COMPOUND, RESIN, PHOTORESIST COMPOSITION AND PROCESS FOR THE PRODUCTION OF PHOTORESIST PATTERNS

专利摘要:
An object of the present invention is to provide a compound, a resin and a resist composition comprising the resin capable of producing a resist pattern with satisfactory CD uniformity (CDU). Disclosed is a compound represented by formula (I) as defined in claim 1, a resin including a structural unit derived from said compound and a resist composition, wherein in formula (I), R1 represents an alkyl group. which may have a halogen atom, a hydrogen atom or a halogen atom; A1 represents a single bond or * -A2-CO-O-; A2 and A3 represent an alkanediyl group; W represents a divalent monocyclic saturated alicyclic hydrocarbon group; R2 and R3 each represents a hydrogen atom or a hydrocarbon group which may have a fluorine atom, etc., R4 represents a hydrogen atom, -CH 2- in the group may be replaced by -O-, -S -, etc., R2 and R3 or R2, R3 and R4 can be bonded to each other to form a ring which may have a fluorine atom or an alkyl group.
公开号:BE1027107B1
申请号:E20205183
申请日:2020-03-19
公开日:2021-02-15
发明作者:Katsuhiro Komuro；Koji Ichikawa
申请人:Sumitomo Chemical Co；
IPC主号:

专利说明:

[0001] [0001] The present invention relates to a compound, a resin comprising a structural unit derived from the compound, a resist composition comprising the resin, and a method for producing a resist pattern using the resist composition. BACKGROUND OF THE INVENTION
[0002] [0002] Patent document 1 mentions resist compositions comprising a resin composed of each structural unit derived from the following compounds.
[0003] [0003] Patent Document 1: JP 2008-268743 A Patent Document 2: JP 2010-254639 A Patent Document 3: WO 2015/045739 Patent Document 4: JP 2016-108553 A Patent Document 5: JP 2015- 108809 A
[0004] An object of the present invention is to provide a compound which forms a resist pattern having a CD (CDU) uniformity better than that of a resist pattern formed from a resist composition comprising a resin having a structural unit derived from the aforementioned compounds. Means for solving problems
[0005] [0005] The present invention includes the following inventions.
[1] [1] A compound represented by the formula (I): R1 | CH = O (I)
[2] [2] A compound according to [1], where W is a cyclopentanediyl group or a cyclohexanediyl group.
[3] [3] Compound according to [1] or [2], where A * is a single bond.
[4] [4] A compound according to any one of [1] to [3], wherein A3 is a methylene group.
[5] [5] A resin comprising a structural unit derived from the compound according to any one of [1] to [4].
[6] [6] The resin according to [5], further comprising a structural unit represented by the formula (a2-A): Hz Ra50 e + Aas0 (a2-A) es (R 51) mb where, in the formula (a2- AT),
[7] [7] The resin according to [5] or [6], further comprising a structural unit having an acid labile group which is different from the structural unit derived from the compound represented by the formula (I).
[8] [8] The resin according to [7], wherein the resin comprising a structural unit having an acid labile group which is different from the structural unit derived from the compound represented by the formula (T) is a resin including at least one unit 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): Lt EF | Lt ä CC
[9] [9] A resist composition comprising the resin according to any one of [5] to [8] and an acid generator.
[10] [10] A resist composition according to [9], further comprising an acid generating salt having an acidity lower than that of an acid generated by the acid generator.
[11] [11] A process for producing a resist pattern, which comprises: (1) a step of applying the resist composition according to [9] or [10] to a substrate, (2) a step of drying the composition applied to form a composition layer, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and (5) a step of developing the heated composition layer .
[0006] [0006] It is possible to produce a resist pattern with satisfactory CD uniformity (CDU) by using a resist composition comprising a resin including a structural unit derived from a compound of the present invention.
[0007] As used herein, unless otherwise indicated, the term "(meth) acrylate" means "at least one selected from the group consisting of acrylate and methacrylate". Terms such as "(meth) acrylic acid" and "(meth) acryloyl" also have the same meaning. When a structural unit having "CH: = C (CH3) -CO-" or "CH: = CH-CO-" is exemplified, a structural unit having both groups is similarly to be considered as cited. for exemple. Further, as used herein, the term "derivative" or "induced" means that a polymerizable C = C bond included in the molecule becomes a -C- C- group upon polymerization. In the groups mentioned in the present description, those capable of exhibiting both linear and branched structures, may have either a linear structure or a branched structure. "A combined group" means a group obtained by linking two or more exemplary groups, and the valence number of which can suitably vary depending on the linkage state. When stereoisomers exist, all stereoisomers are included. As used herein, the term "solid component of the resist composition" means the total amount of components after removing the solvent (E) mentioned below from the total amount of the resist composition.
[0008] [0008] <Compound (I)> The compound of the present invention is a compound represented by formula (I) (hereinafter sometimes called "compound (D"):
[0009] [0009] Examples of the alkyl group for Rt include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n group -pentyl and an n-hexyl group, and an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.
[0010] [0010] Examples of the alkanediyl group having 1 to 6 carbon atoms for A and A include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group and hexane- group. 1,6-diyl; branched alkanediyl groups in which the linear alkanediyl groups have a side chain of alkyl groups (in particular alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group and a tert-butyl group), for example, an ethane-1,1-diyl group, a propane-1,2-diyl group, a butane-1,3-diyl group, a 2-methylpropan-1,3-diyl, a 2-methylpropan-1,2-diyl group, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
[0011] [0011] Examples of the divalent saturated monocyclic alicyclic hydrocarbon group having 3 to 12 carbon atoms for W include a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, a cyclooctanediyl group and the like. Among them, a divalent saturated monocyclic alicyclic hydrocarbon group having 3 to 8 carbon atoms is preferable, a cyclopentanediyl group or a cyclohexanediyl group is more preferable, and a cyclopentanediyl group is even more preferable.
[0012] [0012] Examples of the hydrocarbon group for R ° and R * include a chain hydrocarbon group such as an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and groups obtained by combining these groups.
[0013] Examples of compound (T) include the following.
[0014] It is possible to cite, by way of example, compounds in which a methyl group corresponding to R * is substituted by a hydrogen atom or a halogen atom in the compounds represented by formula (I-1) to formula (I-16) as specific examples of compound (I).
[0015] <Production method of compound (I)> The compound represented by formula (I1) wherein A * of compound (I) is a single bond can be obtained by reacting a compound represented by formula (I1- a) with a compound represented by formula (11-b) in the presence of a basic catalyst in a solvent: R1 ch, NN € (w} 9 y (> R! À, Na cr = t ‚0 À, Ae + - 9 O | R | OR R4 he (I1-a) (I1-b) Re (I1) where all the symbols are as defined above.
[0016] The compound represented by the formula (I2) in which A! of compound (I) is * -A -CO-O- can be obtained by reacting a compound represented by formula (I1-a) with a compound represented by formula (I2-b) in the presence of a basic catalyst in a solvent: R1 HO - M2 CH »OK. O GX &
[0017] [0017] The compound represented by the formula (I2-b) can be obtained by reacting a compound represented by the formula (I1-b) with a compound represented by the formula (I2-e) in the presence of a basic catalyst in a solvent:
[0018] [0018] [Resin] The resin of the present invention is a resin (hereinafter sometimes referred to as "resin (A)") including a structural unit derived from a compound (I) (hereinafter sometimes referred to as "structural unit ( T) ”). The resin (A) can be a homopolymer composed only of one structural unit (I), a copolymer composed of two or more structural units (I), or a polymer comprising one or more structural units other than the structural unit (T ). Examples of structural unit other than structural unit (I) include a structural unit having an acid labile group other than structural unit (I) (hereinafter sometimes referred to as "structural unit (a1)") , a structural unit having a halogen atom other than the structural unit having a labile group in an acid medium (hereinafter sometimes called "structural unit (a4)"), a structural unit having no labile group in the medium acid (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. The "acid labile group" means a group having a leaving group which is removed by contact with an acid, thereby forming a hydrophilic group (eg, a hydroxy group or a carboxy group). The resin (A) preferably includes, in addition to the structural unit (I), a structural unit (s) and / or a structural unit having an acid labile group, more preferably it comprises at least one structural unit (s) and / or at least one structural unit (a1), and more preferably it comprises at least one structural unit (s) and at least one structural unit (a1) or two or more structural units (a1).
[0019] <Structural Unit (a1)> The structural unit (a1) is derived from a monomer comprising a labile group in an acidic medium (hereinafter sometimes called "monomer (a1)").
[0020] [0020] Examples of the alkyl group for R ° *, R22 and R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group and the like. .
[0021] [0021] 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.
[0022] [0022] Examples of group (1) include the following groups.
[0023] [0023] Specific examples of group (2) include the following groups. * represents a binding position. APS PA APS 2e ne SA PA
[0024] The monomer (a1) is preferably a monomer having a labile group in an acidic medium and an unsaturated ethylenic bond, and more preferably a (meth) acrylic monomer having a labile group in an acidic medium.
[0025] The structural unit derived from a (meth) acrylic monomer having a group (1) is a structural unit represented by the formula (a1-0) (hereinafter sometimes called structural unit (a1-0)), a structural unit represented by formula (a1-1) (hereinafter sometimes called structural unit (a1-1)) or a structural unit represented by formula (a1-2) (hereinafter sometimes called structural unit (a1- 2)). Preferably, the structural unit is at least one structural unit chosen from a structural unit (a1-1) and a structural unit (a1-2). These structural units can be used alone, or two or more structural units can be used in combination: Ls Ra01 TL: Rè4 Le Rab | C If C = C
[0026] [0026] R20! R ° * and R °° are preferably a methyl group.
[0027] [0027] The structural unit (a1-0) includes, for example, a structural unit represented by any one of the formula (a1-0-1) to the formula (a1-0-12) and a structural unit wherein a methyl group corresponding to R °% * in structural unit (a1-0) is substituted with a hydrogen atom and is preferably a structural unit represented by any one of the formula (a1-0- 1) to the formula (a1- 0-10). Pr vr + rf (a1-0-1) (a1-0-2) (a1-0-3) (2104) (41.05) (81058) (a1-0-7) (a1-0-8) (a1 -0-9) (a1-0-10) (a1-0-11) (a1-0-12)
[0028] [0028] The structural unit (a1-1) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646A. Among these structural units, a structural unit represented by any one of the formula (a1-1-1) to the formula (a1-1-4) and a structural unit in which a methyl group corresponding to R ° * in l Structural unit (a1-1) is substituted with a hydrogen atom are preferred, and a structural unit represented by any one of formula (a1-1-1) with formula (a1-1-4) is favorite again. | ; Hz H3 Hz> Lon> PET Lon
[0029] [0029] Examples of structural unit (a1-2) include a structural unit represented by any one of the formula (a1-2-1) to the formula (a1-2-6) and a structural unit in which a methyl group corresponding to R °° in the structural unit (a1-2) is substituted with a hydrogen atom, and the structural units represented by the formula (a1-2-2), the formula (a1-2- 5) and formula (a1-2-6) are preferred.
[0030] When the resin (A) includes a structural unit (a1-0), its content is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 40 mol%, on the basis of all the structural units of the resin (A).
[0031] In the structural unit (a1), examples of the structural unit having a group (2) include a structural unit represented by the formula (a1-4) (hereinafter sometimes referred to as “structural unit (a1- 4) "): R332 233) To D (a1-4) (R ne Ra35 where, in the formula (a1-4), R222 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, R ° 53 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, a group alkylcarbonyl having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group, la represents an integer of 0 to 4, and when la is 2 or more, a plurality of R23 may be the same or different from each other, and R ° 5 * 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 R33 and R °° are linked with each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with -C- O- to which R33 and R ° * ° are attached, and -CH> - included in the hydrocarbon group and the divalent hydrocarbon group may be replaced by - O- or -S-.
[0032] Examples of the alkyl group in R °°° and R®3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and more preferably a methyl group.
[0033] In formula (a1-4), R °° is preferably a hydrogen atom, R233 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group and an ethoxy group, and more preferably a methoxy group, 1a is preferably 0 or 1, and more preferably 0, R ° 3 * is preferably a hydrogen atom, and
[0034] [0034] The structural unit (a1-4) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646 A. The structural unit preferably includes the structural units represented by the formula (a1-4- 1) with the formula (a1-4-12) and a structural unit in which a hydrogen atom corresponding to R ° in the structural unit (a1-4) is substituted with a methyl group, and more preferably the units structures represented by the formula (a1-4-1) to the formula (a1-4-5) and the formula (a1-4-10).
[0035] When the resin (A) includes the structural unit (a1-4), the content is preferably 3 to 80 mol%, more preferably 5 to 75 mol%, more preferably 7 to 70 mol%, of more preferably 7 to 65 mol%, more preferably 10 to 60 mol%, based on the total of all structural units of the resin (A).
[0036] The structural unit derived from a (meth) acrylic monomer having a group (2) also includes a structural unit represented by the formula (a1-5) (hereinafter sometimes called "structural unit (a1-5) "). Read Re]“ Et = O LP "ai {Pme (a1-5) 15: fo“ 0 In formula (a1-5), R ° $ represents an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom, a hydrogen atom or a halogen atom, Z represents a single bond or * - (CHz) n3-CO-L ° * -, h3 represents an integer from 1 to 4, and * represents a binding site at L ° *, L ° t, L ° 2, L ° and L ** each independently represent -O- or -S-, s1 represents an integer of 1 to 3, and sl 'represents an integer of 0 to 3.
[0037] [0037] The halogen atom includes a fluorine atom and a chlorine atom and is preferably a fluorine atom. Examples of an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a group. octyl, a fluoromethyl group and a trifluoromethyl group.
[0038] [0038] The structural unit (a1-5) includes, for example, the structural units derived from the monomers mentioned in JP 2010-61117 A. Among these structural units, the structural units represented by the formula (a1-5-1) to formula (a1-5-4) are preferred, and structural units represented by formula (a1-5-1) or formula (a1-5-2) are more preferred.
[0039] When the resin (A) includes the structural unit (a1-5), the content is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, more preferably 5 to 40 mol%, and more preferably 5 to 30 mol%, based on all the structural units of the resin (A).
[0040] The structural unit (a1) also comprises, for example, a structural unit represented by the formula (a1-0X) (hereinafter sometimes called structural unit (a1-0X)):
[0041] [0041] Examples of the saturated hydrocarbon group for R * and R3, include an alkyl group, an alicyclic hydrocarbon group and a group formed by combination thereof.
[0042] [0042] Examples of the aromatic hydrocarbon group for Ar ‘include an aryl group having 6 to 36 carbon atoms, such as a phenyl group, a naphthyl group and an anthryl group.
[0043] [0043] Art is preferably an aromatic hydrocarbon group having 6 to 36 carbon atoms, more preferably a group - phenyl or naphthyl and more preferably a phenyl group.
[0044] [0044] Examples of the structural unit (a1-OX) include the structural units mentioned below and structural units in which a methyl group corresponding to R * in the structural unit (a1-OX) is substituted by a hydrogen atom. The structural unit (a1-OX) is preferably a structural unit (a1-OX-1) to a structural unit (a1-OX-3).
[0045] [0045] When the resin (A) includes a structural unit (a1-OX), its content is usually 5 to 60% by mole, preferably 5 to 50% by mole, and even better still from 10 to 40% by mole. mole, based on all the monomers in the resin (A).
[0046] [0046] Examples of the structural unit (a1) also include the following structural units. Lu Te Lo 2 FO SO # 0 A Ob DD a, CO (a1-3-1) (a1-3-2) (a1-3-3) (a1-3-4) (a1-3-5) ( a1-3-6) (a1-3-7)
[0047] 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%, on the basis of all the structural units of the resin (A).
[0048] <Structural Unit (s)> The structural unit (s) derives from a monomer having no labile group in an acidic medium (hereinafter called “monomer (s)”). The monomer from which the structural unit (s) are derived has no labile group in an acid medium known in the field of resist.
[0049] [0049] <Structural Unit (a2)> The hydroxy group belonging to the structural unit (a2) can be either an alcoholic hydroxy group or a phenolic hydroxy group.
[0050] In 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), R ° 5 represents a hydrogen atom, a halogen atom or an alkyl group having 1 with 6 carbon atoms optionally having a halogen atom, R3! represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group, A2 ° 0 represents a single bond or * -X °° 1- (a252-x252) ap ", and * represents a binding site to carbon atoms to which -R2 ° is bonded, A °° Represents an alkanediyl group having 1 to 6 carbon atoms, x °° 1 and X Each independently represent -O-, -CO-O- or-O-CO- nb represents 0 or 1 , and mb represents an integer of 0 to 4, and when mb is an integer of 2 or more, a plurality of R ° * may be the same or different from each other.
[0051] Examples of the halogen atom in R ° ® include a fluorine atom, a chlorine atom and a bromine atom.
[0052] [0052] Examples of * -X °° 1- (A252-X252) pp ”include * -O-, * -CO-O-, * - O-CO-, * -CO-0-A252-CO- 0-, * -0-CO-A352-0-, * -OA ° -CO-O-, * -CO-0-A% - O-CO- and * -0-CO-A ° 2- 0-CO-. Of these, * -CO-O-, * -CO-0-A92-CO-0- or * -O-A352-CO-O- is preferred.
[0053] [0053] Examples of alkanediyl group include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane group. -1,5-diyl, hexane-1,6-diyl group, butane-1,3-diyl group, group
[0054] [0054] A is preferably a single bond, * -CO-O- or * -CO-O- A252-CO-O-, more preferably a single bond, * -CO-O- or * -CO-O- CH2-CO -O-, and more preferably a single bond or * -CO-O-.
[0055] [0055] mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.
[0056] Examples of structural unit (a2-A) include structural units derived from the monomers mentioned in JP 2010-204634 A and JP 2012-12577 A.
[0057] [0057] When the structural unit (a2-A) is included in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 10 to 70. mole%, more preferably 10 to 60 mole%, and more preferably 10 to 50 mole%, based on all structural units.
[0058] [0058] Examples of a structural unit having an alcoholic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)" ).
[0059] In formula (a2-1), L® is preferably -O- or -O- (CH2) j- CO-O- (fl represents an integer from 1 to 4), and more preferably -O -, R ! is preferably a methyl group, R3! 5 is preferably a hydrogen atom, RS is preferably a hydrogen atom or a hydroxy group, and ol is preferably an integer of 0 to 3, and more preferably 0 or 1.
[0060] [0060] The structural unit (a2-1) includes, for example, the structural units derived from the monomers mentioned in JP 2010-204646 A. A structural unit represented by any one of the formula (a2-1-1) to formula (a2-1-6) is preferred, a structural unit represented by any one of formula (a2-1-1) to formula (a2- 1-4) is more preferred, and a structural unit represented by formula (a2-1-1) or formula (a2-1-3) is more preferred. Hz CHs Ha H Hz CHs Ha H [ers JE: H vid BEE IE OH H Da H 5 0>
[0061] When the resin (A) includes the structural unit (a2-1), the content is usually from 1 to 45 mol%, preferably from 1 to 40 mol%, more preferably from 1 to 35 mol%, more preferably 1 to 20 mol% and more preferably 1 to 10 mol%, based on all the structural units of the resin (A).
[0062] <Structural unit (a3)> The lactone ring belonging to the structural unit (a3) can be a monocyclic ring such as a B-propiolactone ring, a γ-butyrolactone ring or an α-valerolactone ring, or a condensed ring a monocyclic lactone ring and the other ring. Preferably, an γ-butyrolactone ring, an adamantanelactone ring or a bridged ring including a γ-butyrolactone ring structure (eg, a structural unit represented by the following formula (a3-2)) is exemplified.
[0063] [0063] The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3) or the formula (a3-4). These structural units can be included alone, or two or more structural units can be included: Ra18 je In pr | Tot Lot al ter = tet = La (Re des xas & L T $ (R225) (RE) 1 0 oe,, JF
[0064] Examples of the aliphatic hydrocarbon group in R ° *, R322 R ° 23 and R22 include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group. and a tert-butyl group.
[0065] In the formula (a3-1) to the formula (a3-3), preferably L ° * to L ° are each independently -O- or a group in which k3 is an integer of 1 to 4 in * -O- (CH2) es-CO-O-, more preferably -O- and * -O- CH2-CO-O-, and more preferably an oxygen atom, R818 at R °! are preferably methyl, preferably R * and R223 are each independently a carboxy group, a cyano group or a methyl group, and preferably p1, q1 and r1 are each independently an integer of 0 to 2, and more preferably 0 or 1.
[0066] [0066] In formula (a3-4), R ** is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or a group ethyl, and more preferably a hydrogen atom or a methyl group, R225 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 -O-C2H4-CO-O-, and wl is preferably an integer of 0 to 2, and more preferably 0 or 1.
[0067] Examples of structural unit (a3) include structural units derived from monomers mentioned in JP 2010-204646 A, monomers mentioned in JP 2000-122294 A and monomers mentioned in JP 2012-41274 A. The unit structural (a3) is preferably a structural unit represented by any of the formula (a3-1-1), the formula (a3-1-2), the formula (a3-2-1), the formula ( a3- 2-2), formula (a3-3-1), formula (a3-3-2) and formula (a3-4-1) to formula (a3-4-12), and the units in which the methyl groups corresponding to R # 8, RS, R220 and R ° 2 * in the formula (a3-1) in the formula (a3-4) are substituted with hydrogen atoms in the structural units below above.
[0068] [0068] ten} Jon Et ten} dn} tr} tete} V4, Kg 844 HA
[0069] When the resin (A) includes the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 5 to 60 mol%, and more preferably 7 to 50 mol%, on the basis of all the structural units of the resin (A).
[0070] [0070] <Structural unit (a4)> Examples of structural unit (a4) include the following structural units: +4
[0071] Examples of the chain hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group , a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. Examples of a monocyclic or polycyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; and polycyclic alicyclic saturated hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* represents a binding site).
[0072] [0072] Examples of structural unit (a4) include a structural unit represented by at least one selected from the group consisting of formula (a4-0), formula (a4-1), formula (a4-2) , the formula (a4-3) and by the formula (a4-4): R5 ton + (a4-0) O
[0073] Examples of the divalent aliphatic saturated hydrocarbon group in L * include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl 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 group 2-methylpropane-1,2-diyl.
[0074] [0074] L “is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
[0075] Examples of structural unit (a4-0) include the following structural units, and structural units in which a methyl group corresponding to R ° in the structural unit (a4-0) is substituted with an atom of hydrogen in the following structural units:
[0076] [0076] gay Ha
[0077] [0077] Examples of a saturated hydrocarbon group in R ** include a chain saturated hydrocarbon group and a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and groups formed by combining these groups.
[0078] [0078] 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 the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and the halogen atom is preferably a fluorine atom: "—X263—23 ® (a-93) where in the formula (a-g3), x2 * 3 represents an oxygen atom, a carbonyl group, * -O- CO- or * -CO-0-, A ® represents an an aliphatic hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, and * represents a binding site.
[0079] [0079] Examples of the aliphatic 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 , a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group; monocyclic alicyclic hydrocarbon groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* represents a bond): Examples of a group formed by combination include a group obtained by combining one or more alkyl groups or one or more several alkanediyl groups with one or more alicyclic hydrocarbon groups, and include an alkanediyl group-alicyclic hydrocarbon group, an alicyclic hydrocarbon group-alkyl group, an alkanediyl group-alicyclic hydrocarbon group-alkyl group and the like.
[0080] [0080] R ° * 2 is preferably a saturated hydrocarbon group optionally having a halogen atom, and more preferably an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula ( a-g3).
[0081] When R2 * is a saturated hydrocarbon group having the group represented by the formula (a-g3), R ** is more preferably a group represented by the formula (a-g2): x ——A94_ ya44__na47 (a-g2) where, in of formula (a-g2), A24 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms optionally having a halogen atom, X represents ** - O-CO- or ** - CO-O- (** represents a binding site to A2 # 5), A: represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms optionally having an atom of halogen, the total number of carbon atoms of A2% 5, A2 and X ° ** is 18 or less, and at least one of A % and A37 has at least one halogen atom, and * represents a carbonyl group binding site.
[0082] The number of carbon atoms of the aliphatic hydrocarbon group for A ** is preferably 1 to 6, and more preferably 1 to
[0083] The preferred structure of the group represented by formula (a-g2) is the following structure (* is a carbonyl group binding site).
[0084] Examples of alkanediyl group in A ° * include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane- group. 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.
[0085] [0085] Examples of a divalent saturated hydrocarbon group represented by A *, A and A ** in the group represented by formula (a-g1) include a linear or branched alkanediyl group and a monocyclic divalent alicyclic saturated hydrocarbon group, and the groups formed by combining an alkanediyl group and a divalent alicyclic hydrocarbon group. Specific examples thereof 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 1- group. methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like.
[0086] [0086] In a group represented by the formula (a-g1), examples of the group in which X ** is -O-, -CO-, -CO-O- or -O-CO- include the following groups. In the following examples, * and ** each represent a binding site, and ** is a -O-CO-R2 * binding site.
[0087] Examples of structural unit represented by formula (a4-1) include the following structural units, and structural units in which a methyl group corresponding to R ° * in the structural unit represented by formula (a4- 1) in the following structural units is substituted with a hydrogen atom. Hs CHs Hs Hs Ha Hs CH, Jens Jens Jet ere Jet
[0088] Hz Hs Hs Hg H CH CH 3 Ed F PA Pf; ; O o oO 4 oF $ 4e FF2 Fo E FC FoC FG F2G, FF EF, DF2 F Fa E FR FF FH FC CHF, tes FF (a4-1-7) (a4-1-8) (24-1-9 ) (a4-1-10) (a4-1-11) Hs Hs Hz Hz Hg Hs = +} CH CH nl CH = CH Zi er: 0 er: ° 1 2 O 1 2 Oo Î 2 O 1 2 O ot ot OX 0 0 DF, FF Fa F2 SF BF FoC F, FoC FoC FoC F2G ro F, Pr: + + O
[0089] The structural unit represented by the formula (a4-1) is preferably a structural unit represented by the formula (a4-2): Ha R® A4 o (a4-2) ot
[0090] [0090] Examples of the alkanediyl group having 1 to 6 carbon atoms for L *% include the same groups as those mentioned for the alkanediyl group in A ° **, Examples of saturated hydrocarbon group for R include the same groups as those mentioned for R ° *, The alkanediyl group having 1 to 6 carbon atoms in L ** is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.
[0091] Examples of the structural unit represented by the formula (a4-2) include the structural units each of which is represented by the formula (a4-1-1) to the formula (a4-1-11). Examples of the structural unit represented by the formula (a4-2) also include a structural unit in which a methyl group corresponding to R ° in a structural unit (a4-2) is substituted with a hydrogen atom.
[0092] Examples of the structural unit (a4) include a structural unit represented by the formula (a4-3): Ha R °
[0093] [0093] Examples of the alkanediyl group in L ° include those which are the same as those mentioned in the alkanediyl group of A **, The divalent saturated hydrocarbon group optionally having a fluorine atom in A ** is preferably a hydrocarbon group divalent saturated optionally having a fluorine atom and a divalent alicyclic saturated hydrocarbon group optionally having a fluorine atom, and more preferably a perfluoroalkanediyl group.
[0094] In formula (a4-3), L ° is preferably an ethylene group.
[0095] 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). Examples of the structural unit represented by formula (a4-3) also include a structural unit in which a methyl group corresponding to RP in a structural unit (a4-3) is substituted with a hydrogen atom.
[0096] The structural unit (a4) also includes a structural unit represented by the formula (a4-4): Ha RÍ21 |
[0097] Examples of a saturated hydrocarbon group for R * include those which are the same as the saturated hydrocarbon group represented by R2 * 2. R ° 2 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and more preferably an alkyl group having 1 to 6 carbon atoms having a fluorine atom.
[0098] In the formula (a4-4), Af ! is preferably - (CH2); 1-, more preferably an ethylene group or a methylene group, and more preferably a methylene group.
[0099] The structural unit represented by the formula (a4-4) includes, for example, the following structural units and the structural units in which a methyl group corresponding to R * in the structural unit (a4-4) is substituted with a hydrogen atom in the structural units represented by the following formulas.
[0100] [0100] When the resin (A) includes the structural unit (a4), the content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and more preferably 3 to 10 mol%, on the basis of all the structural units of the resin (A).
[0101] [0101] <Structural unit (a5)> Examples of a 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): Ho 51 (a5-1) 55 / R52 where in the formula (a5-1), R ° represents a hydrogen atom or a methyl group, R ”represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom included in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and L °° represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CHz- included in the saturated hydrocarbon group may be replaced by -O- or -CO-.
[0102] [0102] The alicyclic hydrocarbon group in R can be monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon group includes, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. The polycyclic alicyclic hydrocarbon group includes, for example, an adamantyl group and a norbornyl group.
[0103] [0103] Examples of the group in which -CH> - included in the divalent saturated hydrocarbon group represented by L ”is replaced by - O- or -CO- include groups represented by formula (L1-1) to formula ( L1-4). In the following formulas, * and ** each represent a binding site, and * represents a binding site to an oxygen atom.
[0104] [0104] L is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
[0105] [0105] The group represented by the formula (L1-1) includes, for example, the following divalent groups. A AO A Onee Aon A Ones Aaron
[0106] [0106] The group represented by formula (L1-2) includes, for example, the following divalent groups. T0 HT OA H3 H3 3 0 +7 Tho ”Aho” „tor ho”
[0107] [0107] The group represented by the formula (L1-3) includes, for example, the following divalent groups. CHs O 0 O x On DANA es> „OO A Ö CH3
[0108] [0108] The group represented by the formula (L1-4) includes, for example, the following divalent groups. AO A A * dog Q xx> Va * Q # *
[0109] [0109] L ° ”is preferably a single bond or a group represented by the formula (L1-1).
[0110] [0110] Examples of structural unit (a5-1) include the following structural units and structural units in which a methyl group corresponding to R ° in the structural unit (a5-1) is substituted with a hydrogen atom in the following structural units.
[0111] [0111] <Structural unit (II)> The resin (A) can further include a structural unit which is decomposed by exposure to radiation to generate an acid (hereinafter sometimes referred to as "structural unit (IT)"). Specific examples of the structural unit (IT) include the structural units mentioned in JP 2016-79235 A, and a structural unit having a sulfonate group or a carboxylate group and an organic cation in a side chain or a structural unit having a group sulfonio and an organic anion in a side chain are preferred.
[0112] [0112] The structural unit having a sulfonate group or a carboxylate group in a side chain is preferably a structural unit represented by the formula (II-2-A "):
[0113] [0113] Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0114] [0114] X represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X * represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
[0115] [0115] Examples of ZA ”in formula (II-2-A”) include those which are the same as the Z * cation in the salt represented by formula (B1) mentioned later.
[0116] [0116] The structural unit represented by the formula (II-2-A ") is preferably a structural unit represented by the formula (II-2-A): RIIS
[0117] [0117] The structural unit represented by the formula (II-2-A) is preferably a structural unit represented by the formula (II-2-A-1): RI! I3
[0118] [0118] The structural unit represented by the formula (II-2-A-1) is preferably a structural unit represented by the formula (II-2-A-2): No |
[0119] [0119] Examples of the structural unit represented by the formula (II-2-A ") include the following structural units, structural units in which a group corresponding to the methyl group of RI is substituted by a hydrogen atom, a halogen atom (e.g. a fluorine atom) or an alkyl group having 1 to 6 carbon atoms optionally having a halogen atom (e.g. a trifluoromethyl group, etc.) and the structural units mentioned in WO 2012/050015 A. ZA ”represents an organic cation.
[0120] [0120] 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): Rll4 Aon ais (I1-1-1) pl te OVO AlI-RSS Ril2
[0121] [0121] Examples of structural unit including a cation in the formula (II-1-1) include the following structural units and structural units in which a group corresponding to the methyl group of RI is substituted by a hydrogen atom, a fluorine atom, a trifluoromethyl group and the like.
[0122] [0122] Examples of the organic anion represented by A include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion and a carboxylic acid anion. The organic anion represented by A ’is preferably a sulfonic acid anion, and the sulfonic acid anion is preferably an anion included in the previously mentioned salt represented by formula (B1).
[0123] [0123] Examples of the sulfonylimide anion represented by A include the following. F3 FE pr E 0257 CFs O2 CF O2S-CF2 0592 0,8-cC, len ole ol LN O, S-CF3 ne O2S-CF, odd, O, S — CF, F3 Fab Ge
[0124] [0124] Examples of the sulfonylmethide anion include the following.
[0125] [0125] Examples of the carboxylic acid anion include the following. 9 oO hech he A he Hc Ap EH Ae CH3 O
[0126] [0126] Examples of structural unit represented by formula (II-1-1) include structural units represented by the following.
[0128] [0128] When the structural unit (IT) is included in the resin (A), the content of the structural unit (IT) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and more preferably 3 to 10 mol%, based on all the structural units of the resin (A).
[0129] [0129] 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.
[0130] [0130] The resin (A) is preferably a resin composed of a structural unit (I) and a structural unit (a1), a resin composed of a structural unit (I) and a structural unit ( s), a resin composed of a structural unit (I), a structural unit (a1) and a structural unit (s), a resin composed of a structural unit (I), a structural unit (a1), a structural unit (s), a structural unit (a4) and / or a structural unit (a5), a resin composed only of one structural unit (I), or a resin composed only of one structural unit (I) and a structural unit (a4), and preferably a resin composed of a structural unit (I) and a structural unit (a1), a resin composed of a structural unit (T) and a structural unit (s) or a resin composed of a structural unit (D), a structural unit (a1) and a structural unit (s).
[0131] [0131] The structural unit (a1) is preferably at least one selected from the group including a structural unit (a1-0), a structural unit (a1-OX), a structural unit (a1-1) and a unit structural unit (a1-2) (preferably a structural unit having a cyclohexyl group or a cyclopentyl group), and more preferably at least two selected from the group including a structural unit (a1-0), a structural unit (a1-OX ), a structural unit (a1-1) and a structural unit (a1-2) (preferably a structural unit having a cyclohexyl group or a cyclopentyl group).
[0132] [0132] The respective structural units constituting the resin (A) can be used alone, or two or more structural units can be used in combination. By using a monomer from which these structural units are derived, it is possible to produce 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.
[0133] [0133] [Resist composition] The resist composition of the present invention preferably includes a resin (A) and an acid generator known in the field of resist (hereinafter sometimes referred to as "acid generator (B). "). The resist composition of the present invention may further include a resin other than resin (A). The resist composition of the present invention preferably includes a quencher such as an acid generating salt having an acidity lower than that of an acid generated by an acid generator (hereinafter sometimes. referred to as “deactivating agent (C)”), and preferably includes a solvent (hereinafter sometimes referred to as “solvent (E)”.
[0134] [0134]… <Resin other than resin (A)> In the resist composition of the present invention, a resin other than resin (A) can be used in combination therewith. The resin other than the resin (A) is a resin which does not include any structural unit (I), and examples of the resin include a resin comprising a structural unit having an acid labile group and not including any structural unit (T) (hereinafter sometimes called "resin (AY)"), a resin composed only of a structural unit (a4), and a resin composed of a structural unit (a4) and a structural unit (a5 ) (hereinafter, a resin composed only of a structural unit (a4) and a resin composed of a structural unit (a4) and a structural unit (a5) may sometimes be referred to collectively as resin (X)). In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, and more preferably 45 mol% or more, on the basis of basis of the total of all structural units of the resin (X).
[0135] [0135] The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, and more preferably 90% to 99% by mass, based on solid component of the resist composition. When including resins other than resin (A), the total content of resin (A) and resins other than resin (A) is preferably 80% by mass or more and 99% by mass or less, and more preferably from 90% to 99% by weight, based on the solid component of the resist composition. The solid component of the resist composition and the content of the resin can be measured by a known analytical means such as liquid chromatography or gas chromatography.
[0136] [0136] <Acid Generator (B)> A nonionic or ionic acid generator can be used as an acid generator (B). Examples of the nonionic acid generator include the sulfonate esters (e.g. ester 2-
[0137] [0137] Specific examples of the acid generator (B) include compounds generating an acid by 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. 3,779,778, US Patent No. 3,849,137, DE Patent No. 3,914,407 and EP Patent No. 126,712 . Compounds produced by a known process can also be used. Two or more acid generators (B) can also be used in combination.
[0138] The acid generator (B) is preferably an acid generator containing fluorine, and more preferably a salt represented by the formula (B1) (hereinafter sometimes called “acid generator (B1). ”): Qh Z * 7038 Le! SALA (BH) 1 where, in formula (B1), QP! and QP each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, LP! represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CH> - included in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group,
[0139] [0139] Examples of the perfluoroalkyl group represented by Q% and QP include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group and a perfluorohexyl group.
[0140] [0140] 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.
[0141] [0141] The group in which -CHz- included in the divalent saturated hydrocarbon group represented by L ”is replaced by -O- or - CO- includes, for example, a group represented by any one of the formula (b1- 1) to the formula (b1-3). In the groups represented by the formula (b1-1) with the formula (b1-3) and the groups represented by the formula (b1-4) with the formula (b1-11) which are specific examples thereof, * and ** represent a binding site, and * represents a binding to -Y.
[0142] 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.
[0143] [0143] LP is preferably a single bond.
[0144] [0144] 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).
[0145] [0145] Examples of the group represented by formula (b1-3) include groups represented by formula (b1-9) to formula (b1-11). ARS AE SO A
[0146] [0146] In the group represented by the formula (b1-9) to the group represented by the formula (b1-11), when a hydrogen atom included in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before substitution is taken as the number of carbon atoms of the saturated hydrocarbon group.
[0147] [0147] Examples of the group represented by the formula (b1-4) include the following:
[0148] [0148] Examples of the group represented by the formula (b1-5) include the following:
[0149] [0149] Examples of the group represented by the formula (b1-6) include the following: Oo OQ 0 NNT Adr AIT Hs CHs 4 CH3 0 0 Q 0 Ae Athos a “oise“ iso O x Afd AND
[0150] [0150] Examples of a group represented by the formula (b1-7) include the following:
[0151] [0151] Examples of the group represented by the formula (b1-8) include the following:
[0152] [0152] Examples of the group represented by the formula (b1-2) include the following: Ar Ho, ok a x go Ta Hose Hose u A AHA,
[0153] [0153] Examples of the group represented by the formula (b1-9) include the following:
[0154] [0154] Examples of a group represented by the formula (b1-10) include the following:
[0155] [0155] Examples of the group represented by the formula (b1-11) include the following: CH4 OOO 0 D Ö Hi Hi ap AA Jed Jord A y + FU OH Ar FF CH, QF CF, Oo F (F3 9 dr Are poe Ao 0 © F OF 9 F À À À F Ca À CHs 5 A & &
[0156] [0156] Examples of the alicyclic hydrocarbon group represented by Y include the groups represented by formula (Y1) to formula (Y11) and by formula (Y36) to formula (Y38).
[0157] [0157] Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a group glycidyloxy, a group - (CHz); - CO-OR® * or a group - (CH2); a-0-CO-RP! (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, ja represents an integer from 0 to 4 and -CHz- included in an alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -S (O) z- or -CO-, a hydrogen atom included in the group alkyl, alicyclic hydrocarbon group and aromatic hydrocarbon group may be substituted by hydroxy group or fluorine atom) and the like. Examples of the substituent of the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 atoms. carbon, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, a group glycidyloxy, a - (CH2); .- CO-OR® or a - (CHz) ja-O-CO-RP! (where RP! represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or groups obtained by combining these groups, ja represents an integer of 0 to 4, and - CHz- included in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -S (0) z- or -CO-, a hydrogen atom included in the group alkyl, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a hydroxy group or a fluorine atom) and the like.
[0158] [0158] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group and the like. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples thereof include - methylcyclohexyl group, dimethylcyclohexyl group and the like.
[0159] [0159] Examples of Y include the following. CHs CH3 H3C44CH3 AoA 49 erde OH
[0160] [0160] Ö 6 Ç HO 6 {° ae. © 7 7 7 +) EOV A AN Q + Le € to OH
[0161] [0161] Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an adamantyl group which may have a substituent, and -CH> - constituting the alicyclic hydrocarbon group or the adamantyl group. can be replaced by -CO-, -S (O) 2- or -CO-. Y is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, or groups represented by the following formulas.
[0162] [0162] The anion in the salt represented by formula (B1) is preferably an anion represented by formula (B1-A-1) to formula (B1-A-55) [hereinafter sometimes referred to as "anion (B1-A-1) "according to the number of the formula], and more preferably an anion represented by any one of the formula (B1-A-1) to the formula (B1-A-4), the formula (B1- A-9), formula (B1-A- 10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40) and formula (B1-A-47) to formula (B1-A-55).
[0163] [0163]
[0164] [0164] Oo y OP „a2 ak! Lo 7 OSS c ee ab Lab Ve (B1-A-13) (B1-A-14) O ° (B1-A-15) OH 0 X OH a a2 0 QE Q ” OH _ _ O Oo O - 0.87 5 <2 O (B1-A-16) O (B1-A-18) (B1-A-17) OH OH
[0165] [0165]
[0166] [0166] Ong oP! ob R7 op! PL _ N _ A4 - A4 T ° LA és Oo st> Ö Qb2 F Qb2 (B1-A-33); (B1-A-34) (B1-A-35) F
[0167] [0167] a9 Qb a9 Qb „0.6 v0.” ob 9 OS = 0 (B1-A-45) © (B1-a-46) © 9 OOO> L_ 9, b Y 0 + 9 ab ab Ce bt 302 OÙ bl 2 OÙ Q7 AOQA oO _ Os, Aa _ O . YT L oes 08 ° LA4 (B1-A-47) (B1-A-48) (B1-A-49)
[0168] [0168] Examples of the anion in the salt represented by formula (B1) preferably include anions represented by formula (B1a-1) through formula (B1a-34). HO 5 0258 | Ar “048 O 035 O (Bla-1) 9 (Bla-2) (Bla-3)
[0169] [0169]
[0170] [0170] O. AP De OP "
[0171] [0171] Among these, the anion is preferably an anion represented by any one of the formula (B1a-1) to the formula (B1a-3) and of the formula (B1a-7) to the formula (B1a-16), formula (B1a-18), formula (B1a-19) and formula (B1a-22) to formula (B1a-34).
[0172] [0172] Examples of the organic cation of Z * include an organic onium cation, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation and an organic phosphonium cation. 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)
[0173] [0173] Rn (R ° 7) m2 (RP) Rb9 9 R $. Or 5 -2s * -CH-C-R812 R R Rb11 (b2-1) (b2-2) (b2-3) (RES) 2 (RP) CR) + Ey {3S (b2-4); LA AND LG 9 69916 (RP) 2 (RE1S) 2 (RET8) 2/42 1 / (u2 + 1) 5 In formula (b2-1) in formula (b2-4), RP * to RP each represent independently a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms or an aromatic hydrocarbon group having 6 to 36 carbon atoms, a hydrogen atom included in the chain hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, a hydrogen atom included in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group, and a hydrogen atom included in the aromatic hydrocarbon group may be substituted with an at halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms, RP * and RP can form a ring with the sulfur atoms to which R® * and R ”are attached, and -CHz- included in the cycle can be replaced by -O-, -S- or -CO-,
[0174] [0174] 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.
[0175] [0175]
[0176] [0176] Examples of cation (b2-2) include the following cations. + + DQ 0 IDK (b2-c-28) (b2-c-29) (b2-c-30)
[0177] [0177] Examples of cation (b2-3) include the following cations. PC LE) X LEI eo + + CO + (b2-c-31) (b2-c-32) (b2-c-33) (b2-c-34)
[0178] [0178] Examples of cation (b2-4) include the following cations. 0-0 HOO OO (b2-c-35) (b2-c-36) (b2-c-37) HsC HC HaC 3 TD 3 “er Oren (b2-c-38) (b2-c-39) ( b2-c-40)
[0179] [0179] HsC HsC t-C4Hg + ds) zoo 200 H3C (b2-c-41) Ha (02-c-42) (b2-c-43) tC, H9 t-C4Hg t-C4He BA set 9-0 SS CH 3 we © © t-CaHo (b2-c-45) t-CaH4o (b2-c-46) The acid generator (B) is a combination of the aforementioned anions and the aforementioned organic cations, and these can optionally be combined. Examples of the acid generator (B) are preferably combinations of anions represented by any one of formula (B1a-1) to formula (B1a-3) and of formula (B1a-7) to formula (B1a-16), formula (Bla 18), formula (B1a-19) and from formula (B1a-22) to formula (B1a-34) with a cation (b2-1) or a cation (b2-3).
[0180] [0180] Examples of the acid generator (B) are preferably those represented by the formula (B1-1) to the formula (B1-48). Of these, those containing an arylsulfonium cation are preferred, and those represented by formula (B1-1) to formula (B1-3), formula (B1-5) to formula (B1-7), formula (B1-11) to formula (B1-14), formula (B1-20) to formula (B1-26), formula (B1-29) and formula (B1-31) to formula ( B1-48) are particularly preferable.
[0181] [0181] t-C4Ho y © CH} SX ous; HA C Ô Ò Ô He tC, Hs (B1-10) (B1-11) Gen I 9 + D ot es otre a A OR € a (B1-13) (B1-14) (B1-15) SL Q @ , A Ge: VE VS + oct Kp PT T ° At 5 (4 (B1-18) O (B1-17) (B1-16) e _, |
[0182] [0182]
[0183] [0183]
[0184] [0184]
[0185] [0185] No A 0 O Q 0 A 9 @ - 9 g> ° Od de (81-48) (B1-46) X X:
[0186] [0186] In the resist composition of the present invention, the content of acid generator is preferably 1 part by mass or more and 45 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 35 parts by mass or less, based on 100 parts by mass of the resin (A).
[0187] [0187] <Solvent (E)> The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more and 99% by mass or less. The content of the solvent (E) can be measured, for example, by a known analytical means such as liquid chromatography or gas chromatography.
[0188] [0188] <Quencher quencher (C)> Examples of quencher (C) include an acid-generating salt having an acidity lower than that of an acid generated from an acid generator (B) and an organic compound containing basic nitrogen. The content of the deactivating agent (C) is preferably about 0.01 to 15% by mass, more preferably about 0.01 to 10% by mass, more preferably about 0.01 to 5% by mass and preferably still about 0.01 to 3% by weight, based on the amount of the solid component of the resist composition.
[0189] [0189] <Salt generating an acid having an acidity lower than that of the acid generated by the acid generator> The acidity in a salt generating an acid having an acidity lower than that of an acid generated from the generator of acid (B) is indicated by the acid dissociation constant (pKa). Regarding the acid generating salt having lower acidity than an acid generated from the acid generator (B), the acid dissociation constant of an acid generated from the salt usually responds to the inequality following: -3 <pKa, preferably -1 <pKa <7, and more preferably 0 <pKa <
[0190] [0190] Examples of the weak acid internal salt (D) include the following salts. _ 007 -00; ; coo AO 5-0 DH) HQ oo 007 COO oo O0. Fo Ho 040 dp- 6 7 Br 7 CI 7 06 COO 00 00 G- _ SEO GEO oo SP
[0191] [0191] Examples of an organic compound containing basic nitrogen include an amine and an ammonium salt. Examples of the amine include an aliphatic amine and an aromatic amine. Examples of an aliphatic amine include a primary amine, a secondary amine, and a tertiary amine.
[0192] [0192] <Other components> The resist composition of the present invention may also include components other than the components mentioned above (hereinafter sometimes referred to as "other components (F)"). The other components (F) do not are not particularly limited and it is possible to use various additives known in the resist field, for example sensitizers, dissolution inhibitors, surfactants, stabilizers, and dyes.
[0193] [0193] <Preparation of resist composition> The resist composition of the present invention can be prepared by mixing a resin (A) of the present invention and an acid generator (B) and optionally a acid generating salt having an acidity lower than that of an acid generated from the acid generator, a resin (AY), a resin (X), a deactivating agent (C), d 'a solvent (E), and other components (F). The order of mixing these components is any order and is not particularly limited. It is possible to choose, as the temperature during mixing, a suitable temperature of 10 to 40 ° C, depending on the type of the resin, the solvent solubility (E) of the resin and the like. It is possible to choose, as the mixing time, an appropriate time of 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited and it is possible to use mixing with stirring. After mixing the respective components, the mixture is preferably filtered through a filter having a pore diameter of about 0.003 to 0.2 µm.
[0194] [0194] <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,
[0195] [0195] - <Applications>
[0196] [0196] The present invention will be described more specifically by way of examples. The percentages and the parts expressing the contents or the amounts used in the examples are by weight unless otherwise indicated.
[0197] [0197] Example 1: Synthesis of the compound represented by the formula (I-1) | A —Si-CI HO Q | 9 BA _ —— Brzn Ae> xt Zn (I-1-b) (I-1-a) (I-1-c) 49.87 parts of zinc and 500 parts of tert-butylmethyl ether were mixed, which was followed by stirring at 23 ° C for 30 minutes.
[0198] [0198] Example 2: Synthesis of the compound represented by the formula (I-2) | X | + 1 di BA, _ —— BrZzn A> 9 Zn (I-2-b) (I-1-a) (I-2-c) 49.87 parts of zinc and 500 parts of tert-butylmethyl ether have was mixed, which was followed by stirring at 23 ° C for 30 minutes.
[0199] [0199] Example 3: Synthesis of the compound represented by the formula (I-5)
[0200] [0200] Example 4: Synthesis of the compound represented by the formula (I-7) + 2 n, $ Aj, AR - aan Ser To (I-1-b) (I-7-a) (I-7-c ) 3.89 parts of zinc and 40 parts of tert-butylmethyl ether were mixed, followed by stirring at 23 ° C for 30 minutes.
[0201] [0201] Example 5: Synthesis of the compound represented by the formula (I-13)
[0202] [0202] Example 6: Synthesis of the compound represented by the formula (I-4)
[0203] [0203] Example 7: Synthesis of the compound represented by the formula (I-3)
[0204] [0204] Example 8: Synthesis of the compound represented by the formula (I-8) O (0) o te 0 Lie, 0 and „> Br À,> (I-1-b) (I-8-a) ( I-8-c) 3.89 parts of zinc and 40 parts of tert-butylmethyl ether were mixed, then stirred at 23 ° C for 30 minutes.
[0205] [0205] Example 9: Synthesis of the compound represented by the formula (I-9) Ha F q CH3 ° ae; SU oO es, O F Oo O I A + Ho Son A. ©
[0206] [0206] Synthesis of Resin The compounds (monomers) used by addition to acetoxystyrene in the synthesis of the resin are presented below.
[0207] [0207] Example 10 [Synthesis of resin A1] Acetoxystyrene, a monomer (a1-1-3) and a monomer (I-1) were used as monomers, these monomers were mixed in a molar ratio of 38:24:38 [acetoxystyrene: monomer (a1-1- 3): monomer (I-1)] and methyl isobutyl ketone was then added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours followed 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 collection to obtain an A1 resin (copolymer) having a weight average molecular weight of about 5.4 x 103 with a yield of 72%. This A1 resin has the following structural units. {we have tof 5 {0 A1 mp “© OH
[0208] [0208] Example 11 [Synthesis of resin A2] Acetoxystyrene, a monomer (a1-1-3) and a monomer (I-2) were used as monomers, these monomers were mixed in a molar ratio of 38:24:38 [acetoxystyrene: monomer (a1-1-3): monomer (I-2)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A2 resin (copolymer) having a weight average molecular weight of about 5.4 x 103 with a yield of 70%. This A2 resin has the following structural units. CHs H {ct tod, te 15% 0 " OH
[0209] [0209] Example 12 [Synthesis of resin A3] Acetoxystyrene, a monomer (a1-1-3) and a monomer (I-5) were used as monomers, these monomers were mixed in a molar ratio of 38:24:38 [acetoxystyrene: monomer (a1-1- 3): monomer (I-5)] and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A3 resin (copolymer) having a weight average molecular weight of about 5.4 x 103 with a yield of 76%. This A3 resin has the following structural units.
[0210] [0210] Example 13 [Synthesis of resin A4] Acetoxystyrene, monomer (a1-1-3) and monomer (I-7) were used as monomers, these monomers were mixed in a molar ratio. of 38:24:38 [acetoxystyrene: monomer (a1-1- 3): monomer (I-7)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A4 resin (copolymer) having a weight average molecular weight of approximately 5.5 x 103 with a yield of 64%. This A4 resin has the following structural units. Hs Hs fen tof tog, DO + OH VO A
[0211] [0211] Example 14 [Synthesis of resin A5] Acetoxystyrene, a monomer (a1-2-6) and a monomer (I-1) were used as monomers, these monomers were mixed in a molar ratio of 38:38:24 [acetoxystyrene: monomer (a1-2-6): monomer (I-1)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A5 resin (copolymer) having a weight average molecular weight of about 5.2 x 103 with 89% yield. This A5 resin has the following structural units. "5 tou tende 0 9 N Q 9 A5 OH Yo -
[0212] [0212] Example 15 [Synthesis of resin A6] Acetoxystyrene and a monomer (I-1) were used as monomers, these monomers were mixed in a molar ratio of 38:62 [acetoxystyrene: monomer (I- 1)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A6 resin (copolymer) having a weight average molecular weight of d. About 5.3 x 103 with a yield of 67%. This A6 resin has the following structural units. {we will
[0213] [0213] Example 16 [Synthesis of resin A7] Acetoxystyrene, monomer (a1-2-6) and monomer (1-13) were used as monomers, these monomers were mixed in a molar ratio. of 38:38:24 [acetoxystyrene: monomer (a1-2-6): monomer (I-13)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A7 resin (copolymer) having a weight average molecular weight of d. About 5.3 x 103 with 88% yield. This A7 resin has the following structural units.
[0214] [0214] Example 17 [Synthesis of resin A8] Acetoxystyrene, a monomer (a1-2-6) and a monomer (I-4) were used as monomers, these monomers were mixed in a molar ratio of 38:38:24 [acetoxystyrene: monomer (a1-2-
[0215] [0215] Example 18 [Synthesis of resin A9] Acetoxystyrene, a monomer (a1-2-6) and a monomer (I-3) were used as monomers, these monomers were mixed in a molar ratio of 38:38:24 [acetoxystyrene: monomer (a1-2-6): monomer (I-3)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A9 resin (copolymer) having a weight average molecular weight of d. 'about 5.6 x 10 ° with a yield of 80%. This A9 resin has the following structural units. Hs CHs ot tou wigs 5 Q ON Ô d A9 OH Yo -
[0216] [0216] Example 19 [Synthesis of resin A10] Acetoxystyrene, monomer (a1-2-6) and monomer (I-7) were used as monomers, these monomers were mixed in a molar ratio of 38:38:24 [acetoxystyrene: monomer (a1-2-6): monomer (I-7)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A10 resin (copolymer) having a weight average molecular weight of d. About 5.4 x 103 with a yield of 77%. This A10 resin has the following structural units. tp tof tg, 5 ol) 6 A10
[0217] [0217] Example 20 [Synthesis of the resin A11] Acetoxystyrene, a monomer (a1-2-6) and a monomer (I-8) are used as monomers, these monomers were mixed in a molar ratio of 38 : 38: 24 [acetoxystyrene: monomer (a1-2-6): monomer (I-8)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, followed by stirring for 12 hours, then isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A11 resin (copolymer) having a weight average molecular weight of d. 'approximately 5.5 x 103 with a yield of 79%. This resin A11 has the following structural units.
[0218] [0218] Example 21 [Synthesis of resin A12] Acetoxystyrene, a monomer (a1-2-6) and a monomer (1-9) were used as monomers, these monomers were mixed in a molar ratio of 38:38:24 [acetoxystyrene: monomer (a1-2-6): monomer (I-9)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an A12 resin (copolymer) having a weight average molecular weight of d. About 5.2 x 103 with a yield of 71%. This A12 resin has the following structural units. 4 F 1 Hs Let, tof F ter, 5 d where AT 12
[0219] [0219] Synthesis Example 1 [Synthesis of the AX1 resin] Acetoxystyrene and a monomer (IX-1) were used as monomers, these monomers were mixed in a molar ratio of 38:62 [acetoxystyrene: monomer ( IX-1)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an AX1 resin (copolymer) having a weight average molecular weight of d. 'about 5.4 x 10 ° with a yield of 66%. This AX1 resin has the following structural units.
[0220] [0220] Synthesis Example 2 [Synthesis of AX2 Resin] Using acetoxystyrene and a monomer (IX-2) as 5 monomers, these monomers were mixed in a molar ratio of 38:62 [acetoxystyrene: monomer ( IX-2)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an AX2 resin (copolymer) having a weight average molecular weight of d. 'about 5.3 x 10 ° with a yield of 60%. This AX2 resin has the following structural units.
[0221] [0221] Synthesis Example 3 [Synthesis of AX3 Resin] Acetoxystyrene and a monomer (IX-3) were used as monomers, these monomers were mixed in a molar ratio of 38:62 [acetoxystyrene: monomer ( IX-3)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an AX3 resin (copolymer) having a weight average molecular weight of d. 'approximately 5.5 x 10 ° with a yield of 72%. This AX3 resin has the following structural units. Lc, Ho 5 to AX3 o Q OH q 0
[0222] [0222] Synthesis Example 4 [Synthesis of AX4 Resin] Acetoxystyrene and a monomer (IX-4) were used as monomers, these monomers were mixed in a molar ratio of 38:62 [acetoxystyrene: monomer ( IX-4)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an AX4 resin (copolymer) having a weight average molecular weight of d. 'about 5.6 x 10 ° with a yield of 78%. This AX4 resin has the following structural units. Lech Lon, + O AX4 h AT LE,
[0223] [0223] 5 Synthesis Example 5 [Synthesis of AX5 resin] Acetoxystyrene and a monomer (IX-5) were used as monomers, these monomers were mixed in a molar ratio of 38:62 [acetoxystyrene: monomer (IX-5)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an AX5 resin (copolymer) having a weight average molecular weight of d. 'about 5.3 x 10 ° with a yield of 66%. This AX5 resin has the following structural units.
[0224] [0224] Synthesis Example 6 [Synthesis of AX6 resin] Acetoxystyrene and a monomer (IX-6) were used as monomers, these monomers were mixed in a molar ratio of 38:62 [acetoxystyrene: monomer ( IX-6)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an AX6 resin (copolymer) having a weight average molecular weight of d. 'about 5.7 x 10 ° with a yield of 82%. This AX6 resin has the following structural units. “5 to O AX6 ss
[0225] [0225] Synthesis Example 7 [Synthesis of AX7 resin] Acetoxystyrene and a monomer (IX-7) were used as monomers, these monomers were mixed in a molar ratio of 38:62 [acetoxystyrene: monomer ( IX-7)], and methyl isobutyl ketone was added in an amount equal to 1.5 times the total mass of all monomers. To the mixture thus obtained, azobisisobutyronitrile and azobis (2,4-dimethylvarelonitrile) as initiators were added in amounts of 2.1 mole% and 6.3 mole% based on total molar number of all monomers, which was followed by polymerization of the mixture by heating at 73 ° C for about 5 hours. To the polymerization reaction solution thus obtained, a 25% aqueous solution of tetramethylammonium hydroxide was added, which was followed by stirring for 12 hours, followed by isolation by separation. The organic layer thus obtained was poured into a large amount of n-heptane to precipitate a resin, which was followed by filtration and collection to obtain an AX7 resin (copolymer) having a weight average molecular weight of d. 'about 5.1 x 10 ° with a yield of 59%. This AX7 resin has the following structural units.
