Positive resist composition

专利摘要:
PURPOSE: A positive resist composition satisfactory in line edge roughness is provided, and a positive resist composition of excellent quality that can produce patterns prevented from toppling even when there are variations of focus and exposure in fine patterning is provided. CONSTITUTION: The positive resist composition comprises the components of (A) a compound capable of generating an acid upon irradiation with one of an actinic ray and a radiation; (B) a resin that is insoluble or slightly soluble in alkalis, but becomes alkali-soluble under an action of an acid; (C) a basic compound; and (D) a compound comprising at least three hydroxyl groups or at least three substituted hydroxyl groups, and comprising at least one cyclic structure, wherein the component (D) is a compound comprising at least three hydroxyl groups and at least one cyclic structure, and at least one group selected from the hydroxyl groups and other groups of the component (D) is protected with at least one acid-decomposable group, wherein the component (B) is a resin that comprises at least one phenolic hydroxyl group structure and that is capable of decomposing by an action of an acid to increase in solubility in an alkaline developer, wherein the component (B) is a resin comprising an alicyclic hydrocarbon group that is monocyclic or polycyclic and being capable of decomposing by an action of an acid to increase in solubility in an alkaline developer, wherein the component (B) is a resin having a structure wherein at least one fluorine atom is substituted in at least one of a main chain and a side chain of a polymer, and being capable of decomposing by an action of an acid to increase in solubility in an alkaline developer, wherein the positive resist composition further comprises a component of (E) a surfactant comprising at least one of a fluorine atom and a silicone atom, and wherein the positive resist composition further comprises a component of (F) a mixture of a hydroxyl group-containing solvent and a hydroxyl group-free solvent.
公开号:KR20030051186A
申请号:KR1020020057202
申请日:2002-09-19
公开日:2003-06-25
发明作者:후지모리토루；카와베야스마사
申请人:후지 샤신 필름 가부시기가이샤；
IPC主号:

专利说明:

