1-7) (b1-8) In the formula (b1-4), LPS represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. In the formula (b1-5), LP represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH:- included in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-.
[0187] [0187] Examples of the group represented by the formula (b1-3) include the groups represented by the formula (b1-9) to the formula (b1-11). AS oe A I u“
[0188] [0188] In the group represented by formula (b1-9) to the group represented by formula (b1-11), when a hydrogen atom included in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before substitution is taken as the number of carbon atoms of the saturated hydrocarbon group.
[0189] [0189] Examples of the group represented by the formula (b1-4) include the following:
[0190] Examples of the group represented by formula (b1-5) include the following: Q O 0 or Ag of A of 2 Q X CH, Sogn Jr er RAP Ö Hs Hs
[0191] [0191] Examples of the group represented by the formula (b1-6) include the following: NE NN Re At tek O + x" xx k 4x uk CR DR | FOT | M oft 0 x Agtho Loto" Lothor" Ald Al where , * and ** represent a bond, and * represents a bond to Y.
[0192] [0192] Examples of the group represented by the formula (b1-7) include the following:
[0193] [0193] Examples of the group represented by the formula (b1-8) include the following: ee O O of O% ok; Vo x Le I x 7
[0194] [0194] Examples of the group represented by the formula (b1-2) include the following: ee Ho nn As x x Pte HA u Hot, 3 Ha
[0195] [0195] Examples of the group represented by the formula (b1-9) include the following:
[0196] [0196] Examples of the group represented by the formula (b1-10) include the following: Hs Hz Hz ok Ha ok Hs ik xx EE xk 2 xx AO xx OH Ex xx N Hz
[0197] [0197] Examples of the group represented by the formula (b1-11) include the following:
[0198] [0198] 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).
[0199] [0199] 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)ja-CO-OR®! or a group -(CH2);-O-CO-RE (where RP represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or groups obtained by combining these groups, and -CHz- included in an alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2- 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 of 0 to 4).
[0200] [0200] Examples of halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.
[0201] [0201] Examples of Y include the following. (CR O O Ö 2 O DS VE ade ane 0 0 À, AAE. (Y100) + * x vi (7102) (7708) (7104) > (705) (Y106) © O Me A De X N S° LA
[0202] [0202] 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)>- 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).
[0203] [0203] The anion in the salt represented by formula (B1) is preferably an anion represented by formula (B1-A-1) to formula (B1-A-59) [hereinafter sometimes referred to as "anion (B1-A-1)" according to the number of the formula], and more preferably an anion represented by any one of the formula (B1-A-1) to the formula (B1-A-4), the formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40) and formula (B1-A-47) to formula (B1-A-59).
[0204] [0204] OH o on QE Qb2 QE a2 b1 b2 - On A41 - Q Q or A41 7 os TE Oss O3S L ô
[0205] [0205] O O
[0206] [0206] OH 02 Qb! "at Oh ar! gold 5 Q Om F F A41 3 OH L F F OH LA41 O (B1-A-22) (B1-A-23) (B1-A-24) ab! „ab Oo CH; at Ch, - On A41 "038 LAM 038 L ° 3 O O 5 O O (B1-a-25) © (B1-A-26) ©
[0207] [0207] Oz 00 | ST “TO 67° 0 b1 62 O Ô _ TD va Lan O3S L (B1-A-30) (B1-A-31) ï (B1-A-32) OO On pa © ° Ri7 Qh al A Ca _ LA41 9 - F LAN 9 TT “LAI O3S So O O3S EA OOO Qb F Q F (B1-A-33) E (B1-A-34) (B1-A-35)
[0208] [0208]
[0209] [0209] O. O From A From X The „st O oO 9 0 0 0 9 0
[0210] [0210] R to RU each independently represent, for example, an alkyl group having 1 to 4 carbon atoms, and preferably a methyl group or an ethyl group. R® is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms or groups formed by combining these groups, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. THE is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q®* and QP2 are the same as those defined above.
[0211] [0211] Examples of the anion in the salt represented by the formula (B1) preferably include anions represented by the formula (B1a-1) to the formula (B1a-38).
[0212] [0212]
[0213] [0213] kf © | ) € | U no es bon + O + Ö 0 O - F RK SF _ F ae Sao y (Bla-23) 9 (Bla-24) (Bla-25) Mp A Ur or OH _ F _ _ F ee 52 EN (Bla -26) 0 (Bla-27) 9 (Bla-28) A Le - FF - FF 0 (Bla-31) (Bla-29) (Bla-30) O
[0214] Of these, the anion is preferably an anion represented by any one of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a -16), formula (B1a-18), formula (B1a-19) and formula (B1a-22) to formula (B1a-38).
[0215] [0215] 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).
[0216] The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.
[0217] [0217] 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. An alkyl fluoride group having 1 to 12 carbon atoms represents an alkyl group having 1 to 12 carbon atoms which has a halogen atom. Examples of the alkyl fluoride group having 1 to 12 carbon atoms include alkyl fluoride groups such as fluoromethyl group, difluoromethyl group, trifluoromethyl group, perfluorobutyl group and the like. The number of carbon atoms of the alkyl fluoride group is preferably 1 to 9, more preferably 1 to 6, and more preferably 1 to 4.
[0218] [0218] 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.), an aromatic hydrocarbon group having a hydrocarbon group alicyclic (a p-cyclohexylphenyl group, a p-adamantylphenyl group etc.) and the like.
[0219] 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.
[0220] [0220] The cycle formed with the sulfur atoms to which RP and RP5 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-containing ring includes a 3 to 12 membered ring and is preferably a 3 to 7 membered ring and particularly includes the following rings. * represents a bond. dy to to A to to to Q
[0221] [0221] The cycle formed by combining RP and RP!° together can be a monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated ring. This ring includes a 3 to 12 membered ring and is preferably a 3 to 7 membered ring. Examples of the ring include, 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.
