KR101036501B1 - Positive resist composition and patern forming method using the same - Google Patents

Abstract

(Problem) Provided is a positive resist composition having high antireflection substrate aptitude, generation of standing waves, and rectangular profile obtained.

(Solution) a specific repeating unit having on the side chain benzene ring -O-CH (L) -OZ ¹ (wherein Z ¹ represents a group having at least absorption at 248 nm, L represents a hydrogen atom, an alkyl group or an aralkyl group); , -O-CH (L ')-OW (W represents an alkyl group, L' represents a hydrogen atom, an alkyl group or an aralkyl group) at least one of a specific repeating unit and a hydroxystyrene repeating unit on the side chain benzene ring And a resin (A1) that decomposes under the action of an acid to increase its solubility in an alkaline developer, a compound (B) that generates an acid by irradiation with actinic light or radiation, and a solvent (C). Positive resist composition which consists of.

Description

Positive resist composition and pattern formation method using same {POSITIVE RESIST COMPOSITION AND PATERN FORMING METHOD USING THE SAME}

TECHNICAL FIELD This invention relates to the positive resist composition which can be used suitably for manufacture of a semiconductor integrated circuit element, the mask for integrated circuit manufacture, a printed wiring board, a liquid crystal panel, etc.

The initial chemically amplified positive resist composition composed of a photoacid generator and a resin protected with an acid-decomposable group is disclosed in, for example, Patent Document 1 (US Pat. No. 44,916,28). The chemically amplified positive resist composition generates an acid in the exposed portion by irradiation with radiation such as far ultraviolet light, and changes the solubility of the active radiation in the developer and irradiated portion of the irradiated portion by the reaction using the acid. To form a pattern on a substrate.

The positive resist composition containing resin protected by an acid-decomposable group is known variously until now, For example, in patent document 2 (Unexamined-Japanese-Patent No. 5-249682), the polyhydroxy protected by the alkoxy (acetal) group is known. As for a resist composition using a styrene resin, Patent Document 3 (Japanese Patent Laid-Open No. Hei 9-211866) discloses a resist composition using a polyhydroxy styrene resin protected with two other acid decomposers. Japanese Patent Application Laid-Open No. 2000-352822) discloses a resist composition using a resin protected by an acetal group having a heterocyclic group at the terminal via a linking group. Patent Document 5 (Japanese Patent Laid-Open No. 2002-49156) discloses two different acetal groups. Resist compositions using protected polyhydroxystyrene resins are disclosed.

However, the conventional positive resist composition is insufficient in high reflectivity substrate aptitude, and the standing wave remains strongly, and the improvement was calculated | required.

(Patent Document 1) US Patent No. 451628

(Patent Document 2) Japanese Patent Application Laid-Open No. 5-249682

(Patent Document 3) Japanese Patent Application Laid-Open No. 9-211866

(Patent Document 4) Japanese Patent Application Laid-Open No. 2000-352822

(Patent Document 5) Japanese Patent Application Laid-Open No. 2002-49156

An object of the present invention is to provide a chemically amplified positive resist composition in which high reflection substrate aptitude is good, generation of standing waves is suppressed, and a rectangular profile is obtained.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors achieved the said objective and reached completion of this invention with the positive resist composition containing two types of resin which has an acid-decomposable group of a specific structure.

That is, the positive resist composition which concerns on this invention is the following structure.                         

(1) At least one of the repeating unit represented by the following general formula (I), the repeating unit represented by the general formula (II), and the repeating unit represented by the general formula (III), and by the action of an acid A positive resist composition comprising a resin (A1) that decomposes to increase solubility in an alkaline developer, a compound (B) that generates an acid by irradiation with actinic light or radiation, and a solvent (C).

(In Formulas (I) to (III), L and L 'each independently represent a hydrogen atom, an alkyl group, or an aralkyl group; Z ¹ represents a group having at least absorption at 248 nm; W represents an alkyl group; Z ¹ And L, W and L 'may combine with each other to form a 5- or 6-membered ring.)

(2) In (1), Resin (A1) is a repeating unit represented by the following general formula (I '), a repeating unit represented by general formula (II), and a repeating unit represented by general formula (III) A positive resist composition, characterized in that it contains.

(Formula (I '), (II) , (III) of the, L and L' each independently represents a hydrogen atom, an alkyl group, or aralkyl group; Z ² represents a heterocyclic group; X is a carbon number of 1 to 20 An alkylene group, Y represents a divalent linking group, n represents 0 or 1, W represents an alkyl group, and Z ² and L, W and L 'may combine with each other to form a 5 or 6 membered ring. )

(3) Resin (A2) in (1) or (2) which decomposes by the action of an acid having a repeating unit represented by the following general formulas (IV) and (V) to increase its solubility in an alkaline developing solution. A positive resist composition further comprising.

(W 'represents a group represented by the following general formula (Y) in Formula (IV)-(V); x' and y 'represent 1-100, respectively, provided that x' + y '<= 100;

In formula (Y), R <^4> represents a C1-C4 lower alkyl group.)

(4) The pattern formation method characterized by forming a resist film by the resist composition in any one of (1)-(3), and exposing and developing the said resist film.

Hereinafter, the present invention will be described in detail.

In addition, in description of group (atom group) in this specification, the description which does not record substitution and unsubstitution includes what has a substituent as well as not having a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

The positive resist composition of the present invention contains at least one of a repeating unit represented by the general formula (I), a repeating unit represented by the general formula (II), and a repeating unit represented by the general formula (III), It contains the resin (A1) which decomposes by the action of an acid, and the solubility to alkaline developing solution increases, the compound (B) which generate | occur | produces an acid by irradiation of actinic light, or a radiation, and a solvent (C).

Hereinafter, each component mix | blended with the positive resist composition of this invention is demonstrated.

<< resin (A) >>

(A) resin

The positive resist composition of this invention contains resin (A) (henceforth A component) which decomposes by the effect of an acid, and the solubility to alkaline developing solution increases.

The positive resist composition of the present invention is at least one of a repeating unit represented by General Formula (I), a repeating unit represented by General Formula (II), and a repeating unit represented by (III) as resin (A). It contains resin (A1) containing.

(In formulas (I) to (III), L and L 'each independently represent a hydrogen atom, an alkyl group, or an aralkyl group; Z ¹ represents a group having at least absorption at 248 nm; W represents an alkyl group; Z ¹ And L, W and L 'may combine with each other to form a 5- or 6-membered ring.)

The acid-decomposable resin (A) used in the present invention is preferably a case where the repeating unit represented by the general formula (I) is a repeating unit represented by the following general formula (I '), and in particular, the following general formula (I') It is preferable to contain the repeating unit represented by the general formula (II), the repeating unit represented by the general formula (II), and the repeating unit represented by the general formula (III).

(Wherein L and L 'each independently represent a hydrogen atom, an alkyl group, or an aralkyl group; Z ² represents a heterocyclic group; X represents an alkylene group having 1 to 20 carbon atoms; Y represents a divalent linking group) N represents 0 or 1; W represents an alkyl group; Z ² and L, W and L 'may combine with each other to form a 5 or 6 membered ring.)

The alkyl groups of L, L 'and W in the general formula may have a substituent, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pen The C1-C20 linear, branched alkyl group, or cycloalkyl group, such as a methyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, an octyl group, and a dodecyl group, is mentioned.

Examples of the substituent which the alkyl group of W may have include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkylcarbonylamino group, a sulfonylamino group, an alkylthio group, and the like. Is 12 or less carbon atoms.

Examples of the substituent which the alkyl groups of L and L 'may have include an alkoxy group, hydroxyl group, halogen atom, nitro group, acyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, and aralkylthio group. Heterocyclic residues, such as a thiophene carbonyloxy group, a thiophene methyl carbonyloxy group, a pyrrolidone residue, etc. are mentioned, Preferably it is 12 or less carbon atoms.

The alkyl group having a substituent as L and L 'is, for example, cyclohexylethyl group, alkylcarbonyloxymethyl group, alkylcarbonyloxyethyl group, arylcarbonyloxyethyl group, aralkylcarbonyloxyethyl group, alkyloxymethyl group, aryloxymethyl group, Aralkyloxymethyl group, alkyloxyethyl group, aryloxyethyl group, aralkyloxyethyl group, alkylthiomethyl group, arylthiomethyl group, aralkyl thiomethyl group, alkylthioethyl group, arylthioethyl group, aralkylthioethyl group, etc. are mentioned.

Although the alkyl group in these groups is not specifically limited, Any of linear, branched, and cyclic | annular may be sufficient, and you may have substituents, such as the above-mentioned alkyl group and an alkoxy group, further.

Examples of the alkylcarbonyloxyethyl group include cyclohexylcarbonyloxyethyl group, tbutylcyclohexylcarbonyloxyethyl group, n-butylcyclohexylcarbonyloxyethyl group and the like.

Although aryl is not particularly limited, in general, those having 6 to 14 carbon atoms such as a phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthracenyl group are mentioned, and further have substituents such as the alkyl group and alkoxy group described above. Also good.

Examples of the aryloxyethyl group include phenyloxyethyl group, cyclohexylphenyloxyethyl group and the like.

Aralkyl is also not particularly limited, but benzyl groups and the like can be enumerated.

Examples of the aralkylcarbonyloxyethyl group include benzylcarbonyloxyethyl group and the like.

Examples of the aralkyl group of L and L 'in the general formula include those having 7 to 15 carbon atoms such as a substituted or unsubstituted benzyl group and a substituted or unsubstituted phenethyl group.

Preferred substituents on the aralkyl group include alkoxy groups, hydroxyl groups, halogen atoms, nitro groups, acyl groups, acylamino groups, sulfonylamino groups, alkylthio groups, arylthio groups, aralkylthio groups, and the like. For example, an alkoxy benzyl group, a hydroxyl benzