TWI314251B - Positive resist composition and method of forming pattern by using it - Google Patents

Description

[Technical Field] The present invention relates to a positive-type photoresist composition suitable for use in the manufacture of a semiconductor integrated circuit element, a photomask for manufacturing an integrated circuit, a liquid crystal panel, or the like. (2) An initial chemically amplified positive photoresist composition formed by a resin protected by a photoacid generator and an acid-decomposable group in the prior art, for example, as disclosed in Patent Document 1 (US Pat. No. 4,491,628) By. The chemically amplified positive photoresist composition is an acid generated in the exposed portion by radiation irradiation of far ultraviolet light or the like, and the reaction portion of the active radiation and the non-irradiated portion are in the developing liquid by the reaction of the acid as a catalyst. The solubility changes to form a patterned pattern forming material on the substrate. Here, various positive-type resist compositions containing a resin resin which is protected by an acid-decomposable group are known, and alkoxy (acetal) is used, for example, in the patent document 2 (Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. A composition of a polyhydroxystyrene resin protected by two different acid decomposition groups, which is a composition of a polyhydroxystyrene resin which is protected by a base, and a composition of a polyhydroxystyrene resin which is protected by two different acid decomposition groups. In the patent document 4 (Japanese Laid-Open Patent Publication No. 2000-352822), a composition of a resin having an acetal group-protected resin having a heterocyclic group at the terminal via a linking group is disclosed. The composition of the polyhydroxystyrene resin protected by two different awake groups is used. However, in the conventional positive-type photoresist composition, since the high-reflection substrate has insufficient suitability and the standing wave strongly remains, it is desired to improve it. [Patent Document 1] US Patent No. 4 4 9 1 6 2 8 [Invention Patent Document 2] Japanese Patent Publication No. 5 - 2 4 9 6 8 2 [Invention Patent Document 3] Special Kaiping 9 - 2 1 1 。 。 。 。 。 8 2 2 2 2 2 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 Solution to Problem] An object of the present invention is to provide a chemically amplified positive-type photoresist composition which is excellent in suitability for a highly reflective substrate, suppresses generation of standing waves, and can obtain a rectangular profile. [Means for Solving the Problem] After careful investigation, the inventor of the present invention found that a positive-type photoresist composition containing two kinds of resins having a specific structure of an acid-decomposable group can achieve the above purpose and is finally completed. this invention. That is, the positive resist composition of the present invention has the following constitution. (1) A positive-type photoresist composition comprising (A1) a resin which increases the solubility in an alkali developing solution by an acid action, which contains a repeating unit of the formula (I) II) at least one of the repeating unit and the repeating unit represented by the formula (III) '(B) a compound which generates an acid by irradiation with active rays or radiation, and (C) a solvent 1314251

〇>|jt-CLz1

L (ί) wherein L and L' each independently represent a hydrogen atom, an alkyl group or an aralkyl group, Z1 represents a group having at least absorption at 248 nm, W represents an alkyl group, and Z' and L, W and L' may be bonded to each other. The knot forms a 5 or 6 member ring. (2) The positive-type resist composition according to the above (1), wherein the resin (A1) contains a repeating unit represented by the formula (Γ), a repeating unit represented by the formula (Π), and a formula (III). Repetitive unit,

Wherein L and L' each independently represent a hydrogen atom, an alkyl group or an aralkyl group, Z2 represents a heterocyclic group, X represents an alkylene group having 1 to 20 carbon atoms, Y represents a divalent linking group, and η represents 0 or 1 W. Indicates an alkyl group, 1314251 Z2 and L 'W and L, which can be bonded to each other to form a 5 or 6 membered ring. (3) The positive-type photoresist composition according to the above (1) or (2), which further comprises a (A 2) a resin which increases the solubility in an alkali developing solution by an acid action, and the resin Containing repeating units of the formula UV) and (V),

W' represents that the base y represented by the general formula (Y) is not 1 to 100, x, + y, and S100. Η

I - Ο A C0 - R4 ... (丫) ch3 wherein R4 represents a lower alkyl group having 1 to 4 carbon atoms. (4) A pattern forming method for forming a photoresist film by using the photoresist composition recorded in the above-mentioned item, and exposing and developing the photoresist film. [Effect of the Invention] The positive-type resist composition of the present invention has an excellent effect of not exhibiting a standing wave and having a good profile by containing a specific acid-decomposable resin. (4) Embodiment 1314251 [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. The positive resist composition of the present invention comprises (A1) a resin which increases solubility in an image forming liquid by an acid action, and which contains a repeating unit represented by the formula (1) and a formula (II) The repeating unit and at least one of the repeating units represented by the formula (ΠΙ) '(B) a compound which generates an acid by active light or radiation, and (C) a solvent. The components to be blended in the positive resist composition of the present invention are explained below. <<Resin (A)>> The positive resist composition of the present invention contains (A) a resin (A) (hereinafter also referred to as a component A) which increases the solubility in an alkali developing solution by an acid action. In the positive resist composition of the present invention, (A1) contains at least one of a repeating unit represented by the formula (I), a repeating unit represented by the formula (II), and a repeating unit represented by the formula (III). As resin (A),

Wherein L and L' each independently represent a hydrogen atom, an alkyl group or an aralkyl group, Z1 represents a group having at least absorption at 248 nm, W represents an alkyl group, and Z' and L, W and L' may be bonded to each other to form 5 Or 6-member ring. In the acid-decomposable resin (A) used in the present invention, the repeating unit of the formula (I) is preferably a repeating unit represented by the formula (r), particularly preferably a formula (I). The repeating unit shown, the repeating unit represented by the formula (II) and the mouth of the formula (111) are not repeated - early,

Wherein L and L each independently represent a hydrogen atom 'homogeneous or aryl-based Z 2 non-heterocyclic group. X represents an alkylene group having 1 to 20 carbon atoms. γ represents a divalent linking group. n means 0 or 1.

W represents an alkyl group. Z2 and L'W and L' may be bonded to each other to form 5 or 6 members - rim ^ 烷基 The alkyl group of 'L, L' &amp; W in the above formula may have a substituent such as methyl, ethyl or propyl. , isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, _5, octyl, dodecyl, etc. Alkyl or ring-based. The alkyl group which is, for example, an alkoxy group, a transalkyl group, an alkoxycarbonyloxy group, an alkylcarbonylamino group, an alkyl group, may have a peptide atom, a nitro group, an alkylcarbonylsulfonylamino group, an alkylthio group. And the like, preferably a carbon number of 丨2 or less -] 〇 - 1314251 L and L ' of the substituents which may have a substituent, such as an alkoxy group, a hydroxyl group, a halogen atom, a nitro 'fluorenyl group, a decyloxy group, The hydrazine residue, the sulfonylamino group, the alkylthio 'arylthio group, the porphin carbonyloxy group, the thiophene methylcarbonyloxy group, the pyrrolidone residue, and the like are preferably a carbon number 丨2. The following. The alkyl group having a substituent of L and L ' is, for example, a cyclohexylethyl group, an alkyl cordoxymethyl group, a carbonyloxyethyl group, an arylcarbonyloxyethyl group, an aralkyl forged oxy group B. Base, oxymethyl, aryloxymethyl, aralkoxymethyl, alkoxyethyl, aryloxyethyl, aralkyloxyethyl, alkylthiomethyl, arylthio Alkyl, aralkylthiomethyl, alkylthioethyl, arylthioethyl, aralkylthioethyl, and the like. The alkyl group in the group is not particularly limited, and may be any of a chain, a branch, and a ring. Further, a substituent such as the above alkyl group or alkoxy group may be further included. Examples of the above alkylcarbonyloxyethyl group may be a cyclohexylcarbonyloxyethyl group, a tert-butylcyclohexylcarbonyloxyethyl group, a n-butylcyclohexylcarbonyloxyethyl group or the like. The aryl group is also not particularly limited. For example, a general phenyl group, a xylyl group, a tolyl group, a cumyl group, a naphthyl group, a decyl group or the like has a carbon number of 6 to 14 and may further have the above alkyl group or alkane. a substituent such as an oxy group. Examples of the above aryloxyethyl group may be a phenoxyethyl group, a cyclohexylphenoxyethyl group or the like. The aralkyl group is also not particularly limited, and may be, for example, a benzyl group or the like. An example of the above aralkylcarbonyloxyethyl group may be a benzylcarbonyloxyethyl group or the like. -11 - 1314251 The aralkyl group of L and L in the formula may be, for example, 7 to 15 of a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenethyl group, and the like. Preferred substituents of the aryl group may be, for example, an alkoxy group, a hydroxyl group, a dentate atom 'nitro group, a decyl group, a decylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, an aralkylthio group or the like; The aralkyl group having a substituent may, for example, be an alkoxybenzyl group, a hydroxybenzyl group, a phenylthiophenethyl group or the like. The carbon number of the substituent which may have 1, and the arylalkyl group is preferably 1 or less. In the above formula (1), Z1 has a group which absorbs at least at 248 nm, and is a group which absorbs much at 248 nm, but the higher the absorption, the better. The group having a large absorption at 2 4 8 n m is, for example, a group having at least a benzene ring or at least a hetero ring, and preferably a group having a conjugated double bond (containing a parent group). For example, 'arylcarbonyl, heteroarylcarbonyl, condensed cyclic aryl, condensed cyclic heteroaryl, condensed cyclic arylcarbonyl, condensed cycloheteroarylcarbonyl and the like. Further, it is not limited to an aromatic ring such as a phenyl group, and a group having an absorption at 248 nm such as a hetero ring can be used. Further, in this case, it is more preferred to also contain a conjugated double bond (containing a carbonyl group). Z1 is preferably a group represented by -X-(Y)n-Z2, and the repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (I'). In the general formula (I'), specific examples of the exudation group having a carbon number of 1 to 20 and preferably 1 to 1 Å of X are a methylene group, an ethyl group, a propyl group, a butyl group, and a stretching group.戊基, 己己基, 伸庚基's extension of octyl, exfoliation, exfoliation and so on. Among them, an ethyl group, a propyl group, a butyl group and the like are preferred. The above alkylene group may have a substituent, and examples of the substituent thereof are a methyl group, a -12-1314251 ethyl group, a propyl group, a butyl 'phenyl group, a tolyl group, a cyclohexyl group and the like. The above heterocyclic ring of Z2 may have a substituent such as sulfuric acid thiophene, thiophene, furan, pyrrole, benzothiophene, benzofuran, dioxin, imipenem, benzopyrene, three π sitting, Salivation of diterpenoids, etc., as long as it is generally referred to as a heterocyclic structure (a ring of carbon and a hetero atom or a ring formed by a hetero atom), and is not particularly white &lt; and in 'Z2, The above heterocyclic group may have a substituent, a group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, and a hydroxy group. An alkoxycarbonyl group such as an alkoxycarbonyl group or an ethoxycarbonyl group such as a propoxyl group, an isobutoxy group, a second butoxy group or a third butoxy group; or an aralkyl group such as a benzyl group or a phenethyl group; An alkoxy group, a mercapto group, a fluorenyl group such as a fluorenyl group, a fluorenyl group such as a fluorenyl group; An allyloxy-butenoxyoxy group, an aryloxy group such as the above aryl group or a phenoxy group, or a benzyloxy oxime group. The divalent linking group of Y may be, for example, -〇-C(=0)-, -0-, -S--S0-'-Se-, and an alkylene group having 1 to 4 carbon atoms. They can be used individually or in combination. An example of the divalent linking group of Y is preferably -0-C (= 0)-, -0 S02-, -Se-, -0-C(=0)-CH2-. Z1 (or Z2) and L, or W and L' are bonded to each other to form 5 or, for example, a tetrahydropyran ring or a tetrahydrofuran ring. The resin (A 1 ) preferably has a t-restriction of 5 to 60 olefins, cyclotetramethylene, benzothiazole, and pyridine in all repeating units. For example, aryl, -S〇2-, or two or more 6-membered rings of alkane S-n-butoxy group, methoxypropyl phenyl G benzyl fluorenyl group, or the like Ear % (compared

I 1314251 preferably 5 to 30 moles of a repeating unit represented by the formula (1), preferably a repeating unit represented by the formula (r), a formula (II) of 5 to 60 mol% (preferably 5 to 30 mol) The repeating unit shown, 20 to 80 mol% (preferably 40 to 80 mol%) of the repeating unit represented by the formula (III) may further contain other repeating units. The content ratio of the repeating unit represented by the formula (1) or (I,) to the repeating unit represented by the formula (11) in the resin (Α1) is preferably 〇.1〇:1~ 1:0.10, more preferably 0.25:1 to 1:0.25. The resin (A 1 ) of the present invention can be obtained, for example, by dissolving a polymer having a phenolic hydroxyl group in an organic solvent, removing the water in the system by a method such as azeotropic distillation, and then removing the water in the phenolic hydroxyl group. Obtained by introducing the desired acetal group. The polymer having a phenolic hydroxyl group, preferably a hydroxystyrene polymer, may be an acid-decomposable (meth) acrylate copolymer such as a third butyl acrylate or a third butyl methacrylate. . Further, in order to adjust the alkali solubility of the resin (A 1 ), a non-acid-decomposable group can be introduced into a polymer having a phenolic hydroxyl group. The method of introducing the non-acid-decomposable group is preferably a method of copolymerizing styrene, non-acid-decomposable (meth) acrylate, non-acid-decomposable decyl (meth) acrylate, or A method in which an acid-decomposable substituent protects a hydroxyl group of a hydroxystyrene. The substituent of the above non-acid-decomposable group is preferably an ethyl fluorenyl group, a decyl group or a tolsulfonyl group, but is not limited thereto. The above styrenes are, for example, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, iodine, methylstyrene, dimethylstyrene 'ethylstyrene, isopropylstyrene , methoxystyrene, ethoxy 1314251 { phenylethyl benzene, phenyl styrene 't-butyl styrene, third butoxy benzene sulphonate benzene, styrene, benzene benzene, Tributyl styrene, third butoxy styrene. The non-acid-decomposable (meth) acrylates are, for example, (meth)acrylic acid methyl ketone, ethyl (meth) acrylate 'propyl methacrylate, (meth) propyl sulphonic acid Propyl ester, glycidyl (meth)acrylate, benzyl (meth)acrylate, hydroxyethyl (meth)acrylate, and the like. The non-acid-decomposable decylamine (meth)acrylate is, for example, (meth)acrylic acid, phenylamine (meth)acrylate, or isopropylamine (meth)acrylate. Further, the copolymerizable monomer 'e.g. is a maleic acid derivative, a maleic acid wild derivative, (meth)acrylonitrile, vinyl pyrrolidone, vinyl pyridine, vinyl acetate or the like. When the alkali solubility of the resin (A1) is adjusted as described above, a copolymerization component and/or a non-acid-decomposable group may be introduced into the polymer having the above phenolic hydroxyl group insofar as the alkali developability is not impaired. From the viewpoint of dry etching resistance or sensitivity, 'the composition of the polymer having a hydrophobic base group is usually 60 mol% or more, preferably 70 mol% or more, based on the styrene component. The weight average molecular weight of the above dry polymer (polymer having a phenolic hydroxyl group) is measured by gel permeation chromatography (GPC), and the molecular weight (Mw) of polystyrene is preferably 2,000 to 200, 〇〇〇, Excellent 2,500~30,000. When the molecular weight is less than 200,000, it is preferable from the viewpoint of maintaining the solubility of the solution. The vinyl ether compound used in the acetalization reaction is preferably a compound represented by the following formula (A) which can give a unit represented by the formula (1), and a unit represented by the formula (II) can be obtained. The compound represented by the following formula (B) can give a compound represented by the following formula (C) which is a unit represented by the formula (Γ). , 〇/Ζι , enter 0&lt;Ζ2,. General formula (Α) Formula (Β) Formula (C) wherein Ζ, X, Y, Z2, W and η are each synonymous with the above. Specific examples of the compound of the formula (C) are ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, n-hexylethylene. Ether, benzyl vinyl ether, cyclohexyl ethyl vinyl ether, phenoxyethyl vinyl ether, cyclohexylphenoxyethyl vinyl ether ' 4 —carbonylcyclohexylphenoxyethyl vinyl ether, tert-butyl Cyclohexylcarbonyloxyethyl vinyl ether, cyclohexyl thioethyl vinyl ether, n-butylcyclohexylcarbonyloxyethyl vinyl ether, etc., but substantially acetalized with a phenolic hydroxyl group in the polymer Responders, without being limited to the above. Among the above, ethyl vinyl ether, n-propyl ether, isopropyl ether, n-butyl ether, isobutyl ether, tert-butyl ether, and cyclohexyl vinyl ether are preferred. The amount of the two or more vinyl ether compounds used in the reaction is preferably from 5 to 95 mol%, more preferably from 1 to 6 mol%, based on the phenolic hydroxyl group in the polymer having a phenolic hydroxyl group. 〇 耳 %, especially better 〖5~5 〇 Moer%. The organic solvent to be used in the reaction may be an inert solvent, and is not particularly limited, and examples thereof include propylene glycol methyl ether acetate (PGm®), 2-heptanone, and ethyl ethoxypropionate, methyl pyruvate. Ethyl pyruvate, tetrahydrofuran, and the like. Among them, PGMEA and 2-heptanone are preferred. The -16- 1314251 reaction solvent is usually used in an amount of from 1 to 10 parts by mass based on 100 parts by mass of the polymer having a phenolic hydroxyl group. The resin (A 1 ) may be used alone or in combination of two or more. Further, a combination of an acid-decomposable resin (a) synthesized by a polymer having a phenolic hydroxyl group having a phenolic hydroxyl group and a polymer having a phenolic hydroxyl group, and two or more different acetal protection ratios may be selected. A combination of an acid-decomposable resin or the like exhibits photoresist characteristics such as sensitivity, resolution, and contour. The synthesis of the resin (A1) is carried out by dissolving a polymer having a phenolic hydroxyl group in an organic solvent (a solvent inert to the acetalization reaction) previously shown, and optionally removing the moisture in the system by vacuum distillation, and adding Two or more vinyl ether compounds. Two or more kinds of vinyl ether compounds may be added at the same time or may be added in order. The acetalization can be carried out by the addition of an acidic catalyst. As the above acidic catalyst, for example, an inorganic acid or an organic acid can be used. The organic acid is preferably used in the absence of residual metal impurities, more preferably p-toluenesulfonic acid or p-toluenesulfonate pyridinium salt. In order to terminate the acetalization reaction, neutralization is preferably carried out with an alkali compound. From the standpoint of preventing the residual acid and the storage stability of the photoresist, the neutralization system is preferred. The alkali compound to be used is not particularly limited as long as it can neutralize the acid of the added catalyst, and the salt can be removed by a water washing step. The organic base compound is preferred because it does not leave a metal impurity. Specific examples thereof are triethylamine, trimethylamine, pyridine, aminopyridine 'piperidine, imidazole, etc., and particularly preferred are triethylamine and azidine. It is preferred to use ultrapure water to remove salts remaining in the system after the acetalization reaction is completed and after neutralization. -17- i1314251 In the formula (1), the specific examples of the group shown by the -O-CHahO-Z1 are as follows.

-18 - 1314251

-19- 1314251

-20 - 1314251 Η —〇--

Ch3 Η one ο — CH3 Ν

-21 - 1314251

Specific examples of the repeating unit constituting the resin (A 1) of the present invention are as follows. -22- 1314251

-23 - 1314251

-24 - 1314251

-25 - 1314251

I

In the present invention, as the resin of the component (A), in addition to the above resin (Al), it is preferred to further contain a repeating unit represented by the formula (IV) and a repeating unit represented by the formula (V) by an acid action. A resin (A2) which increases the solubility in an alkali developing solution. -26 - 1314251

(IV) (V) In the formulae (IV) to (v), w' represents a group represented by the following formula (Y). X, y, each represents 1 to 100, but x'+y, S1〇〇.

Η—Ο—C—Ο—R4 ...(Y)

I ch3 In the formula (Y), R4 represents a lower alkyl group having 1 to 4 carbon atoms. Hereinafter, the resin (A2) will be described in detail.