[0222] 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. 6 CaHs 6 OS CeH413 CgH47 (b2-c-1) (b2-c-2) (b2-c-3) (b2-c-4) (b2-c-5) (b2c8) (b2-c-7 ) (b2-c8) H3 H3 H3 -C4Hg -C4Hg © © °a © Q = O7 02 Oi OpeO} WHERE H c- tC,H, (b2-c-14) (b2-c-9) (b2- c-10) (b2-c-11) (b2-c-12) (62-013)
[0223] [0223]
[0224] [0224] Examples of cation (b2-2) include the following cations. + + + + DO O+0- OOH (b2-c-28) (b2-c-29) (b2-c-30) (b2-c-50)
[0225] [0225] Examples of cation (b2-3) include the following cations. Q ) O O these AO CC © OS (b2-c-31) (b2-c-32) (b2-c-33) (b2-c-34)
[0226] [0226] Examples of cation (b2-4) include the following cations. H3 (2 (2 (2 (2 + “0 + Á 7 Á }- CH X 4 JCH + X Ss UVUU b2-c-38 (b2--38) (b2-c-36) (52037) (2098) HzC, Hs; "© "© Q ©
[0227] [0227] The acid generator (B) is a combination of the aforementioned anions and the aforementioned organic cations, and these can be optionally combined. Examples of the acid generator (B) are preferably combinations of an anion represented by any one of formula (B1a-1) to formula (B1a-3) and formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula (Bla-19) and from formula (B1a-22) to formula (B1a-38) with a cation (b2-1), a cation (b2-3), a cation (b2-4).
[0228] [0228] Examples of the acid generator (B) are preferably those represented by the formula (B1-1) to the formula (B1-56). Of these, those containing an arylsulfonium cation are preferred, and those represented by the formula (B1-1) to the formula (B1-3), the formula (B1-5) to the formula (B1-7), the 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.
[0229] [0229] € KF Q FK JF : Ö 0, ® (B1-13) LG (B1-14) ° (B1-15) AL a Q Pe Lo MY po Fear of 0572 Ö (B1-17) (B1-18 ) (B1-16) (© JR ' | ù 5 ® Se k X So °s | ' "Os "048 Ö ° (B1-19) 9 (B1-20) (B1-21) 5 [0230]
[0231] [0231]
[0232] [0232]
[0233] In the resist composition of the present invention, the acid generator content is preferably 1 mass part or more and 45 mass parts or less, more preferably 1 mass part or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 40 parts by mass or less, and more preferably 10 parts by mass or less and 40 parts by mass or less based on 100 parts by mass of the resin (A) mentioned above.
[0234] [0234] <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.
[0235] [0235] <“Quencher” deactivating agent (C)> Examples of deactivating agent (C) include a basic nitrogen-containing organic compound or an acid-generating salt having an acidity lower than that of an acid. generated from the acid generator (B). When the composition includes the deactivating agent (C), the content of the deactivating agent (C) is preferably about 0.01 to 15% by weight, more preferably about 0.01 to 10% by weight, more preferably about 0.1 to 5% by weight and more preferably about 0.1 to 3% by weight, based on the amount of the solid component of the resist composition. Examples of the basic nitrogen-containing organic compound include an amine and an ammonium salt. Examples of amine include aliphatic amine and aromatic amine. Examples of aliphatic amine include primary amine, secondary amine and tertiary amine. Examples of amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine , tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, la=dicyclohexylmethylamine, la=tris[2-(2-methoxyethoxy)ethyl]ami ne, 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, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1 ,2-di(4-pyridyl)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di(2-pyridyl)ketone, 4,4"-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine and the like, preferably diisopropylaniline, and more preferably 2,6-diisopropylaniline. Examples of ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate and choline.
[0236] [0236] 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. Examples of acid generating salt having a lower acidity than an acid generated from the acid generating acid (B) include salts represented by the following formulas, a salt represented by the formula (D) mentioned in JP 2015-147926 A (hereinafter sometimes referred to as "weak acid inner salt (D)", and salts mentioned in JP 2012-229206 A, JP 2012-6908 A, JP 2012-72109 A, JP 2011-39502 A and JP 2011-191745 A.
[0237] [0237] Examples of the weak acid inner salt (D) include the following salts. _ 007 700C + 007 oo do 00 “00 0 90 coo” oo COO OO coo COO” Sofon dodo Br CI 007 coo” coo” 00 oo oO, doo dio Fo do dig _ N _
[0238] [0238] <Other components> The resist composition of the present invention may also include components other than the components mentioned above (hereinafter sometimes referred to as "other components (F)"). are not particularly limited and it is possible to use various additives known in the art of resists, for example sensitizers, dissolution inhibitors, surfactants, stabilizers, and colorants.
[0239] [0239] … <Preparation of resist composition> The resist composition of the present invention can be prepared by mixing a resin (A), an acid generator (B) and optionally a resin other than the resin resin (A), solvent (E), deactivating agent (C), and other components (F). The mixing order of these components is any order and it is not particularly limited. It is possible to select, as the temperature during mixing, an appropriate temperature of 10 to 40°C, depending on the kind of the resin, the solvent solubility (E) of the resin and the like. It is possible to choose, as the mixing time, an appropriate time from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited and it is possible to use mixing with agitation.
[0240] <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.
[0241] [0241] <Applications> The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EF) or a resist composition for extreme ultraviolet (UVE) exposure, and particularly suitable as a resist composition for electron beam (EF) exposure or as a resist composition for EUV exposure and the resist composition is useful for fine processing of semiconductors. EXAMPLES
[0242] 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.
[0243] Synthesis Example 1: Synthesis of Compound Represented by Formula (1-17)
[0244] Synthesis Example 2: Synthesis of the compound represented by formula (1-25) in HO 9 Q Ç + CT _. ok F 0_,0 (I-17-d) (I-25-a) T ] (I-25-b)
[0245] Example 1: Synthesis of the compound represented by formula (1-43) — © Oo OMe (I-17-e) Q,
[0246] [0246] Example 2: Synthesis of the compound represented by the formula (1-33) © Oo
[0247] Synthesis Example 3: Synthesis of the compound represented by the formula (1-67) —®© (ON os N—
[0248] Synthesis Example 4: Synthesis of Compound Represented by Formula (1-68)
[0249] [0249] Example 3: Synthesis of the compound represented by the formula (I-49) & R O F
[0250] [0250] Example 4: Synthesis of the compound represented by the formula (I-37) SO” Oo
[0251] Example 5: Synthesis of the compound represented by the formula (1-81) (ON ces OH + E10, „OEL OO OH CL, OEt (I-17-c) oe OH OA 5 (I-81-a) (I-81-b) (I-81-d) 5.00 parts of a compound represented by formula (I-81-a), 0.008 part of a compound represented by formula (I-17-c ) and 50 parts of toluene were mixed, followed by stirring at 23°C for 30 minutes and further raising the temperature to 100°C. To the mixed solution thus obtained, 7, 05 parts of a compound represented by formula (I-81-b) was added at 100°C, followed by stirring at 110°C for 2 hours and further cooling to 23°C. mixture thus obtained, 25 parts of ethyl acetate and 30 parts of ion-exchanged water were added, and after stirring at 23°C for 30 minutes, the organic layer was isolated by separation. organic material thus recovered, 30 parts of ion-exchanged water were added and, after stirring at 23° C. pe Within 30 minutes, the organic layer was isolated by separation. This water washing operation was repeated three times. The organic layer thus obtained was concentrated, and then the concentrated mass was isolated using a column (60 N silica gel (spherical, neutral) 100-210 µm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 10/1) to obtain 2.19 parts of a compound represented by formula (I-81-d).
[0252] [0252] Example 6: Synthesis of the compound represented by the formula (I-71) Oo O
[0253] [0253] Resin Synthesis The compounds (monomers) used in resin synthesis are shown below. H H = Hs Hs tt Er YO N Le
[0254] Example 7 [Synthesis of Resin A1] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (I- 17) as monomers, these monomers were mixed in a molar ratio of 19:25:38:18 [monomer (a1-4-2): monomer (a1-1-3): monomer (a1-2-6): monomer (I-17)] 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 amounts of 1.2 mol% and 3.6 mol% based on the total molar number of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain resin A1 having a mass-average molecular weight of about 5.6 x 103 with a yield of 62%. This Al resin includes the following structural units (a removal rate of one ethoxyethyl group in all ethoxyethyl groups of monomer (a1-4-2) and monomer (1-17) is 100%).
[0255] Example 8 [Synthesis of resin A2] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (1- 17) as monomers, these monomers were mixed in a molar ratio of 19:25:38:18 [monomer (a1-4-2): monomer (a1-1-3): monomer (a1-2-6): monomer (I-17)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitria and azobis (2,4 dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the total molar number of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, the polymerization reaction solution was cooled to 15°C and an aqueous solution of p-toluenesulfonic acid was added, followed by stirring for 6 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain resin A2 having a mass-average molecular weight of about 5.9 x 103 with 58% efficiency. This resin A2 includes the following structural units (a removal rate of one ethoxyethyl group in all ethoxyethyl groups of monomer (a1-4-2) and monomer (I-17) is 72%).
[0256] Example 9 [Synthesis of resin A3] A monomer (a1-1-3), a monomer (a1-2-6) and a monomer (I-17) were used as monomers, these monomers were mixed in a molar ratio of 25:38:37 [monomer (a1-1-3): monomer (a1-2-6): monomer (I-17)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the molar number total of all monomers, followed by polymerization of the mixture by heating to 73°C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain resin A3 having a mass-average molecular weight of about 5.5 x 103 with a yield of 65%. This resin A3 comprises the following structural units (a rate of elimination of an ethoxyethyl group in all the ethoxyethyl groups of the monomer (1-17) is 100%). Hs Hs your ta ÆcH,
[0257] Example 10 [Synthesis of resin A4] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6), a monomer (a2- 1-3), a monomer (a3-4-2) and a monomer (I-17) as monomers, these monomers were mixed in a molar ratio of 12:20:35:3:15:15 [monomer (a1 -4-2): monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (I-17)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the molar number total of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain resin A4 having a mass-average molecular weight of about 5.8x10 with a yield of 63%. This A4 resin includes the following structural units (a removal rate of one ethoxyethyl group in all ethoxyethyl groups of monomer (a1-4-2) and monomer (1-17) is 100%). {on CH ik to Æch, ik tou {ch } 5 O O @ í no C” ‘ Oh) I OH
[0258] Example 11 [Synthesis of resin A5] A monomer (a1-1-3), a monomer (a1-2-6), a monomer (a2-1-3), a monomer (a3- 4-2) and a monomer (I-17) 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 (I-17)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers . To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the total molar number of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, which was followed by stirring for 12 hours and further by further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain resin A5 having a mass-average molecular weight of about 5.4 x 10° with an efficiency of
[0259] Example 12 [Synthesis of resin A6] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (I- 25) as monomers, these monomers were mixed in a molar ratio of 19:25:38:18 [monomer (a1-4-2): monomer (a1-1-3): monomer (a1-2-6): monomer (I-25)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitria and azobis (2,4 dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the total molar number of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain resin A6 having a mass-average molecular weight of about 5.2 x 10° with an efficiency of 59%. This A6 resin includes the following structural units (a removal rate of one ethoxyethyl group in all ethoxyethyl groups of monomer (a1-4-2) and monomer (I-25) is 100%).
[0260] Example 13 [Synthesis of resin A7] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6), a monomer (a2- 1-3), a monomer (a3-4-2) and a monomer (I-25) as monomers, these monomers were mixed in a molar ratio of 12:20:35:3:15:15 [monomer (a1 -4-2): monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (I-25)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the molar number total of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, followed by stirring for 12 hours and further by isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain resin A7 having a mass-average molecular weight of about 5.4 x 103 with a yield of 61%. This A7 resin includes the following structural units (an elimination ratio of one ethoxyethyl group in all ethoxyethyl groups of monomer (a1-4-2) and monomer (I-25) is 100%).