Positive Resist Composition {POSITIVE RESIST COMPOSITION}
[1] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to positive resist compositions used in semiconductor manufacturing processes such as ICs, in the production of circuit boards such as liquid crystals, thermal recording heads, and other optical manufacturing processes. More specifically, the present invention relates to a positive resist composition which is preferable in the case of using an ultraviolet light of 250 nm or less as an exposure light source or an electron beam as an irradiation source.
[2] The chemically amplified positive resist composition is a pattern forming material for forming a pattern on a substrate as follows. By irradiating radiation such as far ultraviolet light, these resist compositions generate an acid in the irradiated region and form a pattern by changing the solubility of the active radiation in the developer and irradiated portion of the irradiated portion by reaction using the acid as a catalyst. You can.
[3] When the KrF excimer laser is used as an exposure light source, a resin mainly composed of poly (hydroxystyrene), which has a small absorption in a 240 nm region, is used as a main component, thereby forming a highly sensitive, high resolution, and desirable pattern. This is a better system than the conventional naphthoquinone diazide / novolak resin system.
[4] However, when a shorter wavelength light source, such as an ArF excimer laser (193 nm), is used as an exposure light source, the compound having an aryl group exhibits a large absorption in the 193 nm region essentially, so that the chemical amplification system is sufficient. It wasn't.
[5] In addition, the use of poly (meth) acrylate as a polymer having a low absorption in the 193 nm wavelength region is described in J. Vac. Sci. Technol. , B9, 3357 (1991), but this polymer has a problem that resistance to dry etching generally performed in semiconductor manufacturing processes is lower than that of conventional phenol resins having aryl groups.
[6] For the recent trend of miniaturization and high efficiency, it has become important to reduce errors due to exposure. In the resist compositions thus far, the exposure margin is narrow, the line edge roughness is poor, and the efficiency is high.
[7] In addition, the recent miniaturization has resulted in a strict aspect ratio with respect to the film thickness, so that the formed pattern tends to be easily recessed. This trend is remarkable in ArF resists, electron beam (EB) resists, vacuum ultraviolet (VUV) resists, and extreme ultraviolet (EUV) resists. Here, the "pattern depression" includes both a depression due to lack of adhesion, a depression due to a lack of strength of the film, and the like.
[8] Accordingly, an object of the present invention is to provide a positive resist composition having excellent edge roughness.
[9] Still another object of the present invention is to provide an excellent positive resist composition which can prevent pattern depression even if the focus and exposure in a fine pattern are varied.
[10] The above object of the present invention is achieved by a positive resist composition comprising the following components. (Hereinafter referred to as Embodiment 1)
[11] (1) (A) a compound which generates an acid by irradiation of actinic light or radiation,
[12] (B) a resin which is insoluble or poorly soluble in alkali but becomes alkali-soluble by the action of an acid,
[13] (C) a basic compound, and
[14] (D) A positive resist composition having at least three hydroxyl groups or substituted hydroxyl groups and containing a compound having at least one cyclic structure.
[15] Hereinafter, preferable embodiment of this invention is shown.
[16] (2) The compound according to claim 1, wherein the compound (D) is a compound having at least three hydroxyl groups and at least one cyclic structure, and the hydroxyl groups and / or other groups are protected by at least one acid-decomposable group. The positive resist composition characterized by the above-mentioned.
[17] (3) The resin (B) is a resin according to claim 1 or 2, wherein the resin (B) has at least one phenolic hydroxyl group structure and is decomposed by the action of an acid to increase the solubility in an alkaline developer. Positive resist composition.
[18] (4) The resin (B) has the monocyclic or polycyclic hydrocarbon structure (monocyclic or polycyclic alicyclic hydrocarbon structure), and the resin (B) is decomposed by the action of acid to increase the solubility in the alkaline developer. A positive resist composition, characterized in that the resin.
[19] (5) The resin (B) has a structure in which a fluorine atom is substituted in the main chain and / or the side chain of the polymer backbone, and the resin (B) is decomposed by the action of an acid so that the solubility in an alkaline developer is increased. A positive resist composition, which is an increasing resin.
[20] (6) The positive resist composition according to any one of items 1 to 5, further comprising (E) fluorine and / or a silicone-based surfactant.
[21] (7) The positive resist composition according to any one of items 1 to 5, wherein (F) a mixed solvent comprising a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group is contained.
[22] Hereinafter, the compound used for this invention is demonstrated in detail.
[23] << (A) Compound which generate | occur | produces an acid by irradiation of actinic light or a radiation >>
[24] The composition of this invention contains the compound (photoacid generator) which generate | occur | produces an acid by irradiation of actinic light or a radiation as a component (A).
[25] Such photoacid generators include photoinitiators of photocationic polymerization, photoinitiators of photoradical polymerization, photochromic agents of dyes, photochromic agents, and known compounds which generate acids by irradiation with actinic rays or radiation, and two or more of them. Mixtures may be selected and used as appropriate.
[26] Other photoacid generators used in the present invention include, for example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenium salts and arsonium salts; Organic halogen compounds; Organometallic / organic halides; photoacid generators having o-nitrobenzyl type protecting groups; Compounds which generate sulfonic acid by photolysis represented by iminosulfonate; And disulfone compounds.
[27] Moreover, the polymer which introduce | transduced the group or compound which generate | occur | produces an acid by irradiation of actinic light or radiation to the main chain or side chain can be used. Examples of such polymers include U.S. Patent No. 3,849,137, German Patent No. 3,914,407, Japanese Patent Publication 26653/1988, Japanese Patent Publication 164824/1980, Japanese Patent Publication 69263/1987, Japanese Patent Publication 146038/1988, Japanese Patent Publication 163452 / The compound described in 1988, Unexamined-Japanese-Patent No. 153853/1987, and Unexamined-Japanese-Patent No. 146029/1988 can be used.
[28] In addition, compounds that generate an acid by light can also be used, as described in US Pat. No. 3,779,778 and EP 125,712.
[29] Among the compounds which generate an acid by irradiation with actinic light or radiation, the compounds particularly effectively used will be described below.
[30] (1) Iodonium salt represented by the following general formula (PAG1), or sulfonium salt represented by the following general formula (PAG2):
[31]
[32] Here, Ar ¹ and Ar ² independently represent a substituted or unsubstituted aryl group. Preferred substituents include alkyl, haloalkyl, cycloalkyl, aryl, alkoxy, nitro, carboxyl, alkoxycarbonyl, hydroxyl, mercapto and halogen atoms.
[33] R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ independently represent a substituted or unsubstituted alkyl group or an aryl group. Preferably, they are a C6-C14 aryl group, a C1-C8 alkyl group, and their substituted derivatives.
[34] Preferred substituents include an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group and a halogen atom for the aryl group, and an alkoxy group having 1 to 8 carbon atoms, a carboxyl group and an alkoxycarbonyl group for the alkyl group.
[35] Z ^- represents a pair anion such as _{^{BF 4 -, AsF 6 -,}} PF 6 -, SbF 6 -, SiF 6 2-, ClO 4 -, CF 3 SO 3 - , such as perfluoro alkane sulfonic acid anion, a pentafluoro- Condensed polynuclear aromatic sulfonic acid anions, anthraquinone sulfonic acid anions, sulfonic acid group-containing dyes and the like, such as robenzenesulfonic acid anion and naphthalene-1-sulfonic acid anion, may be exemplified, but is not limited thereto.
[36] In addition, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ , and Ar ¹ and Ar ² may be bonded via a single bond or a substituent, respectively.
[37] Although the specific example of these onium salts is illustrated below, the range of the photo-acid generator which can be used for this invention is not limited to these.
[38]
[39]
[40]
[41] The onium salts represented by the formulas (PAG1) and (PAG2) are known and can be synthesized using the methods described in US Pat. No. 2,807,648, US Pat. No. 4,247,473 and Japanese Patent Laid-Open No. 101331/1978.
[42] (2) a disulfone derivative represented by the following general formula (PAG3) or an iminosulfonate derivative represented by the following general formula (PAG4):
[43]
[44] Here, Ar ³ and Ar ⁴ independently represent a substituted or unsubstituted aryl group, R ²⁰⁶ represents a substituted or unsubstituted aryl group, and A represents a substituted or unsubstituted alkylene group, alkenylene group or arylene group. .
[45] Although the specific example of these derivatives is demonstrated below, the range of the photo-acid generator which can be used for this invention is not limited to these compounds.
[46]
[47] (3) Daazodisulfone derivatives represented by the following general formula (PAG5):
[48]
[49] Here, R represents a linear, branched or cyclic alkyl group, or a substituted or unsubstituted aryl group.
[50] Although the specific example of these derivatives is demonstrated below, the range of the photo-acid generator which can be used for this invention is not limited to these compounds.
[51]
[52] Moreover, in addition to the said compound, the compound represented by the following general formula (PAG6) can also be used effectively as an acid generator of component (A) of this invention.
[53]
[54] Wherein R ₁ to R ₅ each represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a halogen atom, an alkyloxycarbonyl group or an aryl group, and at least two of R ₁ to R ₅ bond with each other to form a ring structure Also good.
[55] R ₆ and R ₇ each represent a hydrogen atom, an alkyl group, a cyano group or an aryl group.
[56] Y ₁ and Y ₂ each represent an alkyl group, an aryl group, an aralkyl group, or an aromatic group containing a hetero atom, and Y ₁ and Y ₂ may be bonded to each other to form a ring.
[57] Y ₃ represents a single bond or a divalent linking group.
[58] X ⁻ is a non-nucleophilic anion.
[59] Provided that at least one of R ₁ to R ₅ and at least one of Y ₁ or Y ₂ are bonded to each other to form a ring, or at least one of R ₁ to R ₅ and at least one of R ₆ and R ₇ are bonded to each other Form a ring.
[60] In addition, at any one of R <_1> -R <_7> or Y <_1> or Y <_2> position, it couple | bonds through a coupling group and may have two or more structures of formula (PAG6).
[61] The alkyl group of R ₁ to R ₇ is a substituted or unsubstituted alkyl group, and preferably an alkyl group having 1 to 5 carbon atoms. As a specific example of an unsubstituted alkyl group, a methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, and t-butyl group are illustrated.
[62] The alkoxy group in the alkoxy group and alkyloxycarbonyl group of R <_1> -R <_5> is a substituted or unsubstituted alkoxy group, Preferably it is a C1-C5 alkoxy group. As an unsubstituted alkoxy group, a methoxy group, an ethoxy group, a propoxy group, butoxy group etc. can be illustrated.
[63] The aryl group of R ₁ to R ₇ , Y ₁ , Y ₂ is a substituted or unsubstituted aryl group, and preferably an aryl group having 6 to 14 carbon atoms. As an unsubstituted aryl group, a phenyl group, a tolyl group, a naphthyl group, etc. can be illustrated.
[64] As a halogen atom of R <_1> -R <_5> , they are a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
[65] The alkyl group of Y ₁ and Y ₂ is a substituted or unsubstituted alkyl group, and preferably an alkyl group having 1 to 30 carbon atoms. Examples of the unsubstituted alkyl group include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group, and cyclopropyl group, cyclopentyl group and cyclohexyl group. And cyclic alkyl groups such as adamantyl group, norbornyl group and bornyl group.
[66] The aralkyl group of Y ₁ and Y ₂ is a substituted or unsubstituted aralkyl group, and preferably an aralkyl group having 7 to 12 carbon atoms. As an unsubstituted aralkyl group, a benzyl group, a phenethyl group, a cumyl group etc. can be illustrated, for example.
[67] The aromatic group containing a hetero atom represents a C6-C14 aryl group etc. containing hetero atoms, such as a nitrogen atom, an oxygen atom, and a sulfur atom, in each aromatic ring.
[68] As an aromatic group containing the hetero atom of Y <_1> and Y <_2> , it is an aromatic group containing a substituted or unsubstituted hetero atom. As such an aromatic group, heterocyclic aromatic hydrocarbon groups, such as a furanyl group, a thiophenyl group, a pyrrolyl group, a pyridyl group, and an indolyl group, are illustrated, for example.
[69] Y ₁ and Y ₂ may be bonded to each other to form a ring together with S ⁺ in formula (PAG6).
[70] In this case, examples of the group formed by bonding of Y ₁ and Y ₂ include, for example, an alkylene group having 4 to 10 carbon atoms, preferably a butylene group, a pentylene group, a hexylene group, and particularly preferably a butylene group and a pentylene group. can do.
[71] Moreover, Y <_1> and Y <_2> couple | bond, and may contain the hetero atom in the ring formed with S <^+> in Formula (PAG6).
[72] Each of the alkyl group, alkoxy group, alkoxycarbonyl group, aryl group and aralkyl group is substituted with, for example, a nitro group, a halogen atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 5 carbon atoms), and the like. You may be. About an aryl group and an aralkyl group, you may further substitute by the alkyl group (preferably C1-C5).
[73] Moreover, as a substituent of an alkyl group, a halogen atom is preferable.
[74] Y ₃ represents a single bond or a divalent linking group. As a bivalent coupling group, the alkylene group and alkenylene group which may be substituted, -O-, -S-, -CO-, -CONR- (R is a hydrogen atom, an alkyl group, an acyl group), and these two The coupling group formed by combining the above is preferable.
[75] As a non-nucleophilic anion of X <^-> , a sulfonic acid anion, a carboxylic acid anion, etc. can be illustrated, for example.
[76] A non-nucleophilic anion is an anion which is remarkably low in the ability to generate a nucleophilic reaction, and is an anion which can prevent the degradation over time by the intramolecular nucleophilic reaction. This improves the time stability of the resist.
[77] Examples of the sulfonic acid anion include alkyl sulfonic acid anion, aryl sulfonic acid anion, camphor sulfonic acid anion and the like.
[78] As a carboxylic acid anion, an alkylcarboxylic acid anion, an arylcarboxylic acid anion, an aralkyl carboxylic acid anion, etc. are illustrated, for example.
[79] As the alkyl group in the alkyl sulfonic acid anion, preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neo Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group A real group, an ecosyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, etc. can be illustrated.
[80] As an aryl group in an aryl sulfonic acid anion, Preferably, a C6-C14 aryl group, for example, a phenyl group, a tolyl group, a naphthyl group, etc. can be illustrated.
[81] The alkyl group in the alkyl sulfonic acid anion and the aryl group in the aryl sulfonic acid anion may have a substituent.
[82] As a substituent, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group etc. can be illustrated, for example.
[83] As a halogen atom, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. can be illustrated, for example.
[84] As the alkyl group, for example, preferably an alkyl group having 1 to 15 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hex Real group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group Etc. can be illustrated.
[85] As an alkoxy group, Preferably, a C1-C5 alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, butoxy group etc. can be illustrated.
[86] As the alkylthio group, for example, preferably an alkylthio group having 1 to 15 carbon atoms, such as methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec -Butylthio group, pentylthio group, neopentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, undecylthio group, dodecylthio group, tridecylthio group, tetradecyl tea Ogi, pentadecylthio group, hexadecylthio group, heptadecylthio group, an octadecylthio group, a nonadecylthio group, an eicosylthio group etc. can be illustrated. In addition, the alkyl group, the alkoxy group and the alkylthio group may be further substituted with a halogen atom (preferably a fluorine atom).
[87] Examples of the alkyl group in the alkylcarboxylic acid anion include the same groups as the alkyl group in the alkyl sulfonic acid anion.
[88] As an aryl group in an arylcarboxylic acid anion, the same thing as the aryl group in an aryl sulfonic acid anion can be illustrated.
[89] As the aralkyl group in the aralkyl carboxylic acid anion, preferably aralkyl groups having 6 to 12 carbon atoms, for example, benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group and the like can be exemplified.
[90] The alkyl group, the aryl group, and the aralkyl group in the alkyl carboxylic acid anion, the aryl carboxylic acid anion and the aralkyl carboxylic acid anion may have a substituent, and examples of the substituent include the same halogen as in the aryl sulfonic acid anion. Atom, an alkyl group, an alkoxy group, an alkylthio group, etc. can be illustrated.
[91] As another non-nucleophilic anion, phosphorus fluoride, boron fluoride, antimony fluoride etc. can be illustrated, for example.
[92] In the formula (PAG6) of the present invention, at least one of R ₁ to R ₅ and at least one of Y ₁ or Y ₂ are bonded to each other to form a ring, or at least one of R ₁ to R ₅ and R ₇ or At least one of R ₈ is bonded to form a ring. By forming a ring, the compound represented by a formula (PAG6) fixes a three-dimensional structure, and improves photoresolution.
[93] In addition, at any one of R <_1> -R <_7> or Y <_1> or Y <_2> position, it couple | bonds through a coupling group and may have two or more structures of formula (PAG6).
[94] Moreover, it is preferable that the compound of formula (PAG6) is the following general formula (PAG6A) or (PAG6B).
[95]
[96] In formula (PAG6A), R <_1> -R <_4> , R <_7> , Y <_1> , Y <_2> and X <^-> are the same as those in formula (PAG6), respectively, and Y represents a single bond or a bivalent coupling group.
[97] In formula (PAG6B), R <_1> -R <_4> , R <_6> , R <_7> , Y <_1> and X <^-> are the same as those in formula (PAG6), respectively, and Y represents a single bond or a bivalent coupling group.
[98] Examples of the divalent linking group include an alkylene group which may be substituted, an alkenylene group, -O-, -S-, -CO-, and -CONR- (R is a hydrogen, an alkyl group or an acyl group), and two or more of these. A linking group formed by combining these is preferable.
[99] In the formula (PAG6A), as Y, an alkylene group, an alkylene group containing an oxygen atom, an alkylene group containing a sulfur atom is preferable, and specifically, a methylene group, an ethylene group, a propylene group, -CH ₂ -O-, -CH ₂ -S- is preferable, and most preferably, it is a linking group which forms a 6-membered ring like ethylene group, -CH ₂ -O-, and -CH ₂ -S-. By forming the 6-membered ring, the carbonyl plane and the CS ⁺ bond become closer vertically, and the orbital interaction improves the photolysis efficiency.
[100] The compound represented by formula (PAG6A) can be obtained by reacting a corresponding α-halocyclic ketone and a sulfide compound, or by converting the corresponding cyclic ketone into silylenol ether and then reacting the ether with sulfoxide. The compound shown by Formula (PAG6B) can be obtained by making (alpha)-or (beta) -halogenation halide react with arylalkyl sulfide.
[101] Although the specific example of a compound represented by said formula (PAG6) is shown below, this invention is not limited to these.
[102]
[103]
[104]
[105] In the specific examples of the photoacid generator represented by the general formula (PAG6), (PAG6A-1) to (PAG6A-30) and (PAG6B-1) to (PAG6B-12) are preferable.
[106] The compound of the said formula (PAG6) can be used individually by 1 type or in combination of 2 or more types.
[107] The content of the compound of component (A) in the positive resist composition of the present invention is preferably from 0.1 to 20% by weight, more preferably from 0.5 to 20% by weight, even more preferably 1 based on the total solids of the composition. It is -15 weight%.
[108] As a component (A) of this invention, the example of an especially preferable thing among the compounds which generate | occur | produce an acid by irradiation of actinic light or radiation is shown below.
[109]
[110]
[111] << (B) Resin (acid-decomposable resin) which is insoluble or poorly soluble in alkali and becomes alkali-soluble by the action of acid >>
[112] The acid-decomposable resin (B) of the present invention may be any resin as long as it is a resin that is insoluble or poorly soluble in alkali and becomes alkali-soluble due to the action of an acid. Examples of the functional group as an alkali-soluble site include a phenolic hydroxyl group and a carboxyl group. Is preferred.
[113] As acid-decomposable resin (B) of this invention, resin which has at least 1 phenolic hydroxyl group structure, decomposes by the action of an acid, and which the solubility in alkaline developing solution increases is preferable. Specifically, a resin having at least a p-hydroxystyrene unit is preferable. Furthermore, those in which a part of poly (p-hydroxystyrene) is protected with an acid-decomposable group, a copolymer of p-hydroxystyrene with t-butyl acrylate, and derivatives thereof are more preferable.
[114] For example, resins represented by (k-1) to (k-15) composed of repeating units as illustrated below can be applied to the present invention.
[115]
[116] The acid-decomposable resin (B) of the present invention is preferably a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure and increasing solubility in an alkaline developer by the action of an acid. It is especially preferable that it is resin which has a repeating unit containing the alicyclic hydrocarbon site | part represented by (pVI) as a partial structure, or resin containing at least 1 sort (s) chosen from the group of the repeating unit represented by general formula (II-AB). .
[117]
[118] In the formula, R ₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, and Z represents an atomic group forming an alicyclic hydrocarbon group together with a carbon atom. Display. R ₁₂ to R ₁₆ each independently represent a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R ₁₂ to R ₁₄ and any of R ₁₅ and R ₁₆ are represented. One represents an aliphatic hydrocarbon group. R ₁₇ to R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R ₁₇ to R ₂₁ represents an aliphatic hydrocarbon group, R ₁₉ or R ₂₁ is a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. R ₂₂ to R ₂₅ independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. However, R ₂₃ and R ₂₄ may combine with each other to form a ring.
[119]
[120] In formula (II-AB), R ₁₁ ′, R ₁₂ ′ independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent.
[121] Z 'contains two carbon atoms bonded to each other and represents an atomic group for forming an alicyclic structure which may have a substituent.
[122] Moreover, it is preferable that the said general formula (II-AB) is the following general formula (II-A) or general formula (II-B).
[123]
[124] Here, R ₁₃ 'to R ₁₆ ' are independently a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR _5- , a group decomposed by the action of an acid, -C (= O) -X-A '-R ₁₇ ' or an alkyl or cyclic hydrocarbon group which may have a substituent is indicated.
[125] Here, R <_5> represents the alkyl group, cyclic hydrocarbon group, or the following -Y group which may have a substituent.
[126] X represents an oxygen atom, a sulfur atom, -NH-, -NHSO _2- , or -NHSO ₂ NH-.
[127] A 'represents a single bond or a divalent linking group.
[128] In addition, at least two of R ₁₃ 'to R ₁₆ ' may combine to form a ring. n represents 0 or 1.
[129] R ₁₇ 'are, -COOH, represents -COOR _5, -CN, a hydroxyl group, which may have a substituent, an alkoxy group, a group _{-CO-NH-R 6, -CO} -NH-SO 2 -R 6 or a -Y .
[130] R <_6> represents the alkyl group or cyclic hydrocarbon group which may have a substituent.
[131] -Y group;
[132]
[133] Here, R ₂₁ 'to R ₃₀ ' each independently represent a hydrogen atom or an alkyl group which may have a substituent. a and b represent 1 or 2, respectively.
[134] In general formula (pI)-(pVI), as an alkyl group in R <_12> -R <_25> , the linear or branched alkyl group which has 1-4 carbon atoms which may be either substituted or unsubstituted is represented. As this alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group etc. are illustrated, for example.
[135] As the substituent of the alkyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxyl group, alkoxycarbonyl group, nitro And the like can be exemplified.
[136] As an alicyclic hydrocarbon group in R <_11> -R <_25> or the alicyclic hydrocarbon group which Z and a carbon atom form, monocyclic or polycyclic may be sufficient. Specifically, the group which has a C5 or more monocyclic, bicyclic, tricyclic, tetracyclic structure, etc. can be illustrated. 6-30 are preferable and, as for the carbon number, 7-25 are especially preferable. These alicyclic hydrocarbon groups may have a substituent.
[137] Below, the structural example of an alicyclic site | part is shown in an alicyclic hydrocarbon group.
[138]
[139]
[140] In the present invention, preferred examples of the alicyclic moiety include an adamantyl group, noadamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, and cyclohep A methyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group can be illustrated. More preferably, they are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.
[141] As a substituent of these alicyclic hydrocarbon groups, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxyl group, a carboxyl group, and an alkoxycarbonyl group are illustrated. As an alkyl group, lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, isopropyl group, and a butyl group, are preferable, More preferably, the substituent selected from the group which consists of a methyl group, an ethyl group, a propyl group, and an isopropyl group is represented. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group can be illustrated. As said alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be illustrated.
[142] The structure represented by general formula (pI)-(pVI) in the said resin (B) can be used for protection of alkali-soluble group. Examples of the alkali-soluble group include various groups known in the art.
[143] As a specific example of an alkali-soluble group, a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol group are mentioned, A carboxylic acid group and a sulfonic acid group are preferable.
[144] As an alkali-soluble group protected by the structure represented by general formula (pI)-(pVI) in the said resin, Preferably, the group represented by the following general formula (pVII)-(pXI) is illustrated.
[145]
[146] Wherein R ₁₁ to R ₂₅ and Z are the same as defined above.
[147] In the said resin, it is preferable that it is a repeating unit represented with the following general formula (pA) as a repeating unit which has the alkali-soluble group protected by the structure represented by general formula (pI)-(pVI).
[148]
[149] Here, when R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, the three R's may be the same or different.
[150] A is a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amido group, a sulfonamido group, a urethane group, or a combination of two or more groups selected from the group consisting of urea groups Display.
[151] Ra represents a group of any one of the general formulas (pI) to (pVI).
[152] Hereinafter, the specific example of the monomer of the repeating unit represented by general formula (pA) is shown.
[153]
[154]
[155] In General Formula (II-AB), R ₁₁ ′ and R ₁₂ ′ each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent.
[156] Z 'contains the two bonded carbon atoms (C-C) and represents an atomic group for forming an alicyclic structure which may have a substituent.
[157] As a halogen atom in said R <_11>', R <_12>', a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. can be illustrated.
[158] Wherein _{R 11 ', R 12',} R 21 the alkyl group in the '~R _30', C1-10 linear or branched alkyl group and more preferably 1 to 6 carbon atoms of straight or branched It is a gaseous-alkyl group, Especially preferably, they are a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group.
[159] As a substituent in the said alkyl group, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, etc. can be illustrated. As a halogen atom, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. can be illustrated, As an alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be illustrated, A formyl group, an acetyl group, etc. can be illustrated as an acyl group, An acetoxy group etc. can be illustrated as an acyloxy group.
[160] The atomic group for forming the Z 'alicyclic structure is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin (B). Among them, an atom group for forming a pedestrian alicyclic structure that forms a repeating unit of a pedestrian alicyclic hydrocarbon is preferable.
[161] As a skeleton of the alicyclic hydrocarbon formed, what is shown by the following structure, etc. are illustrated.
[162]
[163]
[164] As a skeleton of a preferable aliphatic alicyclic hydrocarbon, in the said structural example, (5), (6), (7), (9), (10), (13), (14), (15), (23) ), 28, 36, 37, 42, 47 are illustrated.
[165] The skeleton of the alicyclic hydrocarbon may have a substituent. As such a substituent, R <_13> -R <_16>'in the said general formula (II-A) and (II-B) can be illustrated.
[166] Among the repeating units having the above-mentioned alicyclic hydrocarbon, the repeating unit represented by the general formula (II-A) or (II-B) is more preferable.
[167] In the general formulas (II-A) and (II-B), R ₁₃ ′ to R ₁₆ ′ each independently represent a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR ₅ , an acid-decomposable group, -C (= O) -X-A'-R ₁₇ 'or an alkyl group which may have a substituent or a cyclic hydrocarbon group is represented.
[168] R <_5> represents the alkyl group, cyclic hydrocarbon group, or the following -Y group which may have a substituent.
[169] X represents an oxygen atom, a sulfur atom, -NH-, -NHSO _2- , or -NHSO ₂ NH-.
[170] A 'represents a single bond or a divalent linking group.
[171] In addition, at least two of R ₁₃ ′ to R ₁₆ ′ may combine with each other to form a ring. n represents 0 or 1.
[172] R ₁₇ 'are, -COOH, represents -COOR _5, -CN, a hydroxyl group, which may have a substituent, an alkoxy group, a group _{-CO-NH-R 6, -CO} -NH-SO 2 -R 6 or a -Y .
[173] R <_6> represents the alkyl group or cyclic hydrocarbon group which may have a substituent.
[174] In the -Y group, R ₂₁ 'to R ₃₀ ' each independently represent a hydrogen atom or an alkyl group which may have a substituent, and a and b each represent 1 or 2.
[175] In the alicyclic hydrocarbon-based acid-decomposable resin according to the present invention, the acid-decomposable group may be contained in the above-C (= O) -X-A'-R ₁₇ ', and is a substituent of Z' of the general formula (II-AB). It may contain as.
[176] As a structure of an acid-decomposable group, it represents with -C (= O) -X <_1> -R <_0> .
[177] In formula, R <_{0> is} tertiary alkyl groups, such as t-butyl group and t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, or 1-cyclohexyloxyethyl group, etc. Alkoxymethyl groups such as 1-alkoxyethyl group, 1-methoxymethyl group or 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3-oxocyclohexyl ester group, 2-methyl-2-adamantyl group, mevalonic lactone residue, etc. can be illustrated. X ₁ is the same as X.
[178] As a halogen atom in said R <_13> -R <_16>', a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. can be illustrated.
[179] As said alkyl group in said R <_5> , R <_6> , R <_13> -R <_16>', a C1-C10 linear or branched alkyl group is preferable, More preferably, it is a C1-C6 linear or branched alkyl group. More preferably, they are a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group.
[180] As said cyclic hydrocarbon group in said R <_5> , R <_6> , R <_13>'-R<_16>', it is a cycloalkyl group, a bridged hydrocarbon, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, adamantyl group, 2-methyl -2-adamantyl group, norbornyl group, bornyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group, norbornane epoxy group, methyl group, isomethyl group, neomentyl group, tetracyclododecanyl group can do.
[181] Examples of the ring formed by bonding at least two of R ₁₃ 'to R ₁₆ ' to each other include a C 5-12 ring such as cyclopentene, cyclohexene, cycloheptane and cyclooctane.
[182] As an alkoxy group in said R <_17>', C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be illustrated.
[183] As a substituent in the said alkyl group, cyclic hydrocarbon group, and alkoxy group, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, an alkyl group, a cyclic hydrocarbon group, etc. can be illustrated. As a halogen atom, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. can be illustrated. As an alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be illustrated, A formyl group, an acetyl group, etc. can be illustrated as an acyl group, As an acyloxy group, The timing can be illustrated.
[184] In addition, an alkyl group and a cyclic hydrocarbon group are illustrated by the above.
[185] As the divalent linking group for A ', an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amido group, a sulfonamido group, a urethane group, or a single or two or more selected from the group consisting of urea groups Combinations of groups are illustrated.
[186] As an alkylene group and substituted alkylene group in said A ', group represented by a following formula can be illustrated.
[187] [C (R _a ) (R _b )] _r-
[188] In formula, R _<a> , R <_b> represents a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, and both may be same or different. As an alkyl group, lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, isopropyl group, and a butyl group, are preferable, More preferably, they are selected from a methyl group, an ethyl group, a propyl group, and an isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group can be illustrated. As an alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be illustrated. As a halogen atom, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. can be illustrated. r represents the integer of 1-10.
[189] In the alicyclic hydrocarbon-based acid-decomposable resin according to the present invention, a group decomposed by the action of an acid includes a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the above general formulas (pI) to (pVI). It may be contained in at least one repeating unit of the repeating unit represented by general formula (II-AB), and the repeating unit of a later copolymerization component.
[190] Various substituents of R ₁₃ ′ to R ₁₆ ′ in General Formula (II-A) or General Formula (II-B) are atomic groups for forming an alicyclic structure in General Formula (II-AB). Or both substituents of the atomic group Z to form a bridged alicyclic structure.
[191] Although the following [II-1]-[II-103] are illustrated as a specific example of the repeating unit represented by the said general formula (II-A) or general formula (II-B), this invention is limited to these specific examples. It doesn't happen.
[192]
[193]
[194]
[195]
[196]
[197]
[198] The acid-decomposable resin of the present invention may further contain a repeating unit having a lactone structure represented by the following general formula (IV).
[199]
[200] Here, R _1a represents a hydrogen atom or a methyl group.
[201] W ₁ represents a bond or a single bond (short group) of two or more groups selected from the group consisting of a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group and an ester group
[202] Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ and Re ₁ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n are each independently an integer of 0 to 3, and m + n is 2 to 6;
[203] Examples of the alkyl group having 1 to 4 carbon atoms represented by Ra _{1 to} Re ₁ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.
[204] In the general formula (IV), examples of the alkylene group represented by W ₁ include groups represented by the following formulas:
[205] -[C (Rf) (Rg)] r _1-
[206] Here, Rf and Rg may be the same or different, and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group or an alkoxyl group. As an alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group, or a butyl group is preferable, and the thing chosen from a methyl group, an ethyl group, a propyl group, and an isopropyl group is more preferable. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxyl group are mentioned. As an alkoxyl group, the alkoxyl group which has 1-4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, is mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom. r ₁ is an integer of 1-10.
[207] Moreover, as a substituent of the said alkyl group, a carboxyl group, acyloxy group, cyano group, alkyl group, substituted alkyl group, halogen atom, hydroxyl group, alkoxyl group, substituted alkoxy group, acetylamido group, alkoxycarbonyl group, and acyl group are mentioned.
[208] Examples of the alkyl group used herein include lower alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, cyclopropyl group, cyclobutyl group or cyclopentyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxyl group are mentioned. An alkoxy group is mentioned as a substituent of a substituted alkoxy group. As an alkoxy group, the alkoxy group which has 1-4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, is mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom.
[209] Although the specific example of the repeating structural unit represented by general formula (IV) is shown below, it is not limited to this:
[210]
[211]
[212] As a specific example of said general formula (IV), (IV-17)-(IV-36) are preferable at the point which an exposure margin becomes more favorable.
[213] Moreover, as a structure of General formula (IV), it is preferable to have an acrylate structure from the point that edge roughness becomes favorable.
[214] Moreover, you may contain the repeating unit which has group represented by either of the following general formula (V-1)-(V-4).
[215]
[216] In General Formulas (V-1) to (V-4), each of R _1b to R _5b independently represents a hydrogen atom or an alkyl group, cycloalkyl group or alkenyl group which may have a substituent. Two of R _1b to R _5b may be bonded to each other to form a ring.
[217] In General Formulas (V-1) to (V-4), examples of the alkyl group represented by R _1b to R _5b include a linear or branched alkyl group, and may have a substituent.
[218] As a linear or branched alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group or de Practical group is preferable.
[219] As a cycloalkyl group represented by R <_1b> -R <_5b> , the alkenyl group which has 3-8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or a cyclooctyl group, is preferable.
[220] As the alkenyl group represented by R _1b to R _5b , an alkenyl group having 2 to 6 carbon atoms such as vinyl group, propenyl group, butenyl group or hexenyl group is preferable.
[221] Moreover, as a ring formed by combining two of R <_1b> -R <_5b> , 3-8 membered rings, such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring, are mentioned.
[222] In formulas (V-1) to (V-4), R _1b to R _5b may be bonded to any of the carbon atoms constituting the cyclic skeleton, respectively.
[223] Preferred examples of the substituent which may be contained in the alkyl group, cycloalkyl group and alkenyl group include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine, chlorine, bromine or iodine), an acyl group having 2 to 5 carbon atoms, The acyloxy group, cyano group, hydroxyl group, carboxyl group, the alkoxycarbonyl group and the nitro group which have 2-5 carbon atoms are mentioned.
[224] General formula (V-1) ~ Examples of the repeating unit having a group represented by (V-4), the general formula (II-A) or (II-B) R ₁₃ in the general dog at least one of '~R _16' Having groups represented by formulas (V-1) to (V-4) (for example, R ₅ of -COOR ₅ represents a group represented by general formulas (V-1) to (V-4)), or the following general The repeating unit etc. which are represented by Formula (AI) can be illustrated.
[225] In general formula (AI), R _b0 represents a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Preferred examples of the substituent which may be contained in the alkyl group represented by R _b0 include those exemplified above as preferred substituents which may be retained by the alkyl group represented by R _1b in the general formulas (V-1) to (V-4). Can be.
[226]
[227] Here, examples of the halogen atom represented by R _b0 include fluorine, chlorine, bromine and iodine. R _b0 is preferably a hydrogen atom.
[228] A 'represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group or a bivalent group which bonded them.
[229] B ₂ represents a group represented by any one of General Formulas (V-1) to (V-4).
[230] In A ', the thing of the following formula is illustrated as this combined bivalent group, for example.
[231]
[232] In the above formula, R _ab and R _bb may be the same or different and each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group or an alkoxyl group.
[233] As an alkyl group, lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, isopropyl group, or a butyl group, are preferable, More preferably, they are selected from a methyl group, an ethyl group, a propyl group, and an isopropyl group. As a substituent of a substituted alkyl group, an alkoxyl group which has a hydroxyl group, a halogen atom, and 1-4 carbon atoms is mentioned.
[234] As an alkoxy group, the alkoxyl group which has 1-4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, is mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom. r1 represents the integer of 1-10, Preferably it is an integer of 1-4. m represents the integer of 1-3, Preferably it is 1 or 2.
[235] Although the specific example of the repeating unit represented by general formula (AI) is listed below, the content of this invention is not limited to these.
[236]
[237]
[238] In addition, the acid-decomposable resin of the present invention may further contain a repeating unit represented by the following general formula (VI).
[239]
[240] Here, A ₆ represents a single bond or a combination of two or more groups selected from the group consisting of a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group and an ester group. R _6a represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, or a halogen atom.
[241] In general formula (VI), group represented by a following formula can be illustrated as an alkylene group of A <_6> .
[242] -[C (Rnf) (Rng)] r-
[243] Here, Rnf and Rng may be same or different, and each mentions a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxyl group. As an alkyl group, lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, are preferable, More preferably, they are selected from a methyl group, an ethyl group, a propyl group, or an isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group are mentioned. As an alkoxy group, the alkoxy group which has 1-4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, is mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom. r is an integer of 1-10.
[244] In the general formula (VI), examples of the cycloalkylene group represented by A ₆ include a cycloalkylene group having 3 to 10 carbon atoms such as a cyclopentylene group, a cyclohexylene group or a cyclooctylene group.
[245] The bridged alicyclic ring containing Z ₆ may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), an alkoxycarbonyl group (preferably having 1 to 5 carbon atoms), an acyl group (for example, a formyl group or a benzoyl group), Acyloxy group (e.g., propylcarbonyloxy group or benzoyloxy group), alkyl group (preferably having 1 to 4 carbon atoms), carboxyl group, hydroxyl group and alkylsulfonylcarbamoyl group (-CONHSO ₂ CH ₃ etc.) Can be mentioned. As the substituent, the alkyl group may be further substituted with a hydroxyl group, a halogen atom or an alkoxy group (preferably having 1 to 4 carbon atoms).
[246] In general formula (VI), the hydrogen atom of the ester group couple | bonded with A <_6> may couple | bond with the carbon atom which comprises the Z ₆ containing bridged alicyclic ring structure.
[247] Although the specific example of the repeating unit represented by general formula (VI) is listed below, it is not limited to these.
[248]
[249] In addition, this acid-decomposable resin may contain the repeating unit which has group represented by following General formula (VII).
[250]
[251] Herein, R _2c to R _4c independently represent a hydrogen atom or a hydroxyl group, provided that at least one of R _2c to R _4c represents a hydroxyl group.
[252] The group represented by the general formula (VII) is preferably a dihydroxy body or a monohydroxy body, more preferably a dihydroxy body.
[253] As a repeating unit which has group represented by general formula (VII), group in which at least 1 of R <_13>'-R<_16>' in said general formula (II-A) or (II-B) is represented by said general formula (VII) What has, for example, R <_5> of -COOR <_5> represents group represented by general formula (VII), the repeating unit represented by the following general formula (AII), etc. can be illustrated.
[254]
[255] Here, R _1c represents a hydrogen atom or a methyl group.
[256] R _2c to R _4c independently represent a hydrogen atom or a hydroxyl group, provided that at least one of R _2c to R _4c represents a hydroxyl group.
[257] Although the specific example of the repeating unit which has a structure represented by general formula (AII) is listed below, it is not limited to these.
[258]
[259] Moreover, you may contain the repeating unit which has group represented by the following general formula (VIII).
[260]
[261] Here, Z ₂ represents -O- or -N (R ₄₁ )-. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or -OSO ₂ -R ₄₂ . R ₄₂ represents an alkyl group, haloalkyl group, cycloalkyl group, or camphor residue.
[262] As said alkyl group in said R <_41> and R <_42> , a C1-C10 linear or branched alkyl group is preferable, More preferably, it is a C1-C6 linear or branched alkyl group, More preferably, a methyl group, Ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.
[263] Examples of the haloalkyl group for R ₄₁ and R ₄₂ include trifluoromethyl group, nonafluorobutyl group, pentadecafluorooctyl group, trichloromethyl group and the like. As a cycloalkyl group in said R <_42> , a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, etc. can be illustrated.
[264] The alkyl group as R ₄₁ and R ₄₂ , the cycloalkyl group as R ₄₂ or camphor residues may have a substituent. As such a substituent, a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom), an alkoxy group (preferably C1-C4, for example, a methoxy group, an ethoxy group, Propoxy group, butoxy group, etc.), acyl group (preferably having 2 to 5 carbon atoms, such as formyl group, acetyl group, etc.), acyloxy group (preferably having 2 to 5 carbon atoms, such as acetoxy group), aryl Group (preferably C6-C14, a phenyl group) etc. can be illustrated.
[265] Although the following [I'-1]-[I'-7] are illustrated as a specific example of the repeating unit represented by said general formula (VIII), this invention is not limited to these specific examples.
[266]
[267] The acid-decomposable resins of component (B), in addition to the repeating structural unit, may be modified in various ways to control dry etching resistance, standard developer aptitude, substrate adhesion, resist profile, and resolution, heat resistance and sensitivity, which are generally required properties of resist. It may contain repeating structural units.
[268] As such a repeating structural unit, although the repeating structural unit corresponded to the following monomer can be illustrated, it is not limited to this.
[269] Thereby, the performance required for the alicyclic hydrocarbon-based acid-decomposable resin, in particular,
[270] (1) solubility in coating solvents,
[271] (2) film forming property (glass transition point),
[272] (3) alkali developability,
[273] (4) film loss (selection of hydrophilic, alkali-soluble groups),
[274] (5) adhesion to the substrate of the non-exposed part,
[275] (6) dry etching resistance,
[276] Fine adjustment of the back and the like becomes possible.
[277] Examples of such monomers include compounds having one addition-polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. can do.
[278] Specific examples thereof include the following monomers:
[279] Acrylic esters (preferably alkyl acrylates having 1 to 10 carbon atoms in the alkyl group):
[280] Methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2 , 2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate and tetrahydrofur Furyl acrylate and the like.
[281] Methacrylic acid esters (preferably alkyl methacrylates having 1 to 10 carbon atoms in the alkyl group):
[282] Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate Acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monometha Methacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like.
[283] Acrylamides:
[284] Acrylamide, N-alkylacrylamides (alkyl groups each having 1 to 10 carbon atoms, for example, methyl group, ethyl group, t-butyl group, ethylhexyl, octyl group, cyclohexyl group and hydroxyethyl group), N, N -Dialkylacrylamides (alkyl groups each having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group and cyclohexyl group), N-hydroxyethyl-N-methylacrylic Amides and N-2-acetamidoethyl-N-acetylacrylamide and the like.
[285] Methacrylamides:
[286] Methacrylamide, N-alkyl methacrylamides (alkyl groups each having 1 to 10 carbon atoms, such as methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group and cyclohexyl group), N, N -Dialkyl methacrylamides (the alkyl group includes an ethyl group, a propyl group and a butyl group), N-hydroxyethyl-N-methylacrylamide and the like.
[287] Allyl Compounds:
[288] Allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyllaurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate and allyl lactate), allyloxyethanol, and the like.
[289] Vinyl ethers:
[290] Alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethyl) Propyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, and tetrahydrofurfuryl Vinyl ethers, etc.).
[291] Vinyl esters:
[292] Vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl aceto acetate, vinyl lactate, Vinyl-β-phenylbutyrate and vinylcyclohexylcarboxylate and the like.
[293] Itaconic acid dialkyls:
[294] Dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and the like.
[295] Dialkyl fumalates or monoalkyl fumalates; Dibutyl fumarate and the like.
[296] Crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilonitrile and the like.
[297] In addition, as long as it is an addition-polymerizable unsaturated compound copolymerizable with the monomer corresponded to the said various repeating units, it may be copolymerized.
[298] In acid-decomposable resins, the molar ratio of each repeating unit is set appropriately to adjust the dry etching resistance of the resist, the standard developer aptitude, the substrate adhesion, the resist profile, or the generally necessary linear resolution, heat resistance, sensitivity, and the like of the resist. .
[299] As a preferable aspect of the alicyclic hydrocarbon type acid-decomposable resin of this invention, the following are illustrated.
[300] (1) containing repeating units having substructures containing alicyclic hydrocarbons represented by the general formulas (pI) to (pVI) (side chain type)
[301] (2) containing repeating units represented by the general formula (II-AB) (backbone type)
[302] However, in (2), the following are further illustrated, for example.
[303] (3) Having repeating unit represented by general formula (II-AB), maleic anhydride derivative and (meth) acrylate structure (hybrid type)
[304] As for content of the repeating unit which has a partial structure containing the alicyclic hydrocarbon represented by general formula (pI)-(pVI), in acid-decomposable resin, 30-70 mol% is preferable in all the repeating structural units, More preferably, Is 35 to 65 mol%, more preferably 40 to 60 mol%.
[305] In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit represented by General Formula (II-AB) is preferably 10 to 60 mol%, more preferably 15 to 55 mol%, further more preferably in all the repeating structural units. Preferably it is 20-50 mol%.
[306] In addition, although content in resin of the repeating structural unit based on the monomer of the said other copolymerization component can also be set suitably according to the performance of a desired resist, In general, the alicyclic hydrocarbon represented by said general formula (pI)-(pVI) is mentioned. 99 mol% or less is preferable with respect to the total total number of moles of the repeating structural unit which has a partial structure containing and the repeating unit represented with the said general formula (II-AB), More preferably, it is 90 mol% or less, More preferably It is less than 80 mol%.
[307] When the composition of this invention is for ArF exposure, it is preferable that resin does not have an aromatic group from the point of transparency to ArF light.
[308] In the case where the positive photosensitive composition of the present invention is irradiated with F ₂ excimer laser light, the resin of component (B) has a structure in which a fluorine atom is substituted in the main chain and / or the side chain of the polymer skeleton, and also in the action of acid. Resin (decomposed also as a fluorine group-containing resin) which is decomposed by decomposition to increase the solubility in an alkali developer is preferable, and at least a portion selected from a perfluoroalkylene group and a perfluoroarylene group is added to the main chain of the polymer skeleton. One or a site selected from the group protecting the OH group of the perfluoroalkyl group, the perfluoroaryl group, the hexafluoro-2-propanol group, and the hexafluoro-2-propanol group, The fluorine-containing resin which has at least one in a side chain is more preferable.
[309] Specifically, it is resin which has at least one repeating unit represented by the following general formula (I)-(X).
[310]
[311] In said general formula, R <_0> , R <_1> represents a hydrogen atom, a fluorine atom, and an alkyl group, a perfluoroalkyl group, a cycloalkyl group, or an aryl group which may respectively have a substituent.
[312] R <_2> -R <_4> represents the alkyl group, the perfluoroalkyl group, the cycloalkyl group, or the aryl group which may have a substituent. In addition, R ₀ and R ₁ , R ₀ and R ₂ , R ₃ and R ₄ may be bonded to form a ring.
[313] R ₅ represents a hydrogen atom, an alkyl group, a perfluoroalkyl group, a monocyclic or polycyclic cycloalkyl group, an acyl group, or an alkoxycarbonyl group which may have a substituent.
[314] R <_6> , R <_7> , R <_8> may be same or different, and represents the alkyl group, perfluoroalkyl group, and alkoxy group which may have a hydrogen atom, a halogen atom, and a substituent.
[315] R <_9> , R <_10> may be same or different and represents the alkyl group or haloalkyl group which may have a hydrogen atom, a halogen atom, a cyano group, and a substituent.
[316] R ₁₁ and R ₁₂ may be the same or different and represent a hydrogen atom, a hydroxyl group, a halogen atom, a halogen atom, a cyano group, an alkoxy group, an acyl group or an alkyl group, cycloalkyl group, alkenyl group, aralkyl group or aryl group which may have a substituent. do.
[317] R <_13> , R <_14> may be same or different and represents the alkyl group or haloalkyl group which may have a hydrogen atom, a halogen atom, a cyano group, and a substituent.
[318] R ₁₅ represents an alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group having a fluorine atom.
[319] R _16, R _17, R ₁₈ may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, an optionally substituted displays good, an alkyl group, a perfluoroalkyl group, an alkoxy group, -CO-OR _15.
[320] R ₁₉ , R ₂₀ and R ₂₁ may be the same or different and represent an alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group or an alkoxy group having a hydrogen atom, a fluorine atom or a fluorine atom. Provided that at least one of R ₁₉ , R ₂₀ , and R ₂₁ is a group other than a hydrogen atom.
[321] A ₁ and A ₂ are a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group which may have a single bond or a substituent, or -O-CO-R _22- , -CO-OR ₂₃ -,- CO-N (R ₂₄ ) -R ₂₅ -is indicated.
[322] R ₂₂ , R ₂₃ , R ₂₅ may be the same or different and may be a single bond or an ether group, ester group, amide group, urethane group or ureide group, a divalent alkylene group, alkenylene group or cycloalkylene group Or an arylene group.
[323] R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a substituent.
[324] n represents 0 or 1, and x, y, z represent the integer of 0-4.
[325] In the present invention, the resin (B) is preferably a fluorine-containing resin having an acid-decomposable group having at least one repeating unit represented by the following general formulas (XI) to (XIII).
[326]
[327] In formula, R <_26> , R <_27> , R <_32> may be same or different, and represents the alkyl group or haloalkyl group which may have a hydrogen atom, a halogen atom, a cyano group, and a substituent.
[328] R ₂₈ and R ₃₃ represent a group of -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), or of the following general formula (XIV).
[329]
[330] Wherein, R _29, R _30, R ₃₁ may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, a substituent, shown by an alkyl group, perfluoroalkyl group, an alkoxy group, -CO-OR ₂₈ in.
[331] R ₃₄ and R ₃₅ may be the same or different and represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group which may be the same or different and may have a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group or a substituent. .
[332] R <_36> , R <_37> , R <_38> and R <_39> may be same or different and represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group which may have a substituent. Two of R ₃₆ , R ₃₇ , and R ₃₈ , or two of R ₃₆ , R ₃₇ , and R ₃₉ may combine to form a ring. In addition, the formed ring may contain an oxo group.
[333] R ₄₀ represents an alkyl group cycloalkyl group, alkenyl group, alkynyl group, aralkyl group or aryl group which may have a substituent.
[334] A ₃ and A ₄ are a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group which may have a single bond or a substituent, or -O-CO-R _22- , -CO-OR ₂₃ -,- CO-N (R ₂₄ ) -R ₂₅ -is indicated.
[335] R ₂₂ to R ₂₅ are the same as described above. Z represents the atomic group which comprises a monocyclic or polycyclic alicyclic group with a carbon atom. n represents 0 or 1.
[336] In the present invention, in order to control physical properties such as hydrophilicity, glass transition point, and transmittance to an exposure light source of the fluorine group-containing resin, or to control the polymerizability during polymer synthesis, the following general formulas (XV) to You may have at least one repeating unit derived from the vinyl compound containing maleic anhydride, a vinyl ether, or a cyano group represented by (XVII).
[337]
[338] Here, R ₄₁ represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a substituent.
[339] R ₄₂ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or haloalkyl group which may have a substituent.
[340] A ₅ is a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group which may have a single bond, a substituent, or -O-CO-R _22- , -CO-OR _23- , -CO-N ( R ₂₄ ) -R ₂₅ -is displayed.
[341] R ₂₂ to R ₂₅ are the same as described above.
[342] Moreover, as a more preferable fluorine-group containing resin in this invention, resin which has at least one repeating unit represented by the following general formula (IA) and (IIA), respectively, and the repeat represented by the following general formula (IIA) and (VIA) Resin which has at least one unit each can be illustrated.
[343] These, resin which has at least one repeating unit represented by the following general formula (IA) and (IIA), respectively, and resin which has at least one each of the repeating unit represented by the following general formula (IIA) and (VIA) is further said general formula You may have a repeating unit represented by (I)-(V).
[344]
[345] In General Formulas (IA) and (IIA), R _1a and R _6a may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, or an alkylene group which may have a substituent.
[346] R _2a , R _3a , R _6a and R _7a may be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group or a substituent, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, An alkenyl group, an aryl group, or an aralkyl group is represented.