[0227] [0227] <Resin> A1 to A12, AX1 to AX7: Resin A1 to Resin A12, Resin AX1 to Resin AX7. <Acid generator (B)> B1-25: salt represented by formula (B1-25), synthesized by the method mentioned in JP 2011-126869 A Pig + O O
[0228] [0228] (Evaluation of the exposure of the resist composition with an electron beam) Each 6 inch diameter silicon wafer was treated with hexamethyldisilazane and then baked on a direct hotplate at 90 ° C for 60 seconds. A resist composition was applied by centrifugal application (“spin coating”) to the silicon wafer so that the thickness of the composition is then 0.04 μm. The coated silicon wafer was prebaked on the direct hot plate at the temperature shown in the "PB" column of Table 1 for 60 seconds. Using a direct electron beam writing system (“ELS-F125 125 keV”, manufactured by ELIONIX INC.), Contact hole patterns (40 nm hole spacing / 17 mm hole diameter nm) were written directly onto the composition layer formed on the wafer while the exposure dose was changed in stages.
[0229] [0229] <CD Uniformity Evaluation (CDU)> In the effective sensitivity, the hole diameter of the resist pattern formed with a hole diameter of 17 nm was determined by measuring 24 times a same hole and the average of the measured values was taken as the average hole diameter. The standard deviation was determined under the conditions where the average diameter of 400 holes around patterns formed with a hole diameter of 17 nm in the same wafer was considered a population.
[0230] [0230] A resist composition comprising a resin including a structural unit derived from a compound of the present invention is capable of producing a resist pattern with satisfactory CD uniformity (CDU), and therefore is suitable for semi-fine processing. -conductor, and is therefore very useful from an industrial point of view.

权利要求:
Claims (14)
[1]
1. A compound represented by formula (T): R1 | CH: =
O (I) 1
CT Na
A of 4 where in formula (I), R * represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, A! represents a single bond or * -A -CO-0-, and * represents a binding site to an oxygen atom, A represents an alkanediyl group having 1 to 6 carbon atoms, W represents a divalent monocyclic saturated alicyclic hydrocarbon group having 3 to 12 carbon atoms, A represents an alkanediyl group having 1 to 6 carbon atoms, R and R3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom (-CHz- included in the hydrocarbon group may be replaced by -O-, -S-, - CO- or -SO--), or R and R ° are bonded to each other to form a ring having 3 to 36 carbon atoms which may have a fluorine atom or an alkyl group having 1 to 12 atoms of carbon (-CHz- included in the alkyl group can be replaced by -O- or -CO-, and -CH: - included in the ring can be replaced by -O-, - S-, -CO- or -SO -), and R * represents a hydrogen atom, or R2, R * and R * are bonded to each other to form a ring having 3 to 36 carbon atoms which may have a fluorine atom or an alkyl group having 1 to 12 carbon atoms (-CH: - included in the alkyl group can be replaced by -O- or -CO-, and -CH: - included in the ring can be replaced by -O-, -S-, -CO- or -SOz-).
[2]
2. A compound according to claim 1, wherein W is a cyclopentanediyl group or a cyclohexanediyl group.
[3]
3. A compound according to claim 1, wherein A! is a single bond.
[4]
4. A compound according to claim 1, wherein A is a methylene group.
[5]
5. A compound according to claim 1, wherein R * and R each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a fluorine atom (-CH> - included in the hydrocarbon group may be replaced by -O-, -S-, - CO - or -SO--), or R and R ° are linked to each other to form a ring having 3 to 16 carbon atoms which may have a fluorine atom or an alkyl group having 1 to 6 carbon atoms (-CH> - included in the group alkyl can be replaced by -O- or -CO-, and -CH> - included in the ring can be replaced by -O-, -S-, -CO- or -SO--), and R * is an atom of hydrogen, or R2, R * and R * are bonded together to form a ring having 3 to 16 carbon atoms which may have a fluorine atom or an alkyl group having 1 to 6 carbon atoms (-CH; - included in the alkyl group can be replaced by -O- or -CO-, and -CH> - included in the ring can be replaced by -O-, -S-, -CO- or -SO7- ).
[6]
6. A compound according to claim 1, wherein the compound is represented by any one of formula (I-1) to formula (I-16):
Ha OH CH, £ tis MAC ex HM Oe HC = Ha = as AS oO; nn = © K © A X $ 3; ï Tes ë sd 8 x © 3 La hd At 2} {3-33 iet} CH 125 Ha CH; 0x a A n RO HO pe, ds en Nee N NN N © Nef i; ex 0 ii | 2 3 if $ 35 SC is 3 ETD LA Fa AT 54 7 Bn) À dt at 9 5 SNS Sd is LN ON EPS # 0 OT re ME OT es OTN ON T0 Oh & À 2; CES {53 {6} {HP} AS € CH e = “9 Otte UH, a X‘ Sa A Er, Hot SN 9 AN 3 to 9; at ; N PA ië sé, N D an. NOT ; ij LS ll Q + Oo n = ET peen Dik, dy Q es, £ À 9} N ON +5 3-43 OH, DH, Ste Et He Hoe Hors, ue, Fes PA ur es seu j 9 Fa È A 9 Fan OO - jo Ted SA el AR md gel, en, © NT = 3 No D Ln (15) 18) 13 ita) To;
[7]
7. A resin comprising a structural unit derived from compound 5 according to claim 1.
[8]
8. The resin according to claim 7, further comprising a structural unit represented by the formula (a2-A):
Hz Ra50
HE Aas0 (a2-A) Don (this mb 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 alkylcarbonyl group having 2 to 4 carbon atoms, carbon, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group, A2 ° 0 represents a single bond or * -X2 ** - (A252-X252) p-, and * represents a binding site at the carbon atoms to which -R °° is attached, A represents an alkanediyl group having 1 to 6 carbon atoms, x °° 1 and X each independently represent -O-, -CO-O- or -O-CO -, nb represents 0 or 1, and mb represents an integer of 0 to 4, and when mb is an integer of 2 or more, a plurality of R ° * may be the same or different from each other.
[9]
9. The resin according to claim 7, further comprising a structural unit having an acid labile group which is different from the structural unit derived from the compound represented by the formula (I).
[10]
10. The resin according to claim 9, wherein the resin comprising a structural unit having an acid labile group which is different from the structural unit derived from the compound represented by formula (I) is a resin including at least one structural unit. selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2): Lt a | The In
CC
OO La 'La2 of Fetim pot Sch ni "(a1-1) (a1-2) where in formula (a1-1) and formula (a1-2), L ° * and L * each independently represent -O - or * -O- (CH>) ki-CO-O-, kl represents an integer from 1 to 7, and * represents a bond to -CO-, R ° * and R® each independently represent a hydrogen atom or a methyl group, R °° and R each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group obtained by combining these groups, m1 represents an integer from 0 to 14, n1 represents an integer from 0 to 10, and n1 'represents an integer from 0 to 3.
[11]
11. A resist composition comprising the resin of claim 7 and an acid generator.
[12]
12. The resist composition of claim 11, further comprising an acid generating salt having an acidity lower than that of an acid generated by the acid generator.
[13]
13. The resist composition of claim 11, wherein the acid generator comprises a salt represented by formula (B1):
+ -0-S LM 7+ - 3 dy (B1) Loe where, in formula (B1), QP! and Q ° each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, LP! represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CH> - included in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH> - included in the hydrocarbon group alicyclic can be replaced by -O-, -S (O) 2- or -CO-, and Z 'represents an organic cation.
[14]
14. A method for producing a resist pattern, which comprises: (1) a step of applying the resist composition of claim 11 to a substrate, (2) a step of drying the applied composition to form a layer. composition, (3) a step of exposing the composition layer, (4) a step of heating the exposed composition layer, and (5) a step of developing the heated composition layer.

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法律状态:
2020-10-28| FG| Patent granted|Effective date: 20201012 |

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2021-04-19| FG| Patent granted|Effective date: 20210215 |

优先权:

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申请号 | 申请日 | 专利标题

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JP2019057228|2019-03-25|

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