In the formula (IV), W' is a group represented by the above formula (Y); and in the formula (Y), a lower alkyl group having 1 to 4 carbon atoms of R4 is, for example, a methyl group, an ethyl group, or a positive group. Propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl and the like. Specific examples of the group represented by the formula (Y) are as follows, but are not limited thereto. -27-1314251 1 '0-C - 0 - CH2CH3 1 - 0 - C - 0 - CH2CH2CH3 ch3 ch3 Η CH3 H j I 1 —0 — C—〇一CH9 ] j —0—C — 0 — CH2CH2CH2CH3 ch3 ch3 CH3 H 9Hs H CH3 . 1 1 1 1 —〇一 C — 0 — CH2CH—CH3 C —0—CH—CH2 —CH3 j ch3 ch3 H CH3 j 1 H j I 1 —〇一 C —〇一 C — CH3 1 j —0 — C — 0—CH3 1 ch3 ch3 ch3

The specific configuration of the structural unit represented by the above formula (IV) is as exemplified below, but the invention is not limited thereto. -28 - 1314251

B ’ I V

The resin (A2) of the present invention may further contain a repeating unit represented by the formula (IV) in addition to the repeating unit represented by the formulae (IV) to (V). -29- 1314251 , %

(VI) In the formula (VI), R6 represents a hydrogen atom or a methyl group, and R7 represents an alkyl 'aryl group or an aralkyl group. Z' represents 0 to 100 (wherein X, y', x' + y' + z' g 1 〇〇 with respect to the formula (ιν), (ν)). Specifically, 'R7' represents a linear, branched alkyl group and a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, and an aralkyl group which may have a substituent. The linear alkyl group or the branched alkyl group of R7 is preferably a carbon number of from 1 to 30, more preferably from 1 to 2, such as methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutylene. Base, tert-butyl, n-pentyl 'isopentyl, third pentyl, n-hexyl, isohexyl, tert-hexyl, n-heptyl, isoheptyl, third heptyl, n-octyl, isooctyl , Orthodecyl, isodecyloctyl, n-decyl, isodecyl, third, third, n-decyl, iso-decyl, n-dodecyl, iso-t- 12, n- thirteen Basis, isotridecyl, n-tetradecyl, isotetradecyl, n-pentadecyl, isopentadecyl, n-hexadecyl, isohexadecyl, n-heptadecyl, iso-heptyl, n-eight Basis, iso-octadecyl, n-xyl-based, iso-nine, and the like. The cycloalkyl group of R7 is preferably a carbon number of 3 to 3 Å, more preferably 3 to 2 Å, and may be a ring-based group having a substituent at the time of forming a ring of carbon to 20, such as a cyclopropyl group or a cyclobutyl group. 'h-pentyl' cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cyclo-ring 'cyclo"cyclotridecyl, cyclotetradecyl, cyclooctyl, cyclohexadecyl Cyclodecyl, cyclohexadeta-cyclohexyl, -30 - 1314251, 4-cyclohexylcyclohexyl, 4-n-hexylcyclohexyl, pentenylcyclohexyl, hexyloxycyclohexyl, pentenyloxy Cyclohexyl and the like. A substituted cycloalkyl group other than these may be used as long as it is within the above range. The aryl group of R7 is preferably a carbon number of 6 to 30, more preferably a carbon number of 6 to 2, such as a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, or 4 -ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4-n-propylphenyl, 3-n-propyl benzyl, 2-n-propyl benzyl, 4-isopropyl basic, 3 -isopropylphenyl, 2-isopropylphenyl, 4-cyclopropylphenyl, 3-cyclopropylphenyl, 2-cyclopropylphenyl, 4-n-butylphenyl, 3-正Butylphenyl, 2-n-butylphenyl, 4-isobutylphenyl, 3-isobutylphenyl, 2-isobutylphenyl, 4-tert-butylphenyl, 3-third Butylphenyl, 2-tert-butylphenyl, 4-cyclobutylphenyl, 3-cyclobutylphenyl, 2-cyclobutylphenyl, 4-cyclopentylphenyl, 4-cyclohexyl Phenyl, 4-cycloheptylphenyl, 4-cyclooctylphenyl, 2-cyclopentylphenyl, 2-cyclohexylphenyl, 2-cycloheptylphenyl, 2-cyclooctylphenyl, 3-cyclopentylphenyl, 3-cyclohexylphenyl, 3-cycloheptylphenyl, 3-cyclooctylphenyl, 4-cyclopentyloxyphenyl, 4-cyclohexyloxyphenyl, 4 - cycloheptyloxyphenyl, 4-cyclooctyloxyphenyl, 2-cyclopentyloxyphenyl, 2-cyclohexyloxy Phenyl, 2-cycloheptyloxyphenyl, 2-cyclooctyloxyphenyl, 3-cyclopentyloxyphenyl, 3-cyclohexyloxyphenyl, 3-cycloheptyloxyphenyl, 3- Cyclooctyloxyphenyl, 4-n-pentylphenyl ' 4-n-hexylphenyl, 4-n-heptylphenyl, 4-n-octylphenyl, 2-n-pentylphenyl, 2-n-hexyl Phenyl, 2-n-heptylphenyl, 2-n-octylphenyl, 3-n-pentylphenyl, 3-n-hexylphenyl, 3-n-heptylphenyl, 3-n-octylphenyl, 2,6-diisopropylphenyl, 2,3 diisopropylphenyl, 2,4-diisopropylphenyl, 3,4-diisopropylphenyl, 3,6-diisobutyl Phenyl, 2,3-di-tris-31 - 1314251 / butylphenyl, 2,4-di-tert-butylphenyl, 3,4-di-tert-butylphenyl, 2,6-di-n-butylphenyl, 2,3-di-n-butylphenyl, 2,4-di-n-butylphenyl, 3,4-di-n-butylphenyl, 2, 6-Di-isobutylphenyl, 2,3-di-isobutyl, 2,4-di-isobutyl, 3,4---isobutylphenyl, 2,6-di- Third amylphenyl, 2,3-di-third amylphenyl, 2,4-di-third amylphenyl, 3,4-di-third amylphenyl, 2,6- Di-isoamylphenyl, 2,3---isopentyl Base, 2,4 - _-isopentylphenyl, 3,4 - _-isopentylphenyl, 2,6-di-n-pentylphenyl, 2,3-di-n-pentylphenyl, 2,4-di-n-pentylphenyl, 3,4-di-n-pentylphenyl, 4-adamantylphenyl, 2-adamantylphenyl, 4-isobornylphenyl, 3- Isobornylphenyl, 2-isobornylphenyl, 4-cyclopentyloxyphenyl, 4-cyclohexyloxyphenyl, 4-cycloheptyloxyphenyl, 4-cyclooctyloxyphenyl, 2-cyclopentyloxyphenyl, 2-cyclohexyloxyphenyl, 2-cycloheptyloxyphenyl, 2-cyclooctyloxyphenyl, 3-cyclopentyloxyphenyl, 3-cyclohexyloxy Phenylphenyl, 3-cycloheptyloxyphenyl, 3-cyclooctyloxyphenyl, 4-n-pentyloxyphenyl, 4-n-hexyloxyphenyl, 4-n-heptyloxyphenyl, 4- n-Octyloxyphenyl, 2-n-pentyloxyphenyl, 2-n-hexyloxyphenyl, 2-n-heptyloxyphenyl, 2-n-octyloxyphenyl, 3-n-pentyloxyphenyl , 3-n-hexyloxyphenyl, 3-n-heptyloxyphenyl, 3-n-octyloxyphenyl, 2,6-di-isopropoxyphenyl' 2,3-di-isopropoxy Phenyl, 2,4-di-isopropoxyphenyl, 3,4-di-isopropoxyphenyl, 2,6-di-t-butoxyphenyl, 2,3- - a third butoxyphenyl group, a 2,4-di-t-butoxyphenyl group, a 3,4-di-t-butoxyphenyl group, a 2,6-di-n-butoxyphenyl group, 2,3-di-n-butoxyphenyl, 2,4-di-n-butoxyphenyl, 3,4-di-n-butoxyphenyl, 2,6-di-isobutoxybenzene , 2,3-di-isobutoxyphenyl, 2,4-di-isobutoxyphenyl '3,4- -32 - 1314251 di-isobutoxyphenyl, 2,6 -di - a third pentyloxyphenyl group, a 2,3-di-pivaloxyphenyl group, a 2,4-di-pivaloxyphenyl group, a 3,4-di-pentyleneoxyphenyl group , 2,6-di-isopentyloxyphenyl, 2,3-di-isopentyloxyphenyl, 2,4--isopentyloxy, 3,4---isopentyloxyphenyl , 2,6 - _-n-pentyloxyphenyl, 2,3-di-n-pentyloxyphenyl, 2,4-di-n-pentyloxyphenyl, 3,4-di-n-pentyloxy Phenyl, 4-adamantyloxyphenyl, 3-adamantyloxyphenyl, 2-goldenyloxy, 4-isobornyloxy, 3-isobornyloxyphenyl, 2-isobornyl The oxyphenyl group or the like may be substituted as long as it is within the above range, and is not limited to the substituents other than the above examples. The aralkyl group of R7 is preferably a carbon number of from 7 to 30, more preferably a carbon number of from 7 to 20, such as phenethyl, 4-methylphenethyl, 3-methylphenethyl or 2-methylphenylethyl. Base, 4-ethylphenethyl, 3-ethylphenethyl, 2-ethylphenethyl, 4-n-propylphenethyl, 3-n-propylphenethyl, 2-n-propylbenzene Ethyl, 4-isopropylphenethyl, 3-isopropylphenethyl, 2-isopropylphenethyl, 4-cyclopropylphenethyl, 3-cyclopropylphenethyl, 2- Cyclopropylphenethyl, 4-n-butylphenethyl, 3-n-butylphenethyl, 2-n-butylphenethyl, 4-isobutylphenethyl, 3-isobutylbenzene Base, 2-isobutylphenethyl, 4-t-butylphenethyl, 3-t-butylphenethyl, 2-t-butylphenethyl, 4-cyclobutylphenethyl, 3-cyclobutylphenethyl, 2-cyclobutylphenethyl, 4-cyclopentylphenethyl, 4-cyclohexylphenethyl, 4-cycloheptylphenethyl, 4-cyclooctylbenzene Ethyl '2-cyclopentylphenethyl, 2-cyclohexylphenethyl, 2-cycloheptylphenethyl, 2-cyclooctylphenethyl, 3-cyclopentylphenethyl, 3-ring Hexyl phenylethyl, 3-cycloheptylphenethyl, 3-cyclooctylphenethyl, 4-cyclopentyloxybenzene , 4-cyclohexyloxyphenethyl, 4-cycloheptyloxyphenethyl ' 4 -cyclooctyloxyphenethyl, -33 - 1314251 2 -cyclopentyloxyphenethyl, 2-cyclohexyl Oxyphenethyl, 2-cycloheptyloxyphenethyl, 2-cyclooctyloxyphenethyl, 3-cyclopentyloxyphenethyl, 3-cyclohexyloxyphenethyl, 3-cycloheptane Oxyphenethyl, 3-cyclooctyloxyphenethyl, 4-n-pentylphenethyl, 4-n-hexylphenethyl, 4-n-heptylphenethyl, 4-n-octylphenethyl , 2-n-pentylphenethyl, 2-n-hexylphenethyl, 2-n-heptylphenethyl, 2-n-octylphenethyl, 3-n-pentylphenethyl, 3-n-hexylbenzene Ethyl, n-heptylphenethyl, 3-n-octylphenethyl, 2,6-diisopropylphenethyl, 2,3 diisopropylphenethyl, 2,4-diisopropyl Phenylethyl, 3,4-diisopropylphenethyl, 3,6-diisobutylphenethyl, 2,3-di-t-butylphenethyl, 2,4-di-third Butylphenethyl, 3,4-di-t-butylphenethyl, 2,6-di-n-butylphenethyl, 2,3-di-n-butylphenethyl, 2,4- Di-n-butylphenethyl, 3,4-di-n-butylphenethyl, 2,6-di-isobutylphenethyl, 2,3-di- Butylphenethyl, 2,4-di-isobutylphenethyl, 3,4-di-isobutylphenethyl, 2,6-di--3-pentylphenethyl, 2,3 -di-p-pentylphenethyl, 2,4-di-p-pentylphenethyl, 3,4-di-p-pentylphenethyl, 2,6-di-isoamylphenyl , 2,3-di-isopentylphenethyl, 2,4-di-isopentylphenethyl, 3,4-di-isopentylphenethyl, 2,6-di-n-pentyl Phenylethyl, 2,3-di-n-pentylphenethyl, 2,4-di-n-pentylphenethyl, 3,4-di-n-pentylphenethyl, 4-adamantylphenyl , 3-adamantylphenethyl, 2-adamantylphenethyl, 4-isobornylphenethyl, 3-isobornylphenethyl, 2-isobornylphenethyl, 4-ring Pentyloxyphenethyl, 4-cyclohexyloxyphenethyl, 4-cycloheptyloxyphenethyl, 4-cyclooctyloxyphenethyl, 2-cyclopentyloxyphenethyl, 2-ring Hexyloxyphenethyl, 2-cycloheptyloxyphenethyl, 2-cyclooctyloxyphenethyl, 3-cyclopentyloxyphenethyl, 3-cyclohexyloxyphenylethyl-34 - t 1314251

, 3-cycloheptyloxyphenethyl, 3-cyclooctyloxyphenethyl, 4-n-pentyloxyphenethyl, 4-n-hexyloxyphenethyl, 4-n-heptyloxyphenethyl , 4-n-octyloxyphenethyl, 2-n-pentyloxyphenethyl, 2-n-hexyloxyphenethyl, 2-n-heptyloxyphenethyl, 2-n-octyloxyphenethyl, 3-n-pentyloxyphenethyl, 3-n-hexyloxyphenethyl, 3-n-heptyloxyphenethyl, 3-n-octyloxyphenethyl, 2,6-di-isopropoxybenzene Ethyl, 2,3-di-isopropoxyphenethyl, 2,4-di-isopropoxyphenethyl, 3,4-di-isopropoxyphenethyl, 2,6-di - tert-butoxyphenethyl, 2,3-di-t-butoxyphenethyl, 2,4-di-t-butoxyphenethyl, 3,4·di-t-butoxy Phenylethyl, 2,6-di-n-butoxyphenethyl, 2,3-di-n-butoxyphenethyl, 2,4-di-n-butoxyphenethyl, 3,4 -di-n-butoxyphenethyl, 2,6-di-isobutoxyphenethyl, 2,3-di-isobutoxyphenethyl, 2,4-di-isobutoxybenzene Ethyl, 3,4-di-isobutoxyphenethyl, 2,6-di-pivaloxyphenethyl, 2,3-di-pivaloxyphenethyl, 2,4 -two-third Oxyphenethyl, 3,4-di-p-pentyloxyphenethyl, 2,6-di-isopentyloxyphenethyl, 2,3-di-isopentyloxyphenethyl, 2 ,4-di-isopentyloxyphenethyl, 3,4-di-isopentyloxyphenethyl, 2,6-di-n-pentyloxyphenethyl, 2,3-di-n-pentoxide Phenylethyl, 2,4-di-n-pentyloxyphenethyl, 3,4-di-n-pentyloxyphenethyl, 4-adamantyloxyphenethyl, 3-adamantyloxybenzene Ethyl, 2-adamantyloxyphenethyl, 4-isobornanyl basic ethyl, 3-isobornylphenethylethyl, 2-isobornyloxyphenethyl, or the above alkyl group via methyl, a substituent such as a propyl group or a butyl group, etc., and the other substituents of the above group include, for example, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, a decylamino group, the above alkyl group, and a methoxy group. 35 - ui425i base, ·&gt; ethoxy, ¥r base ~ branched ethoxy, propoxy, hydroxypropoxy, n-butoxy, ^. ~~ρ ^ oxo-oxyl, second Alkoxycarbonyl group such as butoxy group, third butoxy group, etc., such as alkoxy group, such as butoxy group, acetyl group, acetophenoxycarbonyl group, etc. Aralkyl, aralkoxy, indolyl, ethyl sulfonyl, butyl phthalate® I : &amp; sulfhydryl, hydrazine, etc., alkenyl, vinyloxy, benzoic acid An alkoxycarbonyl group such as an alkoxy group such as a butyl group or an oxyalkylene group. The substituent is an alkyl group having a carbon number of 2020, a carbon number of 3 to 2 〇, a phenol or the like. The above-mentioned reverse. The number of the alkyl group, the number of the lanthanum is extended... The aryl group of 6 to 20 or the carbon number is 7~ The 2 arylalkyl group is preferred. ^ &lt; ¢7 _ 1 BASE can have another substituent. In the case where the resin (A2) contains the resin represented by the above formula (VI), the resin is decomposed by the action of acid, and the enthalpy of enthalpy and _ in the alkali developing solution can be controlled. Further, by introducing the structural unit, it is possible to achieve a J wheel temple with excellent squareness. & _ ^ Further, the amount of the structural unit represented by the general formula (IV) can be effectively adjusted. Specific examples of the repeating unit represented by the general formula (VI) are as follows, but are not limited thereto.

-36 - 1314251

V spoon white B

3 C 2 Η C π2 c

c=o I 〇, ch2ch2ch2ch3

CH I CH3 The resin containing the structural unit represented by the general formula (V) and the general formula (VI) may be reacted with an acid anhydride in the presence of a base resin or a monomer thereof or in the presence of a base with a corresponding halide. The reaction is obtained. In the present invention, the resin (A2) having a group having an increase in solubility in an alkali developing solution by an acid action may contain a structure other than the above-described structures of the general formulae (IV) to (VI) -37 - 1314251 Other monomer units as a copolymerization component. In the present invention, x, y, and z of the resin (A 2) having a group which has a solubility in an alkali developing solution by an acid action preferably satisfy the following conditions. When z' = 0 (when there is no structural unit of the general formula (VI)) 0.05 &lt;x'/〇' + y') &lt;〇.5, more preferably 1&lt;χ, /(χ'+γ, ) &lt;0.45,. z&gt;〇(the structural unit having the general formula (VI)) (1) 0.10&lt;x'/(x,+ y, + z,) &lt;0 5〇, (2 ) 0.0 0 5 &lt; z ' / ( X ' + y, + z,) &lt; 〇 3 5, (3) x,&gt;z,, (4) 0·4&lt;χ'/(χ'+ζ') &lt;0·95, more preferably (1) 0.20&lt;x'/(x,+ y,+ z')&lt;〇.40, (2) 0.01&lt;z'/(x,+ y' + z ')&lt;〇.25, (3) x ' &gt; z ', (4) 0_5 &lt;x'/(x, + z') &lt; 〇.85, in the present invention, since the resin (A2) satisfies the above The condition, while improving the rectangularity of the profile', particularly improves the developmental defects. Moreover, x'+y'+z'=l〇〇. The repeating unit of the repeating unit represented by the formula (IV), the formula (V) and the formula (VI) or another polymerizable monomer may be present in the resin in combination of one kind or two or more kinds. Further, in order to maintain good solubility in the alkali developing solution in the resin contained in the positive resist composition of the present invention, it is also possible to introduce other polymerizable groups capable of introducing an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. Monomer copolymerization. -38 - 1314251 The molecular weight of the above resin (A2) is 2,000 or more, preferably 3,000 to 200,000, preferably 5,000 to 7 Å, 0 Å in terms of weight average molecular weight (Mw: polystyrene standard). Further, the degree of dispersion (Mw/Mn) is preferably 〜4·〇, 吏 is preferably 1.0 〜3 . 〇, the smaller the dispersion, the heat resistance, the image formation property (pattern profile 'defocus latitude The better, etc.) The content of the above resin (A2) in the positive resist composition (excluding the coating solvent) is preferably from 50 to 99% by mass, more preferably from 70 to 97% by mass. Specific examples of the repeating unit of the formula (IV) and the formula (V) constituting the resin (A2), and the repeating unit of the formula (IV) of the formula (V) and the formula (VI) are as shown in However, the invention is not limited thereto. 1314251 B ,

OH

-40- 1314251

Ch2ch2ch2ch3

Ch3

OH

-41 - 1314251

-42- 1314251

c=o I〇, CH2CH3

ό=〇 I〇, CH2CH2CH3

Ch3

-43 - I31425b1

In the present invention, the mixing ratio of the resin (A1) to (A2) which increases the solubility in the alkali developing solution by the action of acid is 0.1S(A1)/{(A1) + (A2)}S0_9 (mass Ratio) preferably 0.2S(A1)/{(A1) + (A2)}S0_8 (mass ratio) better 0.3S(A1)/{(A1) + (A2)}S0.7 (mass ratio) When it is more than 〇. 1 or more, it is preferable from the viewpoints of dry etching resistance, image performance (pattern profile, defocus latitude, etc.), and when the above mixing ratio is less than or equal to 9, from the viewpoint of shortening It is more suitable.

-44 - i i1314251 The content of the acid-decomposable resin (A) in the composition is usually 70 to 98% by mass, preferably 7 5 to 9 6 by mass based on the total solid content of the composition. %, better 8 0~9 6 mass%. <<Compound (B) Producing Acid by Active Light or Radiation Irradiation>> Hereinafter, a compound which generates an acid by active light or radiation irradiation (hereinafter sometimes referred to as "acid generator" "B component" which is usable in the present invention will be described. ). The acid generator usable in the present invention may be selected from a photocationic polymerization photoinitiator, a photoradical polymerization photoinitiator, a pigment photodecolorizer, a photochromic agent, or a microphotoresist. A compound which produces an acid and a mixture thereof when irradiated with active light or radiation. For example, it may be a diazonium salt, an ammonium salt 'scale salt, an iron iodide salt, a phosphonium salt, a selenium iron salt, an arsenic salt, or the like, an organic halogen compound, an organometallic/organic halide, an o-nitrobenzyl type protecting group. A compound represented by an acid generator, an iminosulfonate or the like which decomposes to generate a sulfonic acid compound or a diterpene compound. Further, the compound or the compound which generates an acid by active light or radiation irradiation is introduced into a polymer main chain or a side chain. For example, U.S. Patent No. 3,849,137, German Patent No. 3,9,407, Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound described in Japanese Laid-Open Patent Publication No. SHO-63-145, No. Sho. Further, an acid-producing compound which is exposed during the exposure described in the specification of the U.S. Patent No. 3,7,7,7,7,8, and the European Patent No. 1 2 6,7 1 2 can be used. -45- 1314251 Among the above-mentioned compounds which are decomposed by active light or radiation to cause acid generation, those which are particularly effective are as follows. (1) an iodonium salt represented by the following formula (PAG3) or a phosphonium salt represented by the formula (PAG4)

(PAG3)

R 203 r204_s+ ζ·

R 205·

(PAG4) wherein 'A r 1 and Ar 2 each independently represent a substituted or unsubstituted aryl group, and preferred substituents are, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, A carboxyl group, an alkoxycarbonyl group, a hydroxyl group, a thiol group, and a halogen atom. R2°3, R2°4, and R2°5 each independently represent a substituted or unsubstituted garden group or aryl group. Preferably, it is a aryl group having a carbon number of 6 to 14 and a carbon number of -8 to 8 and a substituted derivative thereof.

Preferred substituents for the aryl group are alkoxy groups having 1 to 8 carbon atoms, alkyl groups having 1 to 8 carbon atoms, nitro groups, carboxyl groups, hydroxyl groups and halogen atoms, and the substituent of the alkyl group is an alkyl group having 1 to 8 carbon atoms. An oxy group, a carboxyl group or an alkoxy group. Z-series mismatched anions, such as 8?4-, human 5?6-, 卩5'6-, 31)1; '6-' siF/, C10/, CF3s〇3, perfluoroalkanesulfonic acid anion A condensed polynuclear aromatic sulfonic acid anion such as a pentafluorobenzene acid extension anion or a naphthalene-1-sulfonic acid anion, an anthracene sulfonate anion, a sulfonic acid group-containing dye, or the like, but the present invention is not limited thereto. R2°3 'R2°4 and R205 two and six, Ar2 can be connected by a single bond or by taking -46 - 1314251. However, the present invention is not limited by the specific examples shown below.

Vt test cf3so? (PAG3-1) (PAG3-2)

f3chO-丨 @~O^cF3 cf3so3g (PAG3-5) CH3 ^CHa 4 (PAG3-7) ' ^ 〇 C^SOg U

-47 - 1314251 s® C-1^25

(PAG4-1)

(PAG4 -10) (PAG4-11)

(PAG4-13) (PAG4-H) The above-mentioned iron salts of the formula (PAG3) and (PAG4) are conventionally known, for example, by U.S. Patent No. 2,8,7,648 and U.S. Patent No. 4,247,473. It is synthesized by the method described in Japanese Patent Laid-Open Publication No. Sho. No. 5-1101, No. 3, No. 3, and the like. (2) an imino derivative represented by the following formula (PAG5) or an iminosulfonate derivative represented by the formula (PAG.6) -48 - 1314251.

People V

Ar3-S02-S02~Ar4 R206~SO2-〇-N (PAG6) (PAG5) wherein Ar3 and Ar4 each independently represent a substituted or unsubstituted aryl 〇R2°6 system Substituted or unsubstituted alkyl, aryl. The A group represents a substituted or unsubstituted alkylene group, an alkenyl group, and an extended aryl group. Specific examples are the compounds shown below, but the invention is not limited thereto. H3C~^^S〇2-S02&quot;Q-CH3 H3CO~^^~S〇2-S02-Q-〇CH3 (PAG5-1) (PAG5-2)

-49- 1314251 i ¥ N - 0 - S〇2 -. Ugly 3 (PAG6-5) (3) A diazonium derivative represented by the following formula (PAG7): 〇

芦-〇_S〇2 〇 Ο

(PAG6-4)

Onsno 1 R

R io=rsHO

G7) PA ./«V wherein R represents a linear, branched or cyclic alkyl group, or a substituted aryl group. Specific examples are as follows, but the invention is not limited thereto.

(PAG7-5) (4) Further, as the acid generator (A), a benzoquinone methyl hydrazine derivative represented by the following formula (I) can be used. -50 - 1314251

In the formula (υ, 1 5 represents no hydrogen atom, no more than a hydrogen atom, a hospital group, a oxy group, a nitro group, a halogen atom 'k oxygen 1 $ @ or ' h~r5) may be bonded to form a ring structural core and a hydrogen atom, an alkyl group, a cyano group or an aryl group. Y|S Υ2 represents an alkyl group, an aryl group, an arylalkyl group or a hetero atom-containing aromatic group which may be bonded to form a ring. Υ3 represents a single bond or a divalent linking group. Χ_ denotes a non-nucleophilic anion. R_~R5 at least one with Υ, or at least one of Υ2 may be bonded to form at least one of the rings' and at least one of Re or R7 may be bonded to form a ring 〇 Any one of them, or in a position from Υι or Υ2, may have two or more structures of the formula (I) via a knot bond. A specific example of the compound represented by the above formula (I) is shown below. This issue is limited by this.

-51 - 1314251

0

(1-2)

CFgSOg-

(1-3)

S〇 4SO3&quot; S+, C4F9SO3- (1-4)

C4F9SO3-·(1-9) o5 (1-6)

-52- 1314251 s+c4f9so3- 〇

〇 〇

s, C4F9SO3- (1-13) 〇

C4F 9SO3-

.OF F F F 0-16) Lu air1

Coo- (1-20) Ο ΓΛ CH3(CH2)7COO- (1-19)

S+ CF3SO3-(1-22) o C4F9S03- S+ C4F 9SO3- (1-24)

-53 - 1314251

(1-33)

(1-40) (Bu 41)

-54- 1314251 ο

Cbf17so3-

(1-43) (1-44)

(1-46) (Bu 47)

(1-50)

(1-52) (1-49) Among the compounds which generate an acid by irradiation with active light or radiation, those exemplified below are particularly preferred. -55 - 1314251

〇11 F23COO

S+ CF3CF2-O-CF2CF2SO3&quot; (z8) (z7)

56- 1314251

Or

(ζ13)

(ζ14) 2 (ζ17)

-57- 1314251

1314251 winter

(z30) (z3l) (z32)

MeO

(z 34)

CF3(CF2)3SO;t CF3{CF2)7S〇3- 36) z37) CF3(CF2)3S〇3- (z38) cf3(cf2)7so3- (z39)

(z 40)

-59- 1314251

CH2CHiCHJCH3 ch2ch2ch2ch3 Ming cf2)3so3, (ζ4η

P3C(CF2)3S〇3- (247). o ch2ch2ch2ch3 CH^CWHa f3c(cf2)3scv (242)

CH.CH^OH 'CHjCHjOH f3c(cf2&gt;3so3· (z43&gt;

A compound of one type or a combination of two or more types of (B) may be used. The content of the compound of the component (B) in the positive resist composition of the present invention is preferably from 0.1 to 20% by mass, more preferably from 0 to 5 to 10% by mass, based on the solid content of the composition. More preferably, it is 1 to 7 mass%. <<Solvent (C)>> The composition of the present invention is applied to a carrier by dissolving the above components and optional components described later in an organic solvent. The solvent to be used is preferably dichloroethylene, 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, methoxypropyl Methyl ester, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, hydrazine, hydrazine-dimethylformamide, dimethyl sulfoxide, hydrazine-methylpyrrolidine Ketone, tetrahydrofuran. These organic solvents can be used alone or in combination of two or more kinds of these -60 - 1314251 organic solvents. Among the above, preferred organic solvents are, for example, 2-heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and lactate. Ester, ethyl lactate 'methyl methoxypropionate, ethyl ethoxy propionate, Ν-methylpyrrolidone' tetrahydrofuran. "Other ingredients used in the present invention"

In the positive resist composition of the present invention, an alkali-soluble resin containing no acid-decomposable group may be blended in addition to the above-mentioned acid-based resin (a) as a resin component to improve sensitivity. The alkali-soluble resin (hereinafter abbreviated as alkali-soluble resin) containing no acid-decomposable group is a resin soluble in alkali, and is preferably a polyhydroxystyrene resin, a novolac resin, or the like. Further, the copolymer resin containing a p-hydroxystyrene unit can be used as long as it is alkali-soluble.

Among them, poly(p-hydroxystyrene), poly(p-/m-hydroxystyrene) copolymer, poly(p-/o-hydroxystyrene) copolymer, poly(p-hydroxystyrene/styrene) copolymer are preferably used. . Further, a poly(alkyl-substituted hydroxystyrene) resin such as poly(4-hydroxy-3-methylstyrene) or poly(4-hydroxy-3,5-dimethylstyrene) can be preferably used, The resin in which a part of the phenolic hydroxyl group of the above resin is alkylated or acetylated is as long as it is alkali-soluble. In addition, in the case of hydrogenation of a part of the nucleus of the above-mentioned resin (more than 30% by mole of all nucleus), it is preferable to improve the transparency, sensitivity, resolution and rectangular shape of the resin. of. In the present invention, the 'addition amount of the above-mentioned alkali-soluble resin containing no acid-decomposable group in the composition' is preferably 2 to 6 with respect to the total weight of the solid content of the composition of -61 - 1314251 ♦ 0% by weight, more preferably 5 to 30% by weight. The positive resist composition of the present invention may further contain an acid-decomposable dissolution-promoting compound, a dye, a plasticizer, a surfactant, a photosensitizer, a basic compound, and a solubility promoting effect on a developing solution, if necessary. Compound. (d) Fluorine-based and/or lanthanide-based surfactants. The positive-type photoresist composition of the present invention contains the above-mentioned (d) surfactants when used in an exposure light source of 250 nm or less, particularly 220 nm or less. A photoresist pattern with good sensitivity and low resolution, adhesion, and development defects can be given. (d) Surfactant (d) The surfactant is, for example, JP-A-62-3664, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950 Zha 63-34540, Special Kaiping 7-230 1 65, Special Kaiping 8-62 8 34, Special Kaiping 9-5443 No. 2, Special Kaiping 9-5 98 8 and Features 20〇2-277862, U.S. Patent No. 5,405, 720, U.S. Patent No. 5,360, 692, U.S. Patent No. 5, 527, 988, U.S. Patent No. 5, 296, 730, U.S. Patent No. 5, 436, 098, U.S. Patent No. 5,576, 143, U.S. Patent No. 5, 295, 151, U.S. As the surfactant described in the specification No. 1, the following commercially available surfactant can be used as it is. Commercially available surfactants which can be used include, for example, EF 3 0 1 , EF303 (manufactured by New Akita Chemicals Co., Ltd.), Floraton FC43 0, 431 (manufactured by Sumitomo 3M), and Mekafa克F171, F173, F176, F189, R08 (Daily Ink (share) system)' Safron S-382, SC101, 102, 103, 104, 105, 1〇6 (Asahi Glass Co., Ltd.), Dunlong A fluorine-based surfactant or a lanthanoid surfactant such as Sesoro S_366 (manufactured by Tatsuo Chemical Co., Ltd.). Further, polyfluorene-62- 4 1314251 oxyalkylene polymer KP-34 1 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a ruthenium-based surfactant. Further, as a surfactant, in addition to the above-mentioned known ones, a fluorine produced by a short-chain polymerization method (also referred to as a short-chain polymer method) or an oligomerization method (also referred to as a polymer-polymerization method) may be used. A polymer having a fluoroaliphatic group obtained by an aliphatic group. The fluoroaliphatic compound can be synthesized by the method described in JP-A No. 2,9-9.

As the polymer having a fluoroaliphatic group, a copolymer of a fluoroaliphatic group and a (poly(alkylene oxide)) acrylate and/or (polyalkylene oxide) methacrylate may be used. Irregular distribution or block copolymerization. Further, the poly(alkylene oxide) group is, for example, a poly(ethylene oxide) group, a poly(propylene oxide) group, a poly(butylene oxide) group, or the like, and may also be a poly(ethylene oxide and a ring). A unit of a pendant base having a different chain length within the same chain length of a base such as a block link of oxypropane. Further, the copolymer of a fluoroaliphatic group-containing monomer and a (poly(alkylene oxide)) acrylate (or methacrylate) is not only a bivalent copolymer but also different types of two or more. A ternary or higher copolymer of a fluoroaliphatic group or a copolymer of two or more (poly)(alkylene oxide) acrylates (or methacrylates). For example, commercially available surfactants may be, for example, Meika F1 78, F-470, F-473, F-476, and F-472 (manufactured by Dainippon Oil Chemical Co., Ltd.). Further, a copolymer of a C6F13 group-containing acrylate (or methacrylate) and (poly(alkylene oxide)) acrylate (or methacrylate) having a C6F13 group acrylate (or methacrylate) Copolymer with (poly(ethylene oxide)) acrylate (or methacrylate) and (poly(propylene oxide)) acrylate (or methyl propyl-63 - 1314251 enoate) with C8Fi7 a copolymer of acrylate (or methacrylate) and (poly(alkylene oxide)) acrylate (or methacrylate) having a C8F17-based acrylate (or methacrylate) and (poly( Ethylene oxide)) a copolymer of acrylate (or methacrylate) and (poly(propylene oxide)) acrylate (or methacrylate) and the like. (d) The amount of the surfactant to be used is preferably 0.0001 to 2% by mass, more preferably o.ooi to 1% by mass based on the total amount of the positive resist composition.

It is possible to use one kind or a combination of two or more kinds of the surfactants. In the positive resist composition of the present invention, (e) a basic compound can be used, and an organic basic compound is more preferable. Therefore, it is preferable because the stability of the storage is improved and the line change due to the PED (post-exposure delay) is small. The organic basic compound which can be preferably used in the present invention is a compound which is more basic than phenol. Among them, a nitrogen-containing basic compound is preferred. In a preferred chemical environment, for example, the following general formulae (A) to (E) are constructed. R251

R250-n-r252 (a) where R25°, R251 and R252 may be the same or different, each representing a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a carbon number of 6 to 2 经 substituted or not A substituted aryl group wherein R251 and R252 are interconnected to form a ring. -64- 1314251 a 0=Ν — ...(8) =C—N=C One (C) !=0一N — ...(D)

R 254 , 255 R253 • G—NI 1 —C—R256 (E) wherein R 2 5 3 , R 2 5 4 , R 2 5 5 , and R may be the same or different, each represents a carbon number of 1 to 6 alkyl. A preferred compound is a nitrogen-containing basic compound having two or more nitrogen atoms in different chemical environments in one molecule. More preferably, the nitrogen-containing test compound has a polycyclic structure. A preferred specific example of the nitrogen-containing polycyclic cyclic compound is a compound represented by the following formula (F).

In the formula (F), Y and Z each independently represent a linear, branched or cyclic alkyl group which may contain a hetero atom. The hetero atom is, for example, a nitrogen atom 'sulfur atom, oxygen atom. The extension base is, for example, a carbon number of 2 to 10's more preferably 2 to 5. The substituent of the alkylene group is, for example, an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a dentate atom or a halogen-substituted alkyl group. Further, specific examples of the compound represented by the formula (F) are as follows -65- 1314251 ·»

I,5-diazabicyclo[4.3.0]indole-5 is rare.

a nitrogen-containing basic compound having two or more nitrogen atoms in different chemical environments in one molecule, particularly preferably a compound having a substituted or unsubstituted amine group and a ring structure containing a nitrogen atom or a compound having an alkylamine group . Particularly preferred compounds are, for example, ruthenium, 1,1 - methylhydrazine, ruthenium, ruthenium, 3,3 -tetramethylguanidine, 2 -amino group, π-position, 3 -arm-based, D-, 4-amine Kela steep, 2 dimethyl dimethyl amide, 4 _ monomethylaminopyridine, 2-ethylaminopyridine, 2 _ (aminomethyl) pyridine, 2-amino-3- Methylpyridine, 2-amino-4-methylpyridinium, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-amino group Ethyl steep, 3-aminopyrrolidine, piperidine, aminoethyl) piperene, n-(2-aminoethyl) vein D, 4-amino-2,2,6,6- Tetramethyl piperidine, 4-piperidylpiperidine, 2-imino group? Pyridine, 1 2 -aminoethyl)pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-p-p-tolylpyrazole, pyridin, 2_( Aminomethyl)-5-methylpyridinium, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrazine, 2-pyrazoline, 3-pyrazoline, N-amino group Morpholine, N-(2-aminoethyl)morpholine, trimethylimidazole, triphenylimidazole, methyldiphenylimidazole, etc. are not limited by these. These basic compounds may be used singly or in combination of two or more. The amount of the basic compound to be used is usually 0.001 to 10 parts by weight, preferably 0. C by weight, based on 100 parts by mass of the component of the component. When the amount is 0.001 part by mass or more, the above effect can be obtained, and if it is 10 parts by weight or less, good sensitivity and development can be obtained. The compound which can be used in the present invention to promote dissolution in the developing solution is 1,0 00. Or a low molecular weight compound having a molecular weight of at least 2 phenolic hydroxyl groups or to a carboxyl group. In the case of a compound having a carboxyl group, an alicyclic or aliphatic compound is preferred for the same reason as described above. The amount of the compound which promotes solubility is from 2 to 50% by mass, more preferably from 5 to 30% by mass based on the polymer of the present invention, to prevent development of the residue and pattern distortion during development. The amount of the soluble compound to be added is preferably 50% by mass or less. The phenolic compound having a molecular weight of at least 1,000, for example, is described in the specification of the Japanese Patent Publication No. Hei 12-38, and the specification of the Japanese Patent Publication No. 49 1 62 1 、, and the European Patent No. 2 199 294. It is easy to synthesize for the skilled person. For example, resorcinol, phloroglucinol, 2,3,4-trihydroxydiphenyl 2,3,4,4, tetrahydroxybenzophenone, 2,3,4,3,4,5 ,-pentahydroxydiphenylacetone-pyrohydrin condensation resin, pyrogallol, 2,4,2,4,-diphenylpyran, 4,4'-thiobis(1,3-dihydroxy)benzene , 2,2',4,4,-tetrahydroxybis' 2,2',4,4'-tetrahydroxydiphenyl sulfite, 2,2',4,4'-tetrahydroxy quinone, ginseng 4-hydroxyphenyl)methane, -bis(4-hydroxyphenyl), cyclohexane 4,4-(α-methylphenylene)bisphenol, α,α,,α'parabenylphenyl)_ι II Isopropylbenzene, (^(^, ", '--(())-hydroxyphenylethyl-4_isopropyl" (solid 1~5. Also: 0 has less one shape, clear. 4- Lithic acid ketone, ketofurfuryl ether phenyl alkane, 3,5-benzene, -67- 1314251 1,2,2- cis (hydroxyphenyl) propane, ginseng (3,5_2 Methyl-4-hydroxyphenyl)propane, 2,2,5,5-indole (4-hydroxyphenyl)hexane, hydrazine, 2-indole (4-hydroxyphenyl) ethane ' 1,1,3 - cis(4-hydroxyphenyl)butane, p-[α,α,α',α,-肆(4-hydroxyphenyl)] -_Toluene, etc. Suitable dyes are oily dyes and basic dyes. Specific examples are oil leaf long # 1 0 1 , oil leaf long # 1 〇 3 'oil ratio cool # 3〗 2, oil Gulin BG, oil blue 0 S, 油布鲁# 6 0 3 ', 油布拉酷Β Υ, Oil Brake BS, Oil Brake Τ-5〇5 (above Ou Lide Chemical Industry Co., Ltd.), Crystal Violet (CI42555), Methyl Purple (CI42535), Rhodamine B (CI45170B), Malachite Green (CI42000), methyl blue (CI52015), etc. In order to increase the acid generation rate during exposure, the photo sensitizer exemplified below may be further added. Specific examples of the photosensitizer are benzophenone, p,p'-tetramethyldiaminobenzophenone, P,P'-tetraethylethylaminobenzophenone, 2-chlorothioxene Ketone, anthrone, 9-ethoxy hydrazine, hydrazine, hydrazine, phenanthrene, porphyrin, benzoin, acridine orange, benzoflavin, sedative-T, 9,10-diphenyl fluorene, 9-Eph, acetophenone, phenanthrene, 2-nitroindole, 5-nitroindole, benzoquinone, chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N- Ethyl 4-nitro-1-naphthylamine, bitter amine, hydrazine, 2-ethyl hydrazine, 2- Tributylphosphonium 1,2-anthracene 3-methyl-1,3-diaza-1,9-benzofluorenone, dibenzylideneacetone, 1,2-naphthoquinone, 3,3' - carbonyl-bis(5,7-dimethoxycarbonylcoumarin) and benzene, etc., but are not limited thereto. Further, the light sensitizer may also use a far-ultraviolet light absorber as a light source. In this case, the light absorbing agent reduces the reflected light from the substrate and reduces the influence of the multiple reflection of the photoresist film to exhibit the effect of the standing wave improvement. -68 - 1314251 The developing solution of the positive resist composition of the present invention can be an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate or ammonia. a primary amine such as propylamine; a secondary amine such as diethylamine or di-n-propylamine; a tertiary amine such as triethylamine or methyldiethylamine; or an alcoholamine such as dimethylethanolamine or triethanolamine. An amide such as melamine or acetamide, a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide; or an aqueous alkaline solution such as a cyclic amine such as pyrrole and piperidine (usually 〇. 1~1 〇 mass%). Further, in the above alkaline aqueous solution, an alcohol or an interface active agent may be added in an appropriate amount. EXAMPLES Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited thereto. [Synthesis Example X 1 ] &lt;Synthesis of 2-thienylmethylcarbonyloxyethyl vinyl ether (X-1)&gt; 100 g of thiophene-2-acetic acid was dissolved in 500 ml of DMAc (N, N-di) In methylacetamide, 31 g of sodium hydroxide was added at room temperature and stirred for a few minutes. 112 g of chloroethyl vinyl ether was added and stirred at 120 ° C for 2 hours (salt precipitation). Ethyl acetate and water were added to the reaction liquid, and liquid separation was carried out, and the mixture was washed three times with water. After drying the obtained organic phase, the above-mentioned subject (X-1) was obtained by concentration and distillation under reduced pressure. The subject matter was identified by N M R. [Synthesis Example X 2 ] &lt;Synthesis of Phenyloxyethyl Ethyl Ether (Χ-1)&gt; In the same manner as in Synthesis Example II-1 except that thiophenecarboxylic acid was used as a raw material, the above target was obtained. Object (X-2) ° -70 - 1314251

[Synthesis Example 3 J &lt;Synthesis of Ethyloxyethoxycarbonylnaphthalene (χ_3)&gt; The above subject matter was obtained by operating in the same manner as in the synthesis example π_丨 except that α-naphthalenecarboxylic acid was used as the raw material. X _ 3 ). [Synthesis Example X 4 ;] &lt;Synthesis of 2-thienylethylvinylether (χ_4)&gt; The same as the synthesis example ΙΙ-1 except that 2-thienyl lithium or 2-thienyl magnesium bromide was used as a raw material The above operation was carried out to obtain the above object (Χ-4).

[Synthesis Example 5] &lt;Synthesis of 2-furylcarbonyloxyethylvinylether (χ_5)&gt; The same procedure as in Synthesis Example 11-1 was carried out except that 2-furylcarboxylic acid was used as a raw material. Subject matter (X - 5). [Synthesis Example 6] &lt;Synthesis of 2-thienylthioethyl vinyl ether (χ-6)&gt;

The above-mentioned subject (Χ-6) was obtained by the same operation as in the synthesis example Η-1 except that 2-thienyl mercaptan was used as the starting material. The structure of the above-mentioned synthesized vinyl ether (X-1) to (Χ-6) is as follows. -71 -

1314251

Χ-5 ο

Χ-6

Synthesis Example 1 (Polymer having a phenolic warp group: Synthesis of Resin R 丨 )) 32.4 g (0.2 mol) of ethoxylated styrene was dissolved in 12 mL of methanol', and stirred under a nitrogen stream at 6 Hey. (: Add 〇. 3 3 g of azobisisobutyronitrile (A IB N ), continue stirring for 12 hours to carry out polymerization. Add dilute hydrochloric acid to the reaction to cut off the ethoxy group, and then steam under reduced pressure. Observe the steam to remove the volatiles. The obtained resin is dissolved again in! 5 liters of methanol, added to a large amount of water, this operation is repeated 3 times, and the obtained resin is dried in a vacuum dryer for 24 hours. Thus, poly(p-phenylphenethyl _-72-1314251, R-1) was obtained. The obtained resin had a weight average molecular weight of 15, 〇〇〇. Synthesis Example 2 (Polymer having a phenolic hydroxyl group: Resin r_2) Synthesis) According to the general method, 3 5.2 5 g (〇. 2 mol) of distilled purified di-butoxy ester and 2.42 g (0.0151 mol) of tributylstyrene were dissolved. In 100 ml of tetrahydrofuran, 0.033 g of azobisisobutyronitrile (AIBN) was added every three hours at 83 ° C, added three times, and finally stirred for 6 hours to carry out polymerization. The reaction solution was poured into 12 ml. 'White resin was precipitated in hexane. The obtained resin was dried and dissolved in 15 〇 ml of tetrahydrofuran, 4N hydrochloric acid was added thereto, and refluxed by refluxing for 6 hours, and then submerged into 5 liters of ultrapure water, and the resin was separated by filtration, washed with water, dried, and dissolved in 200 ml of tetrahydrofuran. 5 liters of ultrapure water was dripped with vigorous stirring, and reprecipitation was repeated. The reprecipitation operation was repeated 3 times. The obtained resin was dried in a vacuum drier at 60 ° C for 24 hours to obtain poly(p-hydroxybenzene). Ethylene/p-butyl butyl styrene) copolymer (resin R-2), the weight average molecular weight of the obtained resin was 1 〇, 〇〇〇. Synthesis Example 3 (Polymer having a phenolic hydroxyl group: Resin R- Synthesis of 3) 40 g (0.33 mol) of p-hydroxystyrene, 10.7 g (0.08 mol) of tributyl acrylate was dissolved in 50 g of dioxane, and 8 g of azobisisobutyronitrile (AIBN) was added. The mixture was heated and stirred at 60 ° C for 8 hours under a nitrogen stream. The reaction solution was poured into 1 200 ml of hexane to precipitate a white resin. The obtained resin was dried and dissolved in acetone in 5 liters of ultrapure water. Re-precipitate by dripping with vigorous stirring. Repeat the reprecipitation operation 3 The obtained -73 - 1314251 resin was dried in a vacuum drier at 60 ° C for 24 hours to obtain a poly(p-light styrene/p-butyl acrylate) copolymer (resin r_3), which was obtained. The weight average molecular weight of the resin was 2 1 , 0 0 〇. Synthesis Example 4 (Synthesis of Acid Decomposable Resin (a): Polymer A, _!) 150 g of poly(p-hydroxystyrene) manufactured by Nippon Soda Co., Ltd. (Resin R-4) (molecular weight 10000) was dissolved in 70 g of propylene glycol monomethyl ether acetate (PG ME A). The solution was depressurized to 20 mmHg at 60 ° C, and about 40 g of solvent remained in the system. The water is distilled away together. Cool to 20. (: So far, add 24% g of 1% p-toluenesulfonic acid in PGMEA solution, then add 9.0 g of ethyl vinyl ether' at room temperature for 1 hour. Next, 49 g of additionally synthesized 2-thienylcarbonyloxyl The vinyl ether (X-2) was added to the reaction mixture and stirred at room temperature for 1 hour. Then, 25 g of a 1% triethylamine in PGMEA solution was added to neutralize 'extract with 600 ml of ethyl acetate to 300 ml. Wash the water 3 times to get the polymer A ' -1 ^