[347] R _50a to R _55a may be the same or different and represent an alkyl group which may have a hydrogen atom, a fluorine atom or a substituent. However, at least one of R _50a to R _55a represents an alkyl group in which a fluorine atom or at least one hydrogen atom is substituted with a fluorine atom.
[348] R _56a represents an alkyl group, a cycloalkyl group, an acyl group or an alkoxycarbonyl group which may have a hydrogen atom or a substituent, and is preferably a hydrogen atom.
[349] R _4a represents a group of the following general formula (IVA) or (VA).
[350]
[351] In general formula (IVA), R <_11a> , R <_12a> and R <_13a> may represent the same or different, and may represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group which may have a substituent.
[352] In general formula (VA), R <_14a> and R <_15a> may be same or different, and represent the alkyl group which may have a hydrogen atom or a substituent. R _16a represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a substituent. Two of R _14a to R _16a may be bonded to each other to form a ring.
[353]
[354] In General Formula (VIA), R _17a1 and R _17a2 may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R _18a represents -C (R _18a1 ) (R _18a2 ) (R _18a3 ) or -C (R _18a1 ) (R _18a2 ) (OR _18a4 ). R _18a1 to R _18a4 may be the same or different and represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group which may have a hydrogen atom or a substituent. R _18a1, R _18a2, R and the two are combined of two or R _18a1, R _18a2, R _18a4 from _18a3 may form a ring. Although A <_0> represents the bivalent coupling group which may have a single bond or a substituent, It is preferable that it is a single bond.
[355] It is preferable that these fluorine-group containing resin is group in which R <_18a> in general formula (VIA) is represented with the following general formula (VIA-A) or general formula (VIA-B). Moreover, it is preferable that at least one of R <_1a> in General formula (IA), R <_5a> in General formula (IIA), and _R17a2 in General formula (VIA) of these fluorine-group containing resin (A) is a trifluoromethyl group. Do.
[356]
[357] In General Formula (VIA-A), R _18a5 and R _18a6 may be the same or different and represent an alkyl group which may have a substituent. R _18a7 represents a cycloalkyl group which may have a substituent.
[358] In General Formula (VIA-B), R _18a8 represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group which may have a substituent.
[359] Moreover, resin which has at least one repeating unit represented by the said General formula (IA) and (IIA), respectively, and resin which has at least one each of the repeating unit represented by the said General formula (IIA) and (VIA) is further a following general formula You may have at least one repeating unit represented by (IIIA) or (VIIA).
[360]
[361] In general formula (IIIA), R <_8a> represents a hydrogen atom, a halogen atom, a cyano group, or the alkyl group which may have a substituent. R _9a and R _10a may be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group or a substituent, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, an alkenyl group, an aryl group or an aralkyl Display the flag.
[362] In General Formula (VIIA), R _19a and R _20a may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R _21a is, may have a hydrogen atom, a halogen atom, the substituent represents an alkyl group or -A ₁ -CN. A ₁ represents a single bond or a divalent linking group.
[363] As said alkyl group, for example, a methyl group, an ethyl group, a propyl group, n-butyl group, a sec-butyl group, a hexyl group, 2-ethylhexyl group, an octyl group can be illustrated preferably, for example as a C1-C8 alkyl group. have.
[364] As a cycloalkyl group, monocyclic may be sufficient and polycyclic may be sufficient. As monocyclic type, it is C3-C8 thing, For example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group can be illustrated preferably. As polycyclic type, it is C6-C20, For example, adamantyl group, norbornyl group, isoboroyl group, canpanyl group, dicyclopentyl group, a-pinel group, tricyclo decanyl group, tricyclo dodecyl group, androstanyl group Etc. can be illustrated preferably. However, the carbon atom in the said monocyclic or polycyclic cycloalkyl group may be substituted by heteroatoms, such as an oxygen atom.
[365] As the perfluoroalkyl group, for example, one having 4 to 12 carbon atoms, specifically, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorooctylethyl group, a perfluorododecyl group, or the like is preferable. It can be illustrated.
[366] As a haloalkyl group, a chloromethyl group, a chloroethyl group, a chloropropyl group, a chlorobutyl group, a bromomethyl group, a bromoethyl group etc. can be illustrated specifically, for example as a haloalkyl group of 1-4 carbon atoms.
[367] As an aryl group, it is a C6-C15 aryl group, specifically, a phenyl group, a tolyl group, a dimethylphenyl group, 2, 4, 6-trimethylphenyl group, a naphthyl group, anthryl group, 9, 10- dimethoxy anthryl Group etc. can be illustrated preferably.
[368] As the aralkyl group, for example, a benzyl group, a phenethyl group, a naphthyl methyl group, or the like can be preferably exemplified as an aralkyl group having 7 to 12 carbon atoms.
[369] As an alkenyl group, a vinyl group, an allyl group, butenyl group, and a cyclohexenyl group can be illustrated specifically, for example as a C2-C8 alkenyl group.
[370] As the alkoxy group, for example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a butoxy group, a pentoxy group, an allyloxy group, an octoxy group, etc. It can be illustrated preferably.
[371] As an acyl group, for example, a formyl group, an acetyl group, propanoyl group, butanoyl group, pivaloyl group, octanoyl group, benzoyl group, etc. can be mentioned specifically, as an acyl group of 1-10 carbon atoms.
[372] As an acyloxy group, a C2-C12 acyloxy group is preferable, For example, an acetoxy group, a propionyloxy group, a benzoyloxy group, etc. can be illustrated.
[373] As an alkynyl group, a C2-C5 alkynyl group is preferable, for example, an ethyl group, a propyl group, a butyl group, etc. can be illustrated.
[374] As the alkoxycarbonyl group, i-propoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, 1-methyl-1-cyclohexyloxycarbonyl group and the like are preferably secondary alkoxycarbonyl groups, more preferably tertiary An alkoxycarbonyl group is illustrated.
[375] As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be illustrated, for example.
[376] As an alkylene group, C1-C8 things, such as the methylene group, ethylene group, propylene group, butylene group, hexylene group, and octylene group which may preferably have a substituent are illustrated.
[377] As an alkylene group, C2-C6 things, such as the ethenylene group, the propenylene group, butenylene group which may preferably have a substituent are illustrated.
[378] As a cycloalkylene group, C5-C8 things, such as the cyclopentylene group and cyclohexylene group, which may preferably have a substituent are illustrated.
[379] As an arylene group, C6-C15 things, such as the phenylene group, tolylene group, and naphthylene group, which may preferably have a substituent are illustrated.
[380] The divalent linking group may be a divalent, alkylene group, cycloalkylene group, alkenylene group or arylene group which may have a substituent or -O-CO-R _22a- , -CO-OR _23a -or -CO-N (R _24a ) -R _25a -is displayed. R _22a , R _23a and R _25a may be the same or different and may have a single bond or an ether group, an ester group, an amide group, a urethane group or a ureide group, a divalent alkylene group, an alkenylene group or a cycloalkylene group Or an arylene group. R _24a represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a hydrogen atom or a substituent.
[381] Examples of the ring formed by bonding of R ₀ and R ₁ , R ₀ and R ₂ , R ₃ and R ₄ are, for example, a 5- to 7-membered ring, specifically, a pentane ring, a hexane ring, a furan ring, and a dioxo substituted with fluorine; A norl ring, a 1, 3- dioxolane ring, etc. are illustrated.
[382] R 2 ~R ₃₆ of _38, or R ₃₆ and R ₃₉ ~R ₃₇ as the two are bonded to form a ring of, for example, a 3 to 8-membered ring, specifically a cyclopropane ring, a cyclopentyl bullet, cyclohexane ring, A furan ring, a pyran ring, etc. can be illustrated preferably.
[383] Two of R _14a ~R _16a dog, R _18a1 as ring ~R formed by combining two or two of R _18a1, R _18a2, R _18a4 from _18a3, and 3 to 8-membered ring is preferred, for example, cyclopropane ring, a cycloalkyl Pentane ring, a cyclohexane ring, a tetramethylene oxide ring, a pentamethylene oxide ring, a hexamethylene oxide ring, a furan ring, a pyran ring, a dioxonol ring, a 1, 3- dioxolane ring, etc. can be illustrated.
[384] Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group, and the alicyclic group formed is monocyclic, having 3 to 8 carbon atoms, for example, cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclo Octyl group can be illustrated preferably. As polycyclic type, it is C6-C20, For example, adamantyl group, norbornyl group, isobornyl group, canpanyl group, dicyclopentyl group, a-pinel group, tricyclo decanyl group, tetracyclo dodecyl group, androstanyl group Etc. can be illustrated preferably.
[385] Substituents substituted with these groups include those having active hydrogens such as alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureide groups, urethane groups, hydroxyl groups and carboxyl groups, and halogen atoms (fluorine atoms, chlorine atoms, bromine atoms). , Iodine atom), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), acyloxy group (acetoxy group, Propanoyloxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group etc.), a cyano group, a nitro group, etc. are illustrated.
[386] Here, although the alkyl group, the cycloalkyl group, and the aryl group are illustrated above, the alkyl group may be further substituted with a fluorine atom and a cycloalkyl group.
[387] Examples of the group exhibiting alkali group solubility by decomposition of the acid contained in the fluorine group-containing resin of the present invention include -OC (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) and -OC (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -O-COO-C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -OC (R ₀₁ ) (R ₀₂ ) COO-C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -COO-C (R ₃₆ ) (R ₃₇ ), (R ₃₈ ), -COO-C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and the like.
[388] R <_36> -R <_39> is as above-mentioned, R <_01> , R <_02> represents the hydrogen atom, the alkyl group, cycloalkyl group, alkenyl group, aralkyl group, or aryl group which may have the substituent shown above.
[389] As a specific example of such an acid-decomposable group, t-butyl group, t-amyl group, 1-alkyl-1-cyclohexyl group, 2-alkyl group-2-adamantyl group, 2-adamantyl-2-propyl group, Acetal groups or acetal ester groups such as ether groups or ester groups of tertiary alkyl groups such as 2- (4-methylcyclohexyl) -2-propyl group, 1-alkoxy-1-ethoxy group and tetrahydropyranyl group, t- Alkyl carbonate group, t-alkylcarbonylmethoxy group, etc. are illustrated.
[390] The sum total of the content of the repeating unit represented by General Formula (I)-(X) is generally 10-80 mol%, Preferably it is 30-70 mol%, More preferably, 35-65 mol% in the whole polymer composition. It is used in the range of.
[391] The content of the repeating units represented by the general formulas (XI) to (XIII) is generally from 0 to 70 mol%, preferably from 10 to 60 mol%, more preferably from 20 to 50 mol% in the overall polymer composition. Used in a range
[392] The content of the repeating units represented by the formulas (XV) to (XVII) is generally 0 to 70 mol%, preferably 10 to 60 mol%, more preferably 20 to 50 mol% in the overall polymer composition. Used in a range
[393] As resin (B) of this invention, it is more preferable to have at least one repeating unit represented by general formula (I)-(III), and at least one repeating unit represented by general formula (IV)-(VI).
[394] Moreover, as resin (B) of this invention, what has at least one repeating unit represented by general formula (IV)-(VI), and at least one repeating unit represented by general formula (VIII)-(X) is mentioned above. Likewise more preferred.
[395] Moreover, as resin (B) of this invention, having at least one repeating unit represented by general formula (IV)-(VII), and at least one repeating unit represented by general formula (XV)-(XVII) is mentioned above. Likewise more preferred.
[396] Thereby, the permeability of 157 nm in resin can fully be improved, and the fall of dry etching resistance can be suppressed.
[397] When resin (B) of this invention has at least one repeating unit represented by general formula (I)-(III), and at least one repeating unit represented by general formula (IV)-(VI), General formula ( The sum of the contents of the repeating units represented by I) to (III) is generally in the range of 0 to 70 mol%, preferably 10 to 60 mol%, more preferably 20 to 50 mol% in the overall polymer composition. Used. The sum total of the content of the repeating unit represented by general formula (IV)-(VI) is generally 10-80 mol%, Preferably it is 30-70 mol%, More preferably, 35-65 mol in the total polymer composition. Used in the range of%.
[398] When resin (B) of this invention has at least one repeating unit represented by general formula (IV)-(VI), and at least one repeating unit represented by general formula (VIII)-(X), General formula ( The sum total of the content of the repeating units represented by IV)-(VI) is generally 10-80 mol%, Preferably it is 30-70 mol%, More preferably, in the range of 35-65 mol% in the whole polymer composition. Used.
[399] The sum total of the content of the repeating unit represented by general formula (VIII)-(X) is 0-70 mol%, Preferably it is 10-60 mol%, More preferably, 20-50 mol in the total polymer composition. Used in the range of%.
[400] When resin (B) of this invention has at least one repeating unit represented by general formula (IV)-(VII), and at least one repeating unit represented by general formula (XV)-(XVII), General formula ( The sum total of the content of the repeating units represented by IV)-(VII) is generally 10-80 mol%, Preferably it is 30-70 mol%, More preferably, in the range of 35-65 mol% in the whole polymer composition. Used.
[401] The sum total of the content of the repeating unit represented by general formula (XV)-(XVII) is 0-70 mol%, Preferably it is 10-60 mol%, More preferably, 20-50 mol in the whole polymer composition. Used in the range of%.
[402] In the fluorine group-containing resin each having at least one repeating unit represented by General Formula (IA) and (IIA), the content of the repeating unit represented by General Formula (IA) is generally 5 to 80 mol%, preferably 10 75 mol%, More preferably, it is 20-70 mol%.
[403] In the fluorine group-containing resin each having at least one repeating unit represented by the general formulas (IA) and (IIA), the content of the repeating unit represented by the general formula (IIA) is generally 5 to 80 mol%, preferably 10 70 mol%, More preferably, it is 20-65 mol%.
[404] In the fluorine group-containing resin each having at least one repeating unit represented by General Formula (IIA) and (VIA), the content of the repeating unit represented by General Formula (IIA) is generally 5 to 80 mol%, preferably 10 70 mol%, More preferably, it is 20-65 mol%.
[405] In the fluorine group-containing resin each having at least one repeating unit represented by General Formula (IIA) and (VIA), the content of the repeating unit represented by General Formula (VIA) is generally 5 to 80 mol%, preferably 10 70 mol%, More preferably, it is 20-65 mol%.
[406] In these fluorine-group-containing resins, the content of the repeating unit represented by General Formula (IIIA) is generally 1 to 40 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%.
[407] In these fluorine-group containing resins, the content of the repeating unit represented by General Formula (VIIA) is generally 1 to 40 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%.
[408] Resin (B) of this invention may copolymerize another polymerizable monomer in addition to the above-mentioned repeating structural unit, and also for the purpose of improving the performance of the positive photosensitive property of this invention.
[409] As a copolymerizable monomer which can be used, what is shown below is contained. For example, addition-polymerizable unsaturated bonds selected from acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters and the like other than those described above. It is a compound which has one.
[410] Specifically, for example, acrylic esters such as alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) acrylate (e.g., methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate) , Octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, penta Erythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate and tetrahydrofurfuryl acrylate, etc.);
[411] Methacrylic acid esters, such as alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) methacrylate (for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate) Acrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5- Hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate and tetrahydrofurfuryl methacrylate Rate, etc.);
[412] Acrylamides such as acrylamides and N-alkylacrylamides (as alkyl groups having from 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl and cyclohex Practical groups and hydroxyethyl groups, etc.), N, N-dialkylacrylamides (as alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, butyl, isobutyl, ethylhexyl and cyclohexyl groups); N-hydroxyethyl-N-methylacrylamide and N-2-acetamideethyl-N-acetylacrylamide and the like;
[413] Methacrylamides such as methacrylamide and N-alkyl methacrylamide (as alkyl groups having from 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl and cyclohexyl groups Etc.), N-aryl methacrylamide (as an aryl group, such as a phenyl group), N, N-dialkyl methacrylamide (as an alkyl group, ethyl group, a propyl group, a butyl group etc.), N, N- diaryl methacrylamide ( Examples of the aryl group include a phenyl group), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide, and the like;
[414] Allyl compounds such as allyl esters (eg, allyl acetate, allyl caprolate, allyl caprylic acid, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetic acid and allyl lactate), allyloxyethanol, and the like;
[415] Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-) 2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether , Tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ether (for example, vinylphenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.) ;
[416] Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl acetate Vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, and the like;
[417] Styrene, such as styrene, alkyl styrene (e.g. methyl styrene, dimethyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, ace Oxymethyl styrene, etc.), alkoxy styrene (e.g., methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene, etc.), halogen styrene (e.g., chloro styrene, dichloro styrene, trichloro styrene, tetrachloro styrene, Fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), carboxystyrene, vinylnaphthalene;
[418] Crotonic acid esters such as alkyl crotonate (eg, butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.); Dialkyl itaconic acid (for example, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc.);
[419] Dialkyl esters of maleic acid or fumaric acid (for example, dimethyl fumarate, dibutyl fumarate and the like), maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleylonitrile and the like. In addition, generally, what is necessary is just the copolymerizable addition-polymerizable unsaturated compound.
[420] Although the specific example of the repeating structural unit represented by general formula (I)-(X) is shown below, this invention is not limited to this.
[421]
[422]
[423]
[424]
[425] Moreover, although the specific example of the repeating structural unit represented by general formula (XI)-(XIII) is shown, this invention is not limited to this.
[426]
[427]
[428] Moreover, although the specific example of the repeating structural unit represented by general formula (XVI)-(XVII) is shown, this invention is not limited to this.
[429]
[430] Although the specific example of the repeating structural unit represented by general formula (IA) is shown below, this invention is not limited to this.
[431]
[432]
[433]
[434] Although the specific example of the repeating structural unit represented by general formula (IIA) is shown below, this invention is not limited to this.
[435]
[436] Moreover, as a specific example of the repeating unit represented by general formula (IIA), (F-40)-(F-45) mentioned above can be illustrated.
[437] Although the specific example of the repeating structural unit represented by general formula (VIA) is shown below, this invention is not limited to this.
[438]
[439]
[440] Moreover, as a specific example of the repeating unit represented by general formula (VIA), (F-29)-(F-38) and (F-47)-(F-54) mentioned above can be illustrated.
[441] Although the specific example of the repeating structural unit represented by general formula (IIIA) is shown below, this invention is not limited to this.
[442]
[443] Although the specific example of the repeating structural unit represented by general formula (VIIA) is shown below, this invention is not limited to this.
[444]
[445] Acid-decomposable resin (B) used for this invention can be synthesize | combined by a normal method (for example, radical polymerization). For example, as a general synthesis method, monomer species are introduced into a reaction vessel in a batch or during the reaction, and if necessary, a reaction solvent such as ether such as tetrahydrofuran, 1,4-dioxane or diisopropyl ether, methyl Ketones, such as ethyl ketone or methyl isobutyl ketone, ester solvents, such as ethyl acetate, or the composition of this invention, such as propylene glycol monomethyl ether acetate mentioned later, are melt | dissolved and made uniform. Thereafter, polymerization is started using a commercially available radical initiator (azo initiator, peroxide, or the like) under an inert gas atmosphere such as nitrogen or argon. If desired, an initiator may be added or added in portions. After completion of the reaction, the reaction product is added to the solvent to recover the desired polymer by a method such as powder or solid recovery. The reaction concentration is at least 20% by weight, preferably at least 30% by weight, more preferably at least 40% by weight. The reaction temperature is 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, and more preferably 50 to 100 ° C.
[446] The repeating structural unit represented by the said specific example may be used individually by 1 type, and may be used in mixture of multiple numbers.
[447] In addition, in this invention, 1 type may be used for resin (B) and it may use it together in multiple numbers.
[448] The weight average molecular weight of Resin (B) which concerns on this invention is 1,000-200,000, More preferably, it is 3,000-20,000 as polystyrene conversion value by GPC method. If the weight average molecular weight is less than 1,000, it is not preferable because of deterioration of heat resistance and dry etching resistance, and if it exceeds 200,000, developability is deteriorated or film formation is deteriorated because the viscosity is very high. Occurs.
[449] The molecular weight distribution is 1-10, Preferably it is 1-5, More preferably, the thing of the range of 1-4 is used. The smaller the molecular weight distribution, the smoother the resolution, resist profile, and sidewall of the resist pattern, and the better the edge roughness.
[450] In the positive resist composition of the present invention, the blending amount of all the resins according to the present invention in the total composition is preferably 40 to 99.99%, more preferably 50 to 99.97% by weight in the total resist solids.
[451] << (C) Basic Compound >>
[452] The positive resist composition of this invention contains a basic compound (B) further. Examples of the basic compound include nitrogen-containing basic compounds.
[453] As the nitrogen-containing basic compound, an organic amine, a basic ammonium salt, a basic sulfonium salt, or the like may be used, so long as it does not deteriorate sublimation or resist performance.
[454] Among these nitrogen-containing basic compounds, organic amines are preferred in terms of excellent image performance. For example, Japanese Patent Publication No. 149640/1988, Japanese Patent Publication No. 249662/1993, Japanese Patent Publication No. 127369/1993, Japanese Patent Publication No. 289322/1993, Japanese Patent Publication No. 249683/1993, Japanese Patent Publication 289340/1993, Japanese Patent Publication No. 232706/1993, Japanese Patent Publication No. 257282/1993, Japanese Patent Publication No. 242605/1994, Japanese Patent Publication No. 242606/1994, Japanese Patent Publication No. 266100/1994, Japanese Patent Publication No. 266110/1994, Japanese Patent Publication No. 317902/1994, Japanese Patent Publication No. 120929/1995, Japanese Patent Publication No. 146558/1995, Japanese Patent Publication No. 319163/1995, Japanese Patent Publication No. 508840 / 1995, Japanese Patent Publication No. 333844/1995, Japanese Patent Publication No. 219217/1995, Japanese Patent Publication No. 92678/1995, Japanese Patent Publication No. 28247/1995, Japanese Patent Publication No. 22120/1996, Japan Patent Publication No. 110638/1996, Japanese Patent Publication No. 123030/1996, Japanese Patent Publication 274312/1997, Japanese Patent Publication No. 166871/1997, Japan Basic compounds described in Japanese Patent Publication No. 292708/1997, Japanese Patent Publication No. 325496/1997, International Application Publication No. 508840/1995, US Patent No. 5,525,453, US Patent No. 5,629,134, US Patent No. 5,667,938 and the like can be used. have.
[455] As a basic compound, the structure of following formula (A)-(E) can be illustrated.
[456]
[457] Here, R ²⁵⁰ , R ^251, and R ²⁵² may be the same or different, and represent a hydrogen atom, a C1-C20 alkyl group, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C6-C20 substituent. Or an unsubstituted aryl group, wherein R ²⁵⁰ and R ²⁵¹ may be bonded to each other to form a ring.
[458] R ₂₅₃ , R ₂₅₄ , R _255, and R ₂₅₆ may be either different or different, and represent an alkyl group having 1 to 10 carbon atoms.
[459] Further preferred compounds are nitrogen-containing compounds having two or more nitrogen atoms of different chemical environments in one molecule, or aliphatic tertiary amines.
[460] Preferably, the nitrogen-containing basic compound is 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,4,0] -7-undecene, 1, 4-diabibicyclo [2,2,2] octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidines, pyridines, anilines, hydroxyalkylanilines, 4,4'-diaminodi Phenyl ether, pyridinium p-toluenesulfonite, 2,4,6-trimethylpyridinium p-toluenesulfonite, tetramethylammonium p-toluenesulfonite, tetrabutylammonium lactate, triethylamine, tributylamine, tri Pentylamine, tri-n-octylamine, tri-i-octylamine, tris (ethylhexyl) amine, tridecylamine and the like.
[461] Among them, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,4-diazabicyclo [ 2,2,2] octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, 4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-hydroxypiperidine , Hexamethylenetetramine, imidazole, hydroxypyridines, pyridines, anilines, 4,4'-diaminodiphenyl ether, triethylamine, tributylamine, tripentylamine, tri-n-octylamine And organic amines such as tris (ethylhexyl) amine, tridecylamine, N, N-di-hydroxyethyl aniline and N-hydroxyethyl-N-ethylaniline.
[462] These basic compounds are used individually or in 2 or more types. The usage-amount of a basic compound is 0.001 to 10 weight% normally, based on solid content of the photosensitive composition, Preferably it is 0.01 to 5 weight%. If it is less than 0.001% by weight, the addition effect of the basic compound is not obtained. On the other hand, if it exceeds 10% by weight, the sensitivity is lowered and the developability of the non-exposed part tends to be deteriorated.
[463] << (D) Compound which has at least 3 or more hydroxyl groups or substituted hydroxyl groups, and also has at least one cyclic structure >>
[464] The positive resist composition of this invention further contains the compound which has (D) at least 3 or more hydroxyl group or substituted hydroxyl group, and has at least 1 cyclic structure.
[465] Here, "a compound having at least three or more hydroxyl groups or substituted hydroxyl groups and having at least one cyclic structure" refers to a compound having a cyclic skeleton such as an alicyclic group as a main skeleton or in a side chain. However, this definition does not include an annular structure capable of constructing an annular ketal structure such as the following structure.
[466]
[467] The cyclic structure is preferably a 5- or 6-membered ring, specifically, a tetrahydrofuran ring or tetrahydropyran ring containing a cyclohexane ring, a cyclopentane ring or ether oxygen.
[468] Substituted hydroxyl group represents the group which consists of a hydroxyl group substituted by the alkyl group, an aralkyl group, an aryl group, etc., ie, an alkoxy group, an aralkyloxy group, an aryloxy group, etc., or an ether structure substituted with an acid-decomposable group or another group.
[469] In addition, an acid-decomposable group means group which decomposes | dissolves with an acid, and specifically, an acetal group, a ketal group, t-butoxycarbonyl group, t-butyl ester group, etc. are shown.
[470] Moreover, you may combine with two hydroxyl groups and form an acid-decomposer like the following structure.
[471]
[472] Here, R ₁ and R ₂ each independently represent an alkyl group, an aralkyl group, and an aryl group, and R ₁ and R ₂ may be bonded to each other to form a ring.
[473] Although these acid-decomposers may have two or more at the same time in the same molecule, it is preferable to have two or more acid-decomposer in the same molecule, and it is preferable that at least one has the following structure.
[474]
[475] As a compound of the component (D) of this invention, it is necessary to have at least 3 or more hydroxyl groups or substituted hydroxyl groups, Preferably it is 3-10 pieces, More preferably, it is preferable to have 4-8 pieces.
[476] As a compound of the component (D) of this invention, as long as it is a compound which satisfy | fills the said requirement, any of the structures shown below may be sufficient, Especially, a cyclic saccharide derivative is preferable.
[477] Specific examples of the skeleton of the cyclic saccharide derivative include arabinose, xylose, rhamnose, galactose, glucose, fructose, plutopyranose, sorbose, mannose, allopyranose, altrose, talos, tagatose, and arabino. Pyranoside, thiogalactopyranoside, mannofyranoside, glucopyranose, glucopyranoside, mannitol, sucrose, paratinose, lactitol, lactose, malturose, maltose, maltoside, maltitol, cello Bioses, turanose, trehalose, melibiose, maltotriose, meletchiose, raffinose, stachiose, maltotetraose, maltohexaose, cyclodextrin and the like.
[478] Examples of the cyclic sugar derivatives are shown below, but the present invention is not limited thereto.
[479]
[480]
[481]
[482]
[483]
[484]
[485]
[486]
[487]
[488] It is preferable to use the compound which has at least 3 hydroxyl group or substituted hydroxyl group and at least 1 cyclic structure (D) with respect to solid content in positive resist composition, 0.1-20 weight%.
[489] << (E) Fluorine and / or silicone type surfactant >>
[490] The positive resist composition of the present invention contains at least the components (A) to (D), but (E) fluorine-based and / or silicon-based surfactants (fluorine-based surfactants and silicon-based surfactants, both fluorine atoms and silicon atoms). It is preferable to further contain any one or 2 types or more of surfactant).
[491] Since the positive resist composition of the present invention contains the surfactant (E), it is possible to give a resist pattern with low adhesion and development defects with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. It becomes possible.
[492] As these surfactants, for example, Japanese Patent Laid-Open No. 36663/1987, Japanese Patent Laid-Open No. 226746/1986, Japanese Patent Laid-Open No. 226745/1986, Japanese Patent Laid-Open No. 170950/1987, Japanese Patent Laid-Open 34540/1988, Japanese Patent Publication No. 230165/1995, Japanese Patent Publication No. 62834/1996, Japanese Patent Publication No. 54432/1997, Japanese Patent Publication No. 5988/1997, US Patent No. 5,405,720 Surfactants described in Nos. 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511 and 5,824,451 can be exemplified. Moreover, the following commercially available surfactant can be used as it is.
[493] Commercially available surfactants include, for example, Eftop EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M), Megafack F171, F173, F176, F189, and R08 (manufactured by Dainippon Ink, Inc.). ), Fluorosurfactants such as Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and Torysol S-366 (manufactured by Toroy Chemical Co., Ltd.) or silicone surfactants. Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.
[494] The amount of the surfactant used is preferably 0.0001 to 2% by weight, more preferably 0.001 to 1% by weight based on the total amount of the positive resist composition (excluding the solvent).
[495] << (F) Organic solvent >>
[496] In the positive resist composition of the present invention, the above components are dissolved in a predetermined organic solvent and used.
[497] Examples of the organic solvent that can be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2- Methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate , Ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like can be exemplified.
[498] In the present invention, the organic solvent may be used alone or in combination, but it is preferable to use a mixed solvent in which a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group are mixed in the structure. Thereby, the generation | occurrence | production of the particle | grains at the time of the storage of the photosensitive composition can be reduced.
[499] Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Propylene glycol monomethyl ether and ethyl lactate are particularly preferred.
[500] As a solvent which does not contain a hydroxyl group, For example, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, (gamma) -butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N , N-dimethylacetamide, dimethyl sulfoxide and the like can be exemplified, among them, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, acetic acid Butyl is particularly preferred, with propylene glycol monomethyl ether acetate, ethyl ethoxy propionate and 2-heptanone being most preferred.
[501] The mixing ratio (weight) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99-99/1, Preferably it is 10/90-90/10, More preferably, it is 20/80-60/40. . A mixed solvent containing 50% by weight or more of a solvent containing no hydroxyl group is particularly preferable in terms of coating uniformity.
[502] << (G) Alkali Soluble Resin >>
[503] The positive resist composition of the present invention may further contain a resin which is insoluble in water and soluble in an alkali developer, which does not contain an acid-decomposable group, thereby improving sensitivity.
[504] In the present invention, novolak resins having a molecular weight of about 1,000 to 20,000 and polyhydroxystyrene derivatives having a molecular weight of about 3,000 to 50,000 can be used as such resins. It is preferable to add and use, or to use in the quantity of 30 weight% or less of the total resin amount.
[505] Moreover, the resin containing a carboxyl group as an alkali-soluble group can also be used. In the resin containing a carboxyl group, in order to improve dry etching resistance, a (meth) acrylic acid of an alicyclic hydrocarbon group having a carboxyl group or a copolymer of a methacrylic acid ester having a monocyclic or polycyclic alicyclic hydrocarbon structure and (meth) acrylic acid or a terminal Resin of ester, etc. can be illustrated.
[506] << Other additives >>
[507] The positive resist composition of the present invention may further contain a dye, a plasticizer, the surfactant (E), a photosensitizer, a compound that promotes solubility in a developer, and the like, as necessary.
[508] The dissolution promoting compound for the developer usable in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less having two or more phenolic OH groups or one or more carboxyl groups. In the case of having a carboxyl group, an alicyclic or aliphatic compound is preferable.
[509] The preferable addition amount of these dissolution promoting compounds is 2-50 weight% with respect to resin (B), More preferably, it is 5-30 weight%. At an added amount exceeding 50% by weight, the development residue deteriorates and new defects such as deformation of the pattern during development occur, which is not preferable.
[510] Such phenolic compounds having a molecular weight of 1000 or less are described to those skilled in the art, for example, with reference to methods described in Japanese Patent Application Laid-Open No. 122938/1992, Japanese Patent Application Laid-Open No. 28531/1990, US Patent No. 4,916,210, and European Patent No. 219294. It can be easily synthesized by
[511] Specific examples of the cycloaliphatic or aliphatic compound having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, and lithocholic acid, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid, and cyclohexanecarboxes. Acid, cyclohexanedicarboxylic acid, etc. are illustrated, but it is not limited to these.
[512] In this invention, surfactant other than the said (E) fluorine type and / or silicone type surfactant can be added. As a specific example, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether; Polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; Polyoxyethylene-polyoxypropylene block copolymers; Sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; Polyoxyethylene sorbate such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Nonionic surfactants, such as a non-fatty fatty acid ester, can be illustrated.
[513] These surfactants may be added alone or in combination of any of them.
[514] << How to use >>
[515] The positive resist composition of this invention dissolves the said component in the predetermined organic solvent, Preferably the said mixed solvent, and apply | coats and uses it on the predetermined | prescribed support body as follows.
[516] That is, the photosensitive composition is applied onto a substrate (e.g., silicon / silicon dioxide coating) by a suitable coating method such as spinner, coater, etc. to be used in the manufacture of the precision integrated circuit device.
[517] After application, it is exposed through a predetermined mask, baked and developed. In this way, a good resist pattern can be obtained. As exposure light here, Preferably it is 250 nm or less, More preferably, it is far ultraviolet of the wavelength of 220 nm or less. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), an X-ray, an electron beam, etc. are illustrated.
[518] In the developing step, an alkaline developer is used as follows. As alkali developing solution of the photosensitive composition, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, primary amines, such as ethylamine and n-propylamine, diethylamine, and di-n Secondary amines such as butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like Alkaline aqueous solutions such as cyclic amines such as quaternary ammonium salts, pyrrole and piperidine can be used.
[519] Furthermore, alcohols and surfactants can be added to the alkaline aqueous solution in an appropriate amount.
[520] Example
[521] Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.
[522] Synthesis Example (1): Synthesis of Resin (1) (Side Chain Type)
[523] 2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were added at a ratio of 55/45, dissolved in methyl ethyl ketone / tetrahydrofuran = 5/5, and 100 ml of a solution having a solid concentration of 20% was dissolved. It prepared. 2 mol% of V-65 by Wako Pure Chemical Industries Ltd. was added to this solution, and this was dripped at 10 ml of methyl ethyl ketone heated at 60 degreeC over 4 hours by nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated for 4 hours, 1 mol% of V-65 was added again, and stirred for 4 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, poured into 3 L of a mixed solvent of distilled water / isopropyl alcohol = 1/1 to crystallize, and the resin 1, which was a precipitated white powder, was recovered.
[524] Polymer composition ratio determined from C ¹³ NMR was 46/54. In addition, the weight average molecular weight of the standard polystyrene conversion calculated | required by GPC analysis was 10700.
[525] Resins (2) to (12) were synthesized in the same manner as in Synthesis Example (1).
[526] The composition ratio and molecular weight of said resin (2)-(12) are shown below. (Repeat units 1, 2, 3, 4 are the numbers from left to right horizontally.)
[527]
[528] Moreover, the structure of resin (1)-(12) is shown below.
[529]
[530]
[531]
[532] Synthesis Example (2): Synthesis of Resin (13) (Main Chain Type)
[533] Norbornenecarboxylic acid t-butyl ester, norbornenecarboxylic acid butyrolactone ester, maleic anhydride (molar ratio 40/10/50) and THF (reaction concentration 60% by weight) are placed in a detachable flask and nitrogen stream Under heating at 60 ° C. After the reaction temperature was stabilized, 2 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to initiate the reaction. Heated for 12 hours. The obtained reaction mixture was diluted twice with tetrahydrofuran and then poured into a mixed solution of hexane / isopropyl alcohol = 1/1 to precipitate white powder. The precipitated powder was collected by filtration and dried to obtain Resin (13) as a target product.
[534] When molecular weight analysis was performed by GPC of the obtained resin (13), it was 8,300 (weight average) in terms of polystyrene. Moreover, the NMR spectrum confirmed that the molar ratio of the norbornene carboxylic acid t-butyl ester / norbornene carboxylic acid butyrolactone ester / maleic anhydride repeating unit of resin (13) was 42/8/50.
[535] Resins 14 to 17 were synthesized in the same manner as in Synthesis Example (2) below.
[536] The composition ratio and molecular weight of said resin (14)-(17) are shown below. (In Table 2, alicyclic olefin unit 1, 2, 3 are the order from the left side horizontally in each structural formula below.)
[537]
[538] In addition, the structures of the resins (13) to (17) are shown below.
[539]
[540] Synthesis Example (3): Synthesis of Resin (18) (Hybrid Type)
[541] Norbornene, maleic anhydride, t-butyl acrylate and 2-methylcyclohexyl-2-propyl acrylate were added to the reaction vessel at a molar ratio of 35/35/20/10, dissolved in tetrahydrofuran to give a solid content of 60% by weight. The solution was prepared. It was heated at 65 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 1 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 8 hours, the reaction mixture was diluted twice with tetrahydrofuran, and then charged into 5 times the volume of hexane of the reaction mixture to precipitate white powder. The precipitated powder was collected by filtration and dissolved in methyl ethyl ketone. The precipitated powder was reprecipitated in a 5-fold volume of hexane / t-butyl methyl ether = 1/1 mixed solvent, and the precipitated white powder was collected by filtration and dried to obtain the target product. Resin (18) was obtained.
[542] When molecular weight analysis was performed by GPC of the obtained resin (18), it was 12100 (weight average) in terms of polystyrene. In addition, the composition of resin (1) from the NMR spectrum was 32/39/19/10 in molar ratio of norbornene / maleic anhydride / tbutyl acrylate / 2-methylcyclohexyl-2-propyl acrylate of this invention.
[543] Resins 19 to 24 were synthesized in the same manner as in Synthesis Example (3).
[544] The composition ratio and molecular weight of the said resin (19)-(24) are shown below.
[545]
[546] In addition, the structures of the resins 18 to 24 are shown below.
[547]
[548] Synthesis Example (4): Synthesis of Resin (25) (Hybrid Type)
[549] Norbornene carboxylic acid t-butyl ester, maleic anhydride, 2-methyl-2-adamantyl acrylate and norbornene lactone acrylate were added to the reaction vessel in a molar ratio of 20/20/35/25, and methyl ethyl ketone It was dissolved in a / tetrahydrofuran = 1/1 solvent to prepare a solution of 60% solids. It was heated at 65 ° C. under a nitrogen stream. When the reaction temperature stabilized, 3 mol% of the radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 12 hours, the reaction mixture was diluted 5 times with tetrahydrofuran, and then charged into 5 times the volume of hexane of the reaction mixture to precipitate white powder. The precipitated powder was dissolved again in a solvent of methyl ethyl ketone / tetrahydrofuran = 1/1, and charged into 5 times hexane / methyl t-butyl ether to precipitate a white powder, which was collected by filtration. This operation was repeated again, and it dried and obtained resin (25) which is a target object.
[550] When molecular weight analysis (RI analysis) of the obtained resin (25) was performed by GPC, it was 11,600 (weight average) in terms of polystyrene, and the amount of residual monomer was 0.4%. The composition of the resin 25 was 18/23/34/25 in a molar ratio of norbornene / maleic anhydride / 2-adamantyl acrylate / norbornene lactone acrylate of the present invention from the NMR spectrum.
[551] Resins 26 to 31 were synthesized in the same manner as in Synthesis Example (4).
[552] The composition ratio and molecular weight of the said resin (26)-(31) are shown below.
[553]
[554] In addition, the structures of the resins 25 to 31 are shown below.
[555]
[556]
[557] Synthesis Example (5): Synthesis of Resin (F1)
[558] 150 ml of 1,1,2-trichloro-trifluoroethylene solution of 9.4 g (0.10 mol) of norbornene and 19.4 g (0.10 mol) of norbornene-2-carboxylic acid t-butyl ester was placed in a 1 L autoclave. Pressurized to 200 psi under nitrogen atmosphere. Further, 20 g (0.20 mol) of tetrafluoroethylene was injected, stirred, and heated at 50 ° C. A 15 ml solution of 1.2 g of 1,1,2-trichlorotrifluoroethylene 1.2 g of di (4-t-butylcyclohexyl) peroxydicarbonate was injected into the reaction solution over 20 minutes, and stirring was continued for 20 hours. . After completion of the reaction, the reaction solution was poured into 2 L of methanol with vigorous stirring to precipitate a white resin. Precipitated resin was filtered and dried under vacuum to obtain 23.5 g of Resin (F1) of the present invention.
[559] The molecular weight of resin (F1) was 6,200 by weight average (Mw) by GPC analysis. In addition, by C ¹³ -NMR measurement, the bar composition of the irradiated resin (F1), the molar ratio to the structural example (F1) / norbornene / (B-16) = was 45/30/25.
[560] Synthesis Example (6): Synthesis of Resin (F2)
[561] The following monomer (a) 14.3 g (0.04 mol), maleic anhydride 3.9 g (0.04 mol), and 2.6 g (0.02 mol) of t-butyl acrylate were dissolved in 100 ml of MEK, and heated at 70 degreeC under nitrogen stream. As a polymerization initiator, 0.2 g of V-601 (made by Wako Pure Chemical Industries, Ltd.) was added, and it stirred for 3 hours. Furthermore, 0.2 g of V-601 was added and stirring was continued for 4 hours. Thereafter, the reaction solution was poured into 1 L of t-butyl methyl ether with vigorous stirring to precipitate a white resin. The precipitated resin was filtered off and dried under vacuum to give 12.1 g of Resin (F2) of the present invention.
[562] The molecular weight of resin (F2) was 8,900 by weight average (Mw) by GPC analysis. C ¹³ structure was also investigated with a composition bar, the molar ratio of the resin (F2) by -NMR measurement example (F-21) / maleic anhydride / (B-4) = 39 /38/23.
[563]
[564] Synthesis Example (7): Synthesis of Resin (F3)
[565] 6.7 g (0.015 mol) of the following monomers (b), 1.4 g (0.006 mol) of 2-methyl-2-adamantane methacrylate, and 1.8 g (0.009 mol) of methatronic lactone methacrylate were 1-methoxy- Dissolved in 30 ml of 2-propanol, and a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) (product of Wako Pure Chemical Industries, Ltd .; brand name V-65) at 70 ° C under nitrogen stream and stirring, 0.1 g and 15.6 g of monomer (b) 15.6 g (0.035 mol), 2-methyl-2-adamantane methacrylate 3.3 g (0.014 mol) and 4.2 g (0.021 mol) of mechatronic lactone methacrylate A 70 ml solution of -2-propanol was added dropwise over 2 hours. After 2 hours, 0.1 g of initiator was added, and the reaction was further performed for 2 hours. Then, it heated up at 90 degreeC and continued stirring for 1 hour. The reaction solution was allowed to cool and then poured into 1 L of ion-exchanged water / methanol (1/1) with vigorous stirring to precipitate a white resin. After drying obtained resin under reduced pressure, 15.8g of resin (F3) of this invention was obtained.
[566] When molecular weight was measured by GPC, it was 10,200 by weight average (Mw). In addition, by C ¹³ -NMR measurement, the bar composition of the irradiated resin (F3), the molar ratio was as structure examples (F-30) / (B -7) / (B-11) = 48/21/31.
[567]
[568] Resins (F4) to (F12) shown in Table 5 were synthesized in the same manner as in Synthesis Examples (5) to (7).
[569] The composition ratio and molecular weight of said resin (F4)-(F12) are shown below.
[570]
[571] Synthesis Example (8): Synthesis of Resin (F13)
[572] Into a 1 L autoclave, 9.4 g (0.10 mole) of norbornene and 35.8 g (0.10 mole) of the following monomer (a) were added 150 ml of 1,1,2-trichloro-trifluoroethylene solution and pressurized to 200 psi under a nitrogen atmosphere. It was. Furthermore, 20 g (0.20 mol) of tetrafluoroethylene were injected | poured, and it stirred, and heated at 50 degreeC. A 15 ml solution of 1.2 g of 1,1,2-trichloro-trifluoroethylene 1.2 g of di (4-t-butylcyclohexyl) peroxycarbonate was injected into the reaction solution over 20 minutes, followed by stirring for 20 hours. Continued. After the reaction was completed, the reaction solution was poured into 2 L of methanol with vigorous stirring to precipitate a white resin. Precipitated resin was filtered and dried under vacuum to obtain 37.4 g of Resin (F13) of the present invention.
[573] The molecular weight of Resin (F13) was 8,800 by weight average (Mw) by GPC analysis. The structure in the composition irradiated bar, the molar ratio of the resin (F13) measured by a ¹³ C -NMR examples (F-1) / (F -21) / norbornene was nen = 48/30/22.
[574]
[575] Synthesis Example (9): Synthesis of Resin (F14)
[576] Instead of the monomer (a) of the synthesis example (8), 32.2 g (0.04 mol) of the following monomer (c) was used, and in the same manner as in the synthesis example (8) below, 34.1 g of the resin (F14) of the present invention was synthesized. It was.
[577] The molecular weight of Resin (F14) was 7,400 by GPC analysis by weight average (Mw). Was also measured by C ¹³ -NMR, bar investigated the composition of resin (F14), the structure example in a molar ratio (F-1) / (F -15) / norbornene = 49/25/26.
[578]
[579] Resins (F15) to (F22) shown in Table 6 were synthesized in the same manner as in Synthesis Examples (8) to (9).
[580] The composition ratio and molecular weight of said resin (F15)-(F22) are shown below.
[581]
[582] Synthesis Example (10): Synthesis of Resin (F23)
[583] The following monomer (a) 14.3 g (0.04 mol), maleic anhydride 3.9 g (0.04 mol), norbornene-2-carboxylic acid perfluorooctylethyl 11.7 g (0.02 mol) were dissolved in 100 ml of MEK, and a nitrogen stream was obtained. Then, it heated at 70 degreeC. As a polymerization initiator, 0.2 g of V-601 (made by Wako Pure Chemical Industries, Ltd.) was added, and it stirred for 3 hours. Furthermore, 0.2 g of V-601 was added and stirring was continued for 4 hours. Thereafter, the reaction solution was poured into 1 L of t-butyl methyl ether with vigorous stirring to precipitate a white resin. Precipitated resin was filtrated and dried under vacuum to obtain 16.2 g of Resin (F23) of the present invention.
[584] By GPC analysis, the molecular weight of Resin (F23) was 8,700 in weight average (Mw). The structure in the composition irradiated bar, the molar ratio of the resin (F23) measured by a ¹³ C -NMR example (F-21) / (F -55) / maleic anhydride, was = 42/18/40.
[585]
[586] Synthesis Example (11): Synthesis of Resin (F24)
[587] 6.7 g (0.015 mol) of the following monomers (b), 2.7 g (0.005 mol) of perfluorooctylethyl methacrylate, 1.2 g (0.005 mol) of 2-methyl-2-adamantane methacrylate, mevalonic lactone 1.0 g (0.005 mol) of methacrylate was dissolved in 30 ml of 1-methoxy-2-propanol, stirred under a stream of nitrogen, and polymerized initiator 2,2'-azobis (2,4-dimethylvaleronitrile at 70 ° C. (Product of Wako Pure Chemical Industries, Ltd .; product name V-65) 0.1 g of monomer (b) 15.6 g (0.035 mol), 6.4 g (0.012 mol) of perfluorooctylethyl methacrylate, 2-methyl-2-a However, a 70 ml solution of 2.8 g (0.012 mol) of methacrylate and 2.4 g (0.012 mol) of mechatronic lactone methacrylate was added dropwise over 2 hours. After 2 hours, 0.1 g of initiator was added, and the reaction was further performed for 2 hours. Then, it heated up at 90 degreeC and continued stirring for 1 hour. The reaction solution was allowed to cool and then poured into 1 L of ion-exchanged water / methanol (1/1) with vigorous stirring to precipitate a white resin. After drying obtained resin under reduced pressure, 21.5 g of resin (F24) of this invention was obtained.
[588] When molecular weight was measured by GPC, it was 10,500 by weight average (Mw). In addition, for example, C ¹³ structure the composition review bar, the molar ratio of the resin (F24) by measuring -NMR (F-30) / (F -48) / (B-7) / (B-11) = 48/15 / It was 18/19.
[589]
[590] Resin (F25)-(F32) shown in Table 6 was synthesize | combined by the method similar to the synthesis examples (10)-(11).
[591] The composition ratio and molecular weight of said resin (F25)-(F32) are shown below.
[592]
[593] Synthesis Example (12): Synthesis of Resin (F33)
[594] 13.5 g (0.05 mol) of 4- [bis (trifluoromethyl) -hydroxymethyl] styrene and 3.4 g (0.05 mol) of methacrylonitrile were dissolved in 100 ml of N, N-dimethylacetamide, and Heated at 70 ° C. As a polymerization initiator, 0.1 g of 2.2'-azobis (2,4-dimethylvaleronitrile) (product of Wako Pure Chemical Industries, Ltd .; product name V-65) was added and stirred for 3 hours. Furthermore, 0.1 g of V-65 was added and stirring was continued for 4 hours. Thereafter, the reaction solution was poured into 1 L of methanol / t-butyl methyl ether with vigorous stirring to precipitate a white resin. The precipitated resin was filtered, dried under vacuum, dissolved in 100 ml of THF, 2.9 g (0.04 mol) of ethyl vinyl ether was added, and a catalytic amount of p-toluenesulfonic acid was added, followed by stirring at room temperature for 8 hours. Triethylamine was added to the reaction solution twice as much as the p-toluenesulfonic acid catalyst to stop the reaction, and the mixture was poured into 3 L of ultrapure water with vigorous stirring. Precipitated resin was filtered and dried to obtain 14.1 g of Resin (F33) of the present invention.
[595] The molecular weight of Resin (F33) was 10,900 by weight average (Mw) by GPC analysis. The structure with a bar, the molar ratio of the irradiated composition, resin (F33) by the ¹³ C -NMR, IR measurement example (F-39) / (F -42) / ( was a C-10 = 16/36/ 48.
[596] Resins (F34) to (F40) shown in Table 8 were synthesized in the same manner as in Synthesis Example (12).
[597] The composition ratio and molecular weight of said resin (F34)-(F40) are shown below.
[598]
[599] Synthesis Example (13): Synthesis of Resin (F42)
[600] In a 100 ml three-necked flask equipped with a reflux tube and a nitrogen introduction tube, 4- (2-hydroxyhexafluoroisopropyl) styrene (from Centralgrass) and 4- (1-methoxyethoxy) styrene Shosho Co., Ltd.) was added at a molar ratio of 50/50, respectively, and then tetrahydroxyfuran was added to adjust 30 g of the total reaction solution having a monomer concentration of 30% by weight. It was heated to 65 ° C. under stirring and nitrogen stream. Azo polymerization initiator V-65 (made by Wako Pure Chemical Industries, Ltd.) was added 5.0 mol% with respect to the number-of-moles of the said 2 monomer total, and it was made to react for 8 hours, stirring under nitrogen stream. 200 ml of hexane was added to the obtained reaction solution, and the produced polymer was precipitated from the solution to separate and purify the unreacted monomer. The polymer composition determined from C ¹³ -NMR was 49/51.
[601] The obtained polymer was analyzed by GPC (in terms of standard polystyrene in THF solution), and the weight average molecular weight was 10,200, the dispersion degree 2.20, and the ratio of the molecular weight of 1,000 or less contained in the polymer was 15% by weight.
[602] Resins (F41) to (F50) shown in Table 9 were synthesized in the same manner as in Synthesis Example (13).
[603] The composition ratio and molecular weight of said resin (F41)-(F50) are shown below.
[604]
[605] Synthesis Example (14): Synthesis of Resin (k-1)
[606] VP15000 (100 g) and propylene glycol monomethyl ether acetate (PGMEA) (400 g) from Nippon Sodachi Co., Ltd. were dissolved in a flask and distilled under reduced pressure to remove azeotropically water and PGMEA.
[607] After confirming that the water content was sufficiently low, ethyl vinyl ether (25.0 g) and p-toluenesulfonic acid (0.02 g) were added, followed by stirring at room temperature for 1 hour.
[608] Tolueneamine (0.03 g) was added to the reaction solution to stop the reaction, water (400 ml) and ethyl acetate (800 ml) were added, decomposed, washed with water, and then washed with water to remove ethyl acetate, water, The azeotropic PGMEA was removed to obtain resin k-1 (30% PGMEA solution) having a substituent according to the present invention.
[609] Resin (k-2)-(k-15) shown in Table 10 were synthesize | combined by the method similar to the synthesis example (14).
[610] The composition ratio and molecular weight of said resin (k-1)-(k-15) are shown below.
[611]
[612] Examples 1 to 49 and Comparative Examples 1 to 10
[613] <Preparation and Evaluation of Positive Resist Composition>
[614] 1.03 g of resins shown in Tables 11 to 13 synthesized in the above Synthesis Examples, 0.05 g of the compound of the present invention, 1.65 mg of the basic compound, and 100 ppm of the entire surfactant shown in Tables 11 to 13, respectively, shown in Tables 11 to 13 The mixture was mixed as described above, and dissolved in propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether (= 7/3) so that the solid content was 11% by weight, respectively, and then filtered through a 0.1 µm microfilter. The positive resist compositions of Comparative Examples 1-10 were prepared.
[615]
[616]
[617]
[618] As a basic compound,
[619] C-1: 1,5-diazabicyclo [4,3,0] -5-nonene
[620] C-2: 1,8-diazabicyclo [5,4,0] -7-undecene
[621] C-3: 4-dimethylaminopyridine
[622] C-4: triphenylimidazole
[623] C-5: diisopropylaniline
[624] C-6: tributylamine
[625] C-7: trioctylamine
[626] C-8: Tridecylamine
[627] C-9: N, N-bis (hydroxyethyl) aniline
[628] C-10: 2,2,6,6-tetramethyl-4-hydroxypiperidine is represented.
[629] As a surfactant,
[630] W-1: Megafac F176 (product of Dainippon Ink Corporation) (fluorine system)
[631] W-2: Megafac R08 (manufactured by Dainippon Ink, Inc.) (Fluorine and Silicon)
[632] W-3: polysiloxane polymer KP-341 (product of Shin-Etsu Chemical Co., Ltd.) (silicone type)
[633] W-4: Toro Sol S-366 (Toroid Chemical Co., Ltd. product)
[634] Is displayed.
[635] (Evaluation test)
[636] First, ARC-25 manufactured by Brewer Science, Inc. was coated with a spin coater on a silicon wafer at a thickness of 30 nm and dried. Thereafter, the positive photoresist composition solution obtained thereon was applied using a spin coater, dried at 115 ° C. for 90 seconds to form a positive photoresist film of about 0.4 μm, and in Examples 1 to 31 and Comparative Examples 1 to 4 thereon. For example, ArF excimer laser (193 nm), Examples 32 to 39 and KrF excimer laser (248 nm) for Comparative Examples 5 to 6, and Examples 40 to 42 and EB irradiation apparatus for Comparative Example 7, were also carried out. About Examples 43-49 and Comparative Examples 8-10, it exposed by F2 excimer laser (157nm).
[637] The post-exposure heat treatment was conducted at 115 ° C. for 90 seconds to develop with 2,38% aqueous tetramethylammonium hydroxide solution, and rinsed with distilled water to obtain a resist pattern profile.
[638] About these, line edge roughness and pattern depression were evaluated as follows. These evaluation results are shown in Table 14.
[639] [Sun Edge Roughness]
[640] The edge roughness is measured by using a scanning scanning electron microscope (SEM) at an edge roughness of an isolated pattern (line width 0.15 탆), and the line pattern edge is detected at a plurality of positions within the measurement monitor, Dispersion of change (3σ) was used as an index of edge roughness. The smaller this value is, the more preferable.
[641] [Pattern Depression]
[642] The obtained pattern was observed with a scanning electron microscope (SEM), and it marked "good" that a pattern depression did not generate | occur | produce or only a little generate | occur | produced it as "bad".
[643]
[644] As is apparent from the results in Table 14, it is found that the positive resist composition of the present invention is excellent in line edge roughness and pattern dent resistance.
[645] The present invention can provide a positive resist composition in which pattern depression is prevented and the line edge roughness is good.

权利要求:
Claims (13)
[1" claim-type="Currently amended] (A) a compound which generates an acid by irradiation of actinic light or radiation;
(B) resins which are insoluble or poorly soluble in alkali but become alkali-soluble under the action of an acid;
(C) basic compounds; And
(D) A positive resist composition comprising a compound having at least three hydroxyl groups or substituted hydroxyl groups, and having at least one cyclic structure.
[2" claim-type="Currently amended] The compound (D) according to claim 1, wherein the component (D) is a compound having at least three hydroxyl groups and at least one cyclic structure, and at least one acid-decomposable group is a compound in which at least one of the hydroxyl group and other groups of the component (D) is protected. A positive resist composition characterized by the above.
[3" claim-type="Currently amended] The positive resist composition according to claim 1, wherein the component (B) is a resin having at least one phenolic hydroxyl group structure and decomposed by the action of an acid to increase the solubility in an alkaline developer.
[4" claim-type="Currently amended] The positive resist composition according to claim 1, wherein the component (B) is a resin having a monocyclic or polycyclic alicyclic hydrocarbon group and decomposed by the action of an acid to increase the solubility in an alkaline developer.
[5" claim-type="Currently amended] 2. The component (B) according to claim 1, wherein the component (B) is a resin having a structure in which one or more fluorine atoms are substituted in at least one of the main chain and the side chain of the polymer, and decomposed by the action of an acid to increase the solubility in an alkaline developer. A positive resist composition characterized by the above.
[6" claim-type="Currently amended] The positive resist composition according to claim 1, further comprising at least one of (E) fluorine and a silicone-based surfactant.
[7" claim-type="Currently amended] (F) The positive resist composition of Claim 1 which further contains the mixed solvent of the solvent containing a hydroxyl group, and the solvent which does not contain a hydroxyl group.
[8" claim-type="Currently amended] The solvent containing the hydroxyl group is one of ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethyl lactate. The positive resist composition characterized by the above-mentioned.
[9" claim-type="Currently amended] The solvent containing no hydroxyl group is propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, and N-methyl. A positive resist composition, characterized in that one of pyrrolidone, N, N-dimethylacetamide, and dimethyl sulfoxide.
[10" claim-type="Currently amended] The positive resist composition according to claim 7, wherein the component (F) contains 50% by weight or more of a solvent containing no hydroxyl group.
[11" claim-type="Currently amended] The positive resist composition according to claim 1, wherein the component (D) contains at least one of a cyclohexane ring, a cyclopentane ring, and a tetrahydrofuran ring or tetrahydropyran ring containing ether oxygen.
[12" claim-type="Currently amended] A positive resist composition according to claim 1, wherein component (D) contains 3 to 10 hydroxyl groups or 3 to 10 substituted hydroxyl groups.
[13" claim-type="Currently amended] The composition (A) is 0.1 to 20% by weight, component (B) is 40 to 99.99% by weight, component (C) is 0.001% to 10% by weight, and component (D) according to claim 1 ) Is 0.1 to 20% by weight of the positive resist composition.

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2001-09-19|Priority to JPJP-P-2001-00285180

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2001-09-19|Priority to JP2001285180

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2002-01-07|Priority to JPJP-P-2002-00000563

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2002-01-07|Priority to JP2002000563A

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2002-09-19|Application filed by 후지 샤신 필름 가부시기가이샤

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2003-06-25|Publication of KR20030051186A

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2009-12-14|Application granted

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2009-12-14|Publication of KR100931617B1

优先权:

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申请号 | 申请日 | 专利标题

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JPJP-P-2001-00285180|2001-09-19|

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JP2001285180|2001-09-19|

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JPJP-P-2002-00000563|2002-01-07|

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JP2002000563A|JP4025074B2|2001-09-19|2002-01-07|Positive resist composition|