[0261] [0261] Example 14 [Synthesis of Resin A8] Monomer (a1-4-2), monomer (a1-1-3), monomer (a1-2-6) and monomer (1 -33) as monomers, these monomers were mixed in a molar ratio of 19:25:38:18 [monomer (al-4-2): monomer (a1-1-3): monomer (a1-2-6) : monomer (I-33)] and methyl isobutyl ketone was mixed in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4 dimethylvaleronitrile) as initiators were added in amounts of 1.2 mol% and 3.6 mol% based on the total molar number of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, followed by stirring for 12 hours and further by isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain resin A8 having a mass-average molecular weight of about 5.2 x 103 with a yield of 60%. This A8 resin includes the following structural units. Hs Hz “5 tog tE CH,
[0262] [0262] Example 15 [Synthesis of Resin A9] A monomer (a1-1-3), a monomer (a1-2-6) and a monomer (I-33) were used as monomers, these monomers were mixed in a molar ratio of 25:38:37 [monomer (a1-1-3): monomer (a1-2-6): monomer (I-33)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the molar number total of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, the polymerization reaction solution was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain an A9 resin having a mass-average molecular weight of about 5.0 x 10° with a yield of 65%. This A9 resin includes the following structural units.
[0263] Example 16 [Synthesis of resin A10] Acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (I-43) were used as monomers, these monomers were mixed in a molar ratio of 37:20:32:11 [acetoxystyrene: monomer (a1-1-3): monomer (a1-2-6): monomer (I-43)] and methyl isobutyl ketone a was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile was added as an initiator in an amount of 7 mol% based on the total molar number of all monomers, which was followed by polymerization of the mixture by heating to
[0264] Example 17 [Synthesis of resin A11] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6), a monomer (a2- 1-3), a monomer (a3-4-2) and a monomer (I-33) as monomers, these monomers were mixed in a molar ratio of 12:20:35:3:15:15 [monomer (a1 -4-2): monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (1-33)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the molar number total of all monomers, followed by polymerization of the mixture by heating to 73°C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain resin A11 having a mass-average molecular weight of about 5.1 x 103 with a yield of 62%. This A11 resin includes the following structural units. ton, toy to to tof Lc DO SO L- Ì an on 1 HM 07 ) SL. 5 OH
[0265] Example 18 [Synthesis of resin A12] A monomer (a1-1-3), a monomer (a1-2-6), a monomer (a2-1-3), a monomer (a3- 4-2) and a monomer (I-33) 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 (I-33)] 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) as initiators were added in amounts of 1.2 mol% and 3.6 mol% based on the molar number total of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, the polymerization reaction solution was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain A12 resin having a mass average molecular weight of about 5.2 x 103 with a yield of 64%. This A12 resin includes the following structural units.
[0266] Example 19 [Synthesis of resin A13] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (I- 68) as monomers, these monomers were mixed in a molar ratio of 19:25:38:18 [monomer (a1-4-2): monomer (a1-1-3): monomer (a1-2-6): monomer (I-68)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitria and azobis (2,4 dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the total molar number of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, the polymerization reaction solution was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain A13 resin having a mass average molecular weight of about 5.3 x 10* with a yield of 60%. This A13 resin includes the following structural units.
[0267] Example 20 [Synthesis of resin A14] Acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (I-67) were used as monomers, these monomers were mixed in a molar ratio of 37:20:32:11 [acetoxystyrene: monomer (a1-1-3): monomer (a1-2-6): monomer (I-67)] and methyl isobutyl ketone in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile was added as an initiator in an amount of 7 mol% based on the total molar number of all monomers, which was followed by polymerization of the mixture by heating to 85 °C for about 5 hours. Then, an aqueous solution of 25% tetramethylammonium hydroxide was added to the polymerization reaction solution, followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain resin A14 having a mass-average molecular weight of about 5.2 x 10° with an efficiency of 63%. This A14 resin includes the following structural units.
[0268] Example 21 [Synthesis of resin A15] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (I- 37) as monomers, these monomers were mixed in a molar ratio of 19:25:38:18 [monomer (a1-4-2): monomer (a1-1-3): monomer (a1-2-6): monomer (1-37)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitria and azobis (2,4 dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the total molar number of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain an A15 resin having a weight-average molecular weight of about 5.3 x 103 with a yield of 63%. This A15 resin includes the following structural units. {ch teg ta tony At 5° > A15 bh MD vO OO, OH
[0269] [0269] Example 22 [Synthesis of resin A16] A monomer (a1-1-3), a monomer (a1-2-6) and a monomer (I-37) were used as monomers, these monomers were mixed in a molar ratio of 25:38:37 [monomer (a1-1-3): monomer (a1-2-6): monomer (1-37)] and methyl isobutyl ketone in an amount of 1.5 times the mass total of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in amounts of 1.2 mol% and 3.6 mol% based on the molar number total of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, the polymerization reaction solution was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain an A16 resin having a mass average molecular weight of about 5.2 x 103 with a yield of 61%. This A16 resin includes the following structural units. Hs Hz A tou toa ÆcH,
[0270] Example 23 [Synthesis of resin A17] Acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (I-49) were used as monomers, these monomers were mixed in a molar ratio of 37:20:32:11 [acetoxystyrene: monomer (a1-1-3): monomer (a1-2-6): monomer (I-49)] and methyl isobutyl ketone a was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile was added as an initiator in amounts of 7 mol% based on the total molar number of all monomers, which was followed by polymerization of the mixture by heating to 85 °C for about 5 hours. Then, an aqueous solution of 25% tetramethylammonium hydroxide was added to the polymerization reaction solution, followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain resin A17 (copolymer) having a mass average molecular weight approximately 5.5 x 103 with a yield of 60%. This A17 resin includes the following structural units.
[0271] Example 24 [Synthesis of resin A18] A monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6), a monomer (a2- 1-3), a monomer (a3-4-2) and a monomer (I-37) as monomers, these monomers were mixed in a molar ratio of 12:20:35:3:15:15 [monomer (a1 -4-2): monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (I-37)] 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% by mole and 3.6 mol% by mole on the based on the total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and collection to obtain an A18 resin having a weight-average molecular weight of about 5. 2 x 103 with a yield of 60%. This A18 resin includes the following structural units.
[0272] Example 25 [Synthesis of resin A19] A monomer (a1-1-3), a monomer (a1-2-6), a monomer (a2-1-3), a monomer (a3- 4-2) and a monomer (I-37) 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 (I-37)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers . To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the molar number total of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, the polymerization reaction solution was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain an A19 resin having a mass average molecular weight of about 5.3 x 103 with a yield of 63%. This A19 resin includes the following structural units. or all td ton) {cn EN 6 . H
[0273] [0273] Example 26 [Synthesis of resin A20] A monomer (a1-1-3), a monomer (a1-2-6) and a monomer (I-71) were used as monomers, these monomers were mixed in a molar ratio of 25:38:37 [monomer (a1-1-3): monomer (a1-2-6): monomer (I-71)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the molar number total of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, the polymerization reaction solution was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain an A20 resin having a mass-average molecular weight of approximately 5.5 x 103 with a yield of 58%. This A20 resin includes following structural units.
[0274] Example 27 [Synthesis of resin A21] Acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (I-81) were used as monomers, these monomers were mixed in a molar ratio of 37:20:32:11 [acetoxystyrene: monomer (a1-1-3): monomer (a1-2-6): monomer (I-81)] and methyl isobutyl ketone in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile was added as an initiator in an amount of 7 mol% based on the total molar number of all monomers, which was followed by polymerization of the mixture by heating to 85 °C for about 5 hours. Then, an aqueous solution of 25% tetramethylammonium hydroxide was added to the polymerization reaction solution, followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain resin A21 having a mass-average molecular weight of about 5.7 x 10° with an efficiency of 55%. This A21 resin includes the following structural units.
[0275] [0275] Example 28 [Synthesis of Resin A22] Monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3 -4-2) and a monomer (1-71) 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 (I-71)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the molar number total of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, the polymerization reaction solution was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain A22 resin having a mass average molecular weight of about 5.4 x 10° with a yield of 59%. This A22 resin includes the following structural units. te ru tf and tof 0 and YY A OH L Ao
[0276] [0276] Synthesis Example 5 [Synthesis of resin AX1] Monomer (ax-1), monomer (ax-2) and monomer (I-17) were used as monomers, these monomers were mixed in a molar ratio of 30:30:40 [monomer (ax-1): monomer (ax-2): monomer (I-17)] and methyl isobutyl ketone was added in an amount of 1.5 times the total mass of all the monomers. To the mixture thus obtained, azobisisobutyronitria and azobis (2,4 dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol% based on the total molar number of all monomers, followed by polymerization of the mixture by heating at 73°C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, followed by stirring for 12 hours and further isolation by separation. The organic layer thus recovered was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and further collection to obtain an AX1 resin having a mass-average molecular weight of about 5.4 x 10° with an efficiency of 66%. This AX1 resin includes the following structural units (a removal rate of one ethoxyethyl group in all ethoxyethyl groups of the monomer (1-17) is 100%). #CHz; we tc N 0 0 AX1 + nC48H37 OO i 07 0 ) CsF17 © OH
[0277] [0277] <Preparation of resist composition> A mixture obtained by mixing and dissolving the respective components shown in Table 1 was filtered through a fluororesin filter having a pore diameter of 0.2 µm to prepare compositions of resist.
[0278] [0278] <Resin> A1 to A22, AX1: Resin A1 to Resin A22, Resin AX1. <Acid generator (B)> B1-43: salt represented by formula (B1-43)
[0279] [0279] (Evaluation of resist composition exposure with electron beam) Each 6 inch diameter silicon wafer was treated with hexamethyldisilazane and then baked on a direct hot plate at 90°C for 60 seconds. A resist composition was applied by centrifugal application (“spin coating”) on the silicon wafer so that the thickness of the composition was then 0.04 μm. The coated silicon wafer was prebaked on the direct hot plate at the temperature shown in the "PB" column of Table 1 for 60 seconds to form a composition layer. By means of a "HL-800D 50 keV" direct electron beam writing system, manufactured by Hitachi, Ltd.), patterns of lines and spaces were written directly onto the composition layer formed on the wafer while the exposure dose was changed stepwise.
[0280] [0280] Evaluation of line edge roughness (LER): Line edge roughness was determined by measuring a roughness width of the irregularity in the wall surface of the resist pattern produced at the effective sensitivity by means of a scanning electron microscope. The results are shown in Table 2.
[0281] [0281] (Evaluation of exposure of resist composition with an electron beam: development of butyl acetate) Each silicon wafer, 6 inches in diameter, was treated with hexamethyldisilazane and then baked on a plate. direct heating at 90°C for 60 seconds. A resist composition was applied by centrifugal application (“spin coating”) on the silicon wafer so that the thickness of the composition was then 0.04 μm. The coated silicon wafer was prebaked on the direct hot plate at the temperature shown in the "PB" column of Table 1 for 60 seconds to form a composition layer. By means of a "HL-800D 50 keV" direct electron beam writing system, manufactured by Hitachi, Ltd.), patterns of lines and spaces were written directly onto the composition layer formed on the wafer while the exposure dose was changed stepwise.
[0283] [0283] Evaluation of the line edge roughness (LER): The line edge roughness was determined by measuring a roughness width of the irregularity in the wall surface of the resist pattern produced at the effective sensitivity by means of a microscope. scanning electronics. The results are shown in Table 3.
[0283] [0283] The resist composition comprising the resin of the present invention is suitable for fine processing of semiconductors due to obtaining a resist pattern with satisfactory line edge roughness (LER), and therefore is industrially very useful.