Synthesis Examples 5 to 13 (Acid-decomposable resin (a): Synthesis of polymer A'_2 to A'-l 0) Using a polymer having a phenolic hydroxyl group (dry polymer) shown in Table 1 below, 2 An acid-decomposable resin was synthesized in the same manner as in Synthesis Example 4 except for the vinyl ether, to obtain polymers A'-2 to A, _12. Further, as the resin (C-1) for the comparative example, only one type of vinyl ether was used, and the mixture was synthesized in the same manner as above (ethyl ethanoic acid: 27 g, dry polymer R-1). -74 - 1314251 Table 1 Acid-decomposable polymer dry polymer (150 g) 1 gram of vinyl ether used) 2 g of vinyl ether used) Synthesis Example 5 Α'·2 R-2 X-2 (40) Ethyl vinyl ether (9·〇) Synthesis Example 6 Α,-3 R-3 X-2(35) Ethyl vinyl ether (7·〇) Synthesis Example 7 Α, _4 Rl X-6 (40) Ethylethylene Ether (9.0) Synthesis Example 8 Α, -5 R1 X-2 (49) Isobutyl vinyl ether (11·〇) Synthesis Example 9 Α,·6 Rl Xl (48) Ethyl vinyl ether (9.0) Synthesis Example 10 Α,-7 Rl X-5(47) Isobutyl vinyl ether (11.0) Synthesis Example 11 Α'-8 Rl Xl (47) Ethyl vinyl ether (9.0) Synthesis Example 12 Α, -9 Rl X-3 ( 35) Isobutyl vinyl ether (11.0) Synthesis Example 13 Α, -10 R-3 X-4 (25) Ethyl vinyl ether (17.0) Synthesis Example 14 Α,·11 R-4 X-2(60) B Vinyl ether (45.0) Synthesis Example 15 Α, -12 R-4 X-3 (25) _ Comparative Example 1 C-1 R1 - ethyl vinyl ether (27.0) Synthesis Example-14 (Synthesis of Resin B'-l In a flask, VP15000 (100 g) and propylene glycol monomethyl ether acetate (PGMEA) (4 g) manufactured by Nippon Soda were dissolved, distilled under reduced pressure, and water and PGMEA were removed by azeotropic distillation. After confirming that the water content was sufficiently lowered, ethyl vinyl ether (2 5.0 g) and p-toluenesulfonic acid (〇·〇 2 g) were added, and the mixture was stirred at room temperature for 1 hour. Triethylamine (3 g) was added to the reaction mixture to stop the reaction. Water (4 ml) and ethyl acetate (800 ml) were added, and the mixture was separated and washed with water. Distillation 1314251 j PG EA EA of ethyl acetate, water, and azeotropic component was removed to obtain an alkali-soluble resin B,-1 (3 Ο % PG EA EA solution) having a substituent according to the present invention. Synthesis Example-1 5 (Synthesis of Resin B, · 2) Polymerization of p-ethoxy styrene monomer (or pair) using 2,2'-azobisisobutyric acid dimethyl ester (AIBN) as an initiator The butoxystyrene monomer and the cyclohexyl acrylate monomer are deprotected with hydrochloric acid or the like to obtain a p-hydroxystyrene/cyclohexyl acrylate copolymer (9〇/i〇) r_4. Resin R-4 (1 gram) and propylene glycol monomethyl ether acetate (PGMEA) (4 gram) were dissolved in a flask to carry out vacuum distillation, and water and PGMEA were removed by azeotropic distillation. After confirming that the water content was sufficiently lowered, ethyl vinyl ether (25 g) and p-toluenesulfonic acid (0.02 g) were added, and the mixture was stirred at room temperature for 1 hour.

Triethylamine (0.03 g) was added to the reaction mixture, the reaction was stopped, water (40 ml) and ethyl acetate (800 ml) were added, and the mixture was separated, washed with water, and then evaporated to dryness under reduced pressure. Ethyl acetate, water, and azeotrope PGMEA' were obtained to obtain an alkali-soluble resin 8,-2 (30% PG EA EA solution) having a substituent according to the present invention. Synthesis Example-16 (Synthesis of Resin B'-3) The ethyl vinyl ether of Synthesis Example-14 was changed to isobutyl vinyl ether, and a resin B'-3 was obtained in the same manner as in the the the Synthesis Example-17 (Synthesis of Resin B'-4) The ethyl vinyl ether of Synthesis Example-14 was changed to a tert-butyl vinyl ether, and a resin B was obtained in the same manner as in Synthesis Example-1. 4. Each solution of the above-mentioned acid-decomposable resin was adjusted so that -76- 1314251 E in PG EA EA: a very strong standing wave [contour] was observed by SE Μ to observe the profile of the obtained pattern. Perform the following three levels of assessment. 1 : Rectangular 2 : Almost no cone is seen, but roughly rectangular 3 = obvious cone

1314251 %

〇7^8@Η3°-〇^80^ (D-2)

/^, 9 . ν2 ο . ΟΗ4-0 ο ο (D-3) The surfactant is: wl : Mekafak F176 (made by Dainippon Ink Chemical Industry Co., Ltd.) (Fluorine) W-2 : Mei Kappa R08 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) (fluorine and polyoxyalkylene) W-3 : polyoxyalkylene polymer ΚΡ-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

W-4: Polyethylene oxide phenyl ether W-5: Dunlong yello S-366 (made by Don Long Yi Chemical Co., Ltd.) W-6 : Mekafak F475 (Daily Ink Chemical Industry ( (Fly) (Fluorine) W-7: Copolymer with C6FI3 group and copolymer of (poly(propylene oxide)) acrylate and (poly(propylene oxide) methacrylate w_8: having C6F13 group The basic compound of acrylate and (poly(ethylene) and propyloxy and ethoxylated blocks) acrylate is: 80-

1314251 DBN: 1,5-diazabicyclo[4_3.0]non-5-ene DMAP : 4-indole, fluorene-dimethylaminopyridine 1:2,4,5-triphenylimidazolium: tri-n-butylamine oxime: tri-n-octylamine DCMA: dicyclohexylmethylamine DCEA: dicyclohexylethylamine. The results of Table 2 are known from the examples. The positive-type photoresist composition system can obtain the results of the satisfactory standing wave and the profile, respectively, and the optical t-resistance composition of the comparative example has a standing wave remaining and the profile is poor. ^ 81 -

Claims (1)

1314251 No. 92132662 / Application: J: Positive-type photoresist composition and pattern forming method using the same" (Amended on May 30, 2008) Pick-up, patent application scope: 1. A positive-type photoresist composition a resin comprising (Α) a resin which is decomposed by an acid to increase solubility in an alkali developing solution, a compound which generates an acid by irradiation with active light or radiation, and (C) a solvent; wherein (Α) a resin The content 'is 70 to 98% by mass based on the mass of the entire solid content of the composition; and the (Α) resin is a unit containing the formula (II) which is not repeating, and the formula (II) The repeating unit and the (Α1) resin of the repeating unit represented by the formula (III), and the weight average molecular weight (Mw: polystyrene standard) of the (Α1) resin is 2,000 to 200,000; (B) the content of the compound is relative to The mass of all the solid components of the composition is from 0.1 to 20% by mass; In the formulae (1'), (II), and (III), L and L' each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a third group. Base, Z2 represents ethylene sulfide, cyclotetrahydrothiophene, thiophene, furan, pyrrole, benzene 1314251 thiophene, benzofuran, benzopyrrole, triple trap, imidazole, benzimidazole, triazole, thiadiazole, thiazole, or Pyrrolidone, X represents methylene, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, Y represents -0-C (= 0). -〇-, -S-, -S〇2-, -SO-, -Se-, -0-C(=0)-CH2- &gt; n represents 0 or 1, W represents methyl, ethyl 'C Base, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, or dodecyl, Z2 and L, W and L' may be bonded to each other The knot forms a 5 or 6 member ring. 2. The positive-type resist composition according to claim 1, wherein the (A) resin is at least one of a repeating unit containing (A1) resin and having the formula (IV) and formula (V) ( A2) a resin, and the weight average molecular weight (Mw: polystyrene standard) of the (A2) resin is 3,000 to 200,000, and the content of (A1) + (A2) is relative to the mass of all solid components of the composition. The ratio is 70 to 98% by mass, and the mixing ratio of the resin (A1) to (A2) is 0·1 S (A1)/{(A1) + (A2)} S 0.9 (mass ratio); (IV) (V) In the formula (IV), (v), ^ 100 &gt; 1314251 W, the base y represented by the formula (γ) represents Uioo, X, +y Η I (Y) O—C— 〇—R4 where R4 does not represent the base of the carbon number 1~4. 3. A pattern forming method for forming a photoresist film by using a positive photoresist composition as follows: exposing and developing the photoresist film, and the positive photoresist composition comprises (A) by acid a resin which decomposes to increase the solubility in an alkali developing solution' (B) a compound which generates an acid by irradiation with active rays or radiation, and (C) a solvent; wherein (A) the content of the resin is relative to the composition The mass of all solid components of the material is '7 to 98% by mass; and (A) the resin is a repeating unit having the formula (I'), a repeating unit represented by the formula (II), and a formula ( (A1) Resin of the repeating unit shown in III), and the weight average molecular weight (Mw: polystyrene standard) of the (A1) resin is from 2,00 Å to 200,000; (B) the content of the compound relative to the composition The mass of all the solid components is 'o·1 to 20% by mass; (11), (III) (!!!) Formula (I' 1314251 L and L' each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl 'isopropyl group, a n-butyl group, an isobutyl group, or a tert-butyl group, and Z 2 represents Ethylene sulfide, cyclotetrahydrothiophene, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triterpene, imidazole, benzimidazole, triazole, thiadiazine, thiazole, or pyrrolidone, X represents methylene, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, and Y represents _〇.C( = 〇)-, _0_, _S_, _S〇", _S0_, .Se_, -oc(=o)-ch2·, n represents _0 or 1, W represents methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, a third butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, an octyl group, or a dodecyl group, and Z2 and L, W and L' may be bonded to each other to form a 5 or 6 membered ring. The pattern forming method of item 3, wherein the (A) resin is a resin containing (A1) resin and at least one of the repeating units represented by the general formula (IV) and the general formula (V), and (A2) resin Weight average molecular weight (Mw: poly The ethylene standard) is 3,000 to 200,000, and the content of (A1) + (A2) is 70 to 98% by mass based on the total solid content of the composition, and the resins (A1) and (A2) The mixing ratio is 0.1S (A1) / {(A1) + (A2)} S 0.9 (mass ratio); 1314251 In the formulae (IV) and (V), W' represents a group represented by the formula (Y), and X' and y' each represent 1 to 1 00, X' + y' S 1 00, Η - Ο - C~ ~ O—R4 ... (Y) I ch3 wherein R4 represents a hospital base having a carbon number of 1 to 4.