权利要求:
Claims (30)
[1]
1. A resin comprising a structural unit represented by formula (I), and 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): R1 your X (|) | 1 Ar Jk | Are{o—R2] n where, in formula (I), R* represents a hydrogen atom or a methyl group, xt represents a single bond or -CO-O-* (* represents a binding site at Ar *), X represents -CO-O-*, -O-*, -O-CO-*, -O-CO-(CH>)mm-O-* or -O-(CH>)nn-CO-O-* ( * represents a binding site at Ar”), mm and nn represent 0 or 1, Art and Ar” each independently represent an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, R2 each independently represents an atom of hydrogen or an acid-labile group, or when there are two or more R*, two R may combine to form a group having a cyclic acetal structure, n represents an integer of 1 to 3, and when n is an integer of 2 or more, a plurality of R may be the same or different from each other:
HE THE
CC
O O La’ La2 ee Joon RT eo nt! (a1-1) (a1-2) where, in formula (a1-1) and formula (a1-2), Lt and L each independently represent -O- or *-O- (CH>)y:- CO-O-, k1 represents an integer from 1 to 7, and *represents a binding site at -CO-, R°* and R® each independently represent a hydrogen atom or a methyl group, R°° and R each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups, m1 represents an integer of 0 to 14, nl represents an integer of 0 to 10, and nl' represents an integer of 0 to 3.
[2]
2. The resin of claim 1, wherein X* is a single bond.
[3]
3. The resin of claim 1, wherein X* is -CO-O-* or -O-* (* represents an Art binding site).
[4]
4. The resin according to claim 1, wherein Ar and Ar each independently represent an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent.
[5]
5. The resin according to claim 1, wherein n is 1 or 2.
[6]
6. The resin of claim 1, wherein the acid labile group in R is a group represented by formula (1a) or a group represented by formula (2a): O Raa1
Aj Pee (1a)
naa Raa3 where in formula (Ia), R°*, R22 and R®* each independently represents 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 R22 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 R222 are bonded,
naa represents 0 or 1, and * represents a bond: Raat’
% me (2a) Raa2'
where in formula (2a), R22! and R®7 each independently represents 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 R* may be bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms with -CX°- to which R°°* and R°5 are bonded, and -CHz- included in the group hydrocarbon and the heterocyclic group can be replaced by -O- or -S-,
X represents an oxygen atom or a sulfur atom, * represents a bonding position.
[7]
7. The resin of claim 1, wherein R is hydrogen, or n is 2 or more and two R* combine to form a group having a cyclic acetal structure.
[8]
8. The resin according to claim 6, wherein R is a hydrogen atom or a group represented by formula (2a), or n is 2 or more and two R's combine together to form a group having a cyclic acetal structure.
[9]
9. The resin according to claim 1, wherein n is 2 or more and two R2 combine to form a group having a cyclic acetal structure, the group formed by two R* is a group represented by formula (3a): * pet (3a), Rab2 where, in formula (3a), R®! and R® each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R* and RP can be bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms with carbon atoms at which R@* and R°P are bonded, and -CH>- included in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O- or -CO-, and * represents a bond to an oxygen atom.
[10]
10. The resin according to claim 1, wherein the structural unit represented by formula (I) is represented by any one of the following structural units:
H Hz H CHs Lu te SS TET 15+
O O Q 0 0 ° © A © 0% 2 OH 9
OH
OH (1-1) (1-2) (1-3) (1-4) OH
H H H CH fet tet fet Tet
OO 0° 9 ë 6 OH 1-7 OH H Hs H Hz Pat Pf PET PF 0 Ö a 9 Le 9 O 2 oO LP (1-9) (1-10) ÖH (1-11) (1-12) OH H CHs H CHs LA} RE dt PET
O O O 0
O OH OH A HO OH ó
OH OH
OH HO OH - OH - OH 13) (1-14) (15) (1-16)
H CHs H CH3 Pit rf tzt PET 070 9 050 O
O 9° Or NP 9 NP Ar ” > 8 x ” f (1-17) (1-18) (1-19) (1-20) rat VER at St 2 ç O O 2 5 2% 8 Oak © da À
O be Dik y 99 À Ak > y > x (1-21) X (1-22) (29) X (1-24) H CH3 H CH3 Pat Tort PET Tt O 9 O O Q | On | 2 ò 2 Qu ü > 8 De 9 [ (1-25) f (1-26) (1-27) (1-28) CHs Hs m {+ tr Pgt es © © © ©
O O Gas Of GX QUX 030 00 90 919 > > > > (1-29) (1-30) (1-31) (1-32)
HCH, HCH,
PET NET PET PER
O O do d 0°9 A © Oo Ó Os Q A OH OH y, OH Q
OH OH (1-33) (1-34) OH (1-35) (1-36) HCH, HCH, Pz Pf gt PET
O O d 6 Q 9 oo A,
OH
OH H (1-37) OH OH A, (1-38) H
ÖH (1-39) (1-40) HCH, rat Pf
O 6 € © O °C Dd Q
OH
OH (1-41) (42) OH
H CH H CH Lu Tet PET TSI
O O
O O x 9
O 9 oo Ô On © 7 of Oo 9
O OL + p of (1-43) (1-44) (1-45) (1-46)
be Pt gt ft
O O OO 9 © 9 y % % € o Ï es + à, + of (1-47) (1-48) of (1-49) (1-50)
O ee. … 6 pe pl t, of el 07 Q Oo oO e) + Q, + ©
O O (1-51) SF (1-53) (1-54) +
H H Pat Pat Pa Pat oo 070 9 Q, ee 9, es Ö % on 5 Qx (1-57) 7 (1-55) (1-56) (1-58)
H F5} F5} Fa} rot oe 070 oo O À A 5 4% HO du OH O du OH y of (39) (-60) (1-61) ] (1-62) Y
HH
H CH rot Fat Vol PET oo 070 SV 00 HO
F F Y OH a Su (1-63) (1-64) (1-65) (1-66)
H H H H var ro! Lou ri O 070 070 OO Or oO A 1 WHERE 00 OH (1-67) (1-68) (1-69) (1-70)
H CH H CH, “iron | CHs “iron “fet | == | | == |
Ó Ó 9 OH 9 A Ô ( X OH OH > OH À od
H OH OH Gl
OH (1-71) (1-72) (1-73) (1-74) H CH3 H CHs “iron Tet “iron Tet 9 | Ó © | Ó OP 9 TO 0
OH OH on A me pe
OH H OC (1-75) (1-76) OH (1-77) (78)
H CH rat Pt
O
Ó ed 9 Oo oe OC ©
OH OC
OH (1-79) (1-80)
H CH FE} tat PET Jon
O O
G Ó 9 SC Q 9 4 © > Lu ce >
Y (81) (1-82) (1-83) (1-84)
I u Hd SF 0 9 9 6 32.9
O QT Ö &> a °° D ee 0 > Da _
O (1-85) (1-86) (1-87) (1-88) H Hz c H CH Hz PE} dr 1 6 te
O O a 9 € 9 07 0 O O O OC pe ee Da € O O. Ga co.
O O (1-89) (1-90) (1-91) (1-92)
[11]
11. The resin according to claim 1, further comprising a structural unit represented by the formula (a2-A): Ho Re» - Laco (a2-A)
OH a51 (RS) b where, in the formula (a2-A), R°5 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom , R2! 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, A2°0 represents a single bond or *-X°°1-(a252-x252)ap=, and * represents a bond site to the carbon atoms to which -R°° is bonded, A represents an alkanediyl group having 1 to 6 carbon atoms, x°°1 and X each independently represent -O-, -CO-O- or -O-CO-, nb represents 0 or 1, and mb represents an integer of 0 to 4, and when mb is an integer of 2 or more, a plurality of R °* can be the same or different from each other.
[12]
12. The resin according to claim 1, further comprising a structural unit represented by the formula (a2-1): Ho Ra14 | = | Las (a2-1) Gold
H Ra16 where in formula (a2-1), L°* represents -O- or *-O-(CHz)z-CO-O-, k2 represents an integer from 1 to 7, and * represents a binding site a-CO- R2!* represents a hydrogen atom or a methyl group, R°15 and RE each independently represent a hydrogen atom, a methyl group or a hydroxy group, and 01 represents an integer of 0 to 10.
[13]
13. The resin according to claim 1, further comprising a structural unit represented by any one of formula (a2-1), formula (a3-2), formula (a3-3) and formula (a3 -4): Ra18 true ie 7 | Forest tert Tst Tort aa 165 Xxas 6 a7 (R@@1) 4 ie re (re, ar © oO
O (a3-1) (a3-2) (a3-3) (a3-4) where in formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L°*, L° and L° each independently represent -O- or a group represented by *-O-(CH>)(3-CO-O- (k3 represents an integer from 1 to 7 ), L°” represents -O-, *-OL°8-0-, *-OL°8-CO-O-, *-OL°8-CO-OL°*- CO-O- or *-OL °8-0-CO-L°°-0-, L® and L°° each independently represent an alkanediyl group having 1 to 6 carbon atoms, * represents a bonding site to a carbonyl group, RAS R°19 and RO each independently represent a hydrogen atom or a methyl group, R22* represents an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, a hydrogen atom or a halogen atom, X°* represents -CHz- or an oxygen atom, R°21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R322, R223 and R225 each independently represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, p1 represents an integer from 0 to 5, q1 represents an integer from 0 to 3, rl represents an integer from 0 to 3,
w1 represents an integer from 0 to 8, and when pl, q1, rl and/or wl is/are 2 or more, a plurality of R°*, R322 R°° and/or R°°° may be the same or different one another.
[14]
14. The resin according to claim 1, further comprising a structural unit represented by the formula (a1-4): R332 R333 | 5 a34 (97-4); ne Ra35 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 to carbon atoms at which -R °* is bonded, A22 represents an alkanediyl group having 1 to 6 carbon atoms, x231 and X each independently represent -O-, -CO-O- or -0-CO-, nc represents 0 or 1,
la 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, and R°34 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 R335 and R°°° may be bonded with each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with -C- O- to which R® and R°° are bonded, and -CH>- included in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-.
[15]
15. A resist composition comprising the resin of claim 1 and an acid generator.
[16]
16. The resist composition according to claim 15, wherein the acid generator comprises a salt represented by the formula (B1): a1 + -Q4S [61 Z* Os > Sy (BIJ) 2 QP2 where, in the formula (B1), QP! and QP each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, LP represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -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 -CH:- included in the group alicyclic hydrocarbon can be replaced by -O-, -S(O)2- or -CO-, and
Z* represents an organic cation.
[17]
17. The resist composition according to claim 15, further comprising an acid-generating salt having a lower acidity than an acid generated by the acid generator.
[18]
18. A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to claim 15 to a substrate, (2) a step of drying the applied composition to form a layer composition, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and (5) a step of developing the heated composition layer.
[19]
19. A compound represented by formula (IA): R1 CH2=—C ,
AI TO (A) | (Box) 9
O R R3 where, in formula (IA), R* represents a hydrogen atom or a methyl group, xt represents a single bond or -CO-O-* (* represents a binding site to Ar”),
X represents -CO-O-*, -O-*, -O-CO-*, -O-CO-(CH>)mm-O-* or -O-(CH>)nn-CO-O-* ( * represents a benzene ring bonding site), mm and nn represent 0 or 1, Art represents an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, R* and R* each independently represents a hydrogen or an acid labile group, or R* and R* may combine to form a group having a cyclic acetal structure, R° represents a halogen atom, an alkyl fluoride group having 1 to 6 carbon or an alkyl group having 1 to 12 carbon atoms, and -CH>- included in the alkyl group and the alkyl fluoride group may be replaced by -O- or -CO-, and n' represents an integer of 0 to 3, and when n' is 2 or more, a plurality of R° may be the same or different from each other.
[20]
20. The compound of claim 19, wherein X* is a single bond.
[21]
21. The compound of claim 19, wherein X is -CO-O-* or -O-* (* represents a benzene ring binding site).
[22]
22. The compound of claim 19, wherein n° is 0.
[23]
23. The compound of claim 19, wherein R* and R* are hydrogen, or R3 and R* combine together to form a group having a cyclic acetal structure.
[24]
24. The compound according to claim 19, wherein Art is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent.
[25]
25. The compound of claim 19, wherein the acid labile group in R3 and R* is a group represented by formula (1a) or a group represented by formula (2a):
O Raa1 Aj Pee (1a) naa Raa3 where, in formula (Ia), R°*, R22 and R®* 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 R22 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: Raat' % me (2a) Raa2' where in the formula (2a), R22! and R®7 each independently represents 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 R* may be bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms with -CX - to which R°°* and R°3 are bonded, and -CHz- included in the group hydrocarbon and the heterocyclic group can be replaced by -O- or -S-, X represents an oxygen atom or a sulfur atom, * represents a bonding position.
[26]
26. The compound according to claim 25, wherein R* and R* have a hydrogen atom or a group represented by formula (2a), R3 and R* combine together to form a group having a cyclic acetal structure.
[27]
27. The compound according to claim 19, wherein R* and R* combine to form a group having a cyclic acetal structure, the group formed by two R* is a group represented by formula (3a): * x. (3a), Rab2 where, in the formula (3a), R®! and R® each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R* and RP can be bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms with carbon atoms at which R@* and R°P are bonded, and -CH>- included in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O- or -CO-, and * represents a bond to an oxygen atom.
[28]
28. The compound according to claim 19, said compound represented by formula (IA) being a compound represented by formula (IA1) or a compound represented by formula (IA2), R1 R! oml oml X , | (AT) | (IA2) Ar! Ar! x x qu — 5 ©; In 05 O Rt R3 ( Rs ) n' Rt, Xt, X*, mm, nn, Art, R3, R*, R° and n' are as defined in claim 19.
[29]
29. The compound according to claim 19, said compound of formula (IA) is represented by any one of the following compounds: H CH, H CH CH, ch CH, ch
O O
Ó Ó O0 00
OH OH
H HO H
OH OH (IA-13) (A-14) (IA-15) (IA-16)
H CHs H CH3 CH, CH, CH, CH, OÖ De 9 > » 6 % 8 0 Oo 07 ton 1 <a 2 x oo Os) O ok f T° > 0-0 fx (IA-19) (IA- 20) (A21) (IA-22) CH N CH 2nd CH n CH ps Lu €; to 00 O 9 | JL k Q, Oo od Aix x On ó 00 (© NP A y 5 x [ (IA-23) (IA-24) (IA-27) (IA-28) CHs Hs CH, cn 4 > 4 ó 9 O © q 0 0 Dik OX Ok ook OÖ OO 970 (IA-29) (IA-30) (IA-31) (IA-32)
H CHs H CH3 CH» ne CH, ch O ‘ O 9 9 070 2 9 07” © O 07 © À OH oe
OH OH
OH OH
OH OH
OH (IA-33) (IA-34) (IA-35) (IA-36) H CH3 H CH CH, Ch CH, CH, ne 0 ° W ‘ 9 d Ö 9 9 + Ô
OH AL OH OH 070 Su Ce OH
OH (IA-37) (IA-38) OH (IA-39) (IA-40) H CHs CH, Ch
O
Ó °C © oO OO t,
Oh Q
OH
OH
OH (IA-41) (IA-42)
N CH H CH 4 ae 4 on 9 Ó 9 9 O
At 9 oO 0 +
SF (A3) (1A44) (A45) (A-46) H CH3 H CHs
CH CH CH CH 9 9 c ] O0 ( ) Ô
Ö + 5, + OL Ö + (IA-47) (IA-48) + (IA-49) (IA-50) H CHs H CHs CH, CH»CH, CH;
O 1; FE % $ À 2 © SE A 9 A 9
O 9 Q Ô EN + D + ° 9 Ö (1A-51) (1A-52) + (IA-53) meot
A H H Cc CH > © > , o o 079 070 9 Ö ae D pe ï
N(1A-57) . (1A-55) (1A-56) (1A-58)
H
H H H F 7 7 0 oo oo 079 9 0 A A 3, oP OH OH or Y x a (lA-59) (IA-60) (IA-61) (IA-62)
H
H H 7 CH, " CH, CF ° ‘ oe) O OÖ 99 HO
OH D, F OH ' OH on OH
OH OH _ (1A-66) (63) (A64) (1A-65)
H CH3 H CH3 CH, ne CH, HX
O O A 2 9 OH oo to 2 OH TO OH OH 070
HOH
X X
OH(IA-71)(A-72)(IA-73)(IA-74)HCHCH; H CH CH3
CH CH, year 2 year
Ö Ö ea 7 A 2
OH OH * X A
H OH OH (IA-75) (IA-76) OH (IA-77) (A-78) H CH3 CH, ne
O
O LE 9 O 00
OH X t
OH OC
OH (IA-79) (JA-80)
H CH H CH3 4 FT % 7
O O
O O
O 1 O © A © CX > 070 O A OÖ ( I O ° X >Q De — 0 O — OL
O (IA-81) (IA-82) (IA-83) (IA-84) H CH3 H Hz CH; CH» CH» cut
O O
0. Oo /— Ö & > LE a 0 6} — OÖ O > 2 a (IA-85) (IA-86) (IA-87) (IA-88) H CH3 H CHs
CH "9 HX "9 Se
Ó Ó A y © SG Gé > 07 ee DO O Oo O. Oo O co OGA
Y Y (IA-89) (IA-90) (IA-91) (IA-92)
[30]
30. A resin comprising a structural unit derived from the compound according to claim 19.

类似技术:

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公开号 | 公开日 | 专利标题

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JP6169848B2|2017-07-26|Salt, resist composition and method for producing resist pattern

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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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JP2019228374|2019-12-18|

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JP2020035989|2020-03-03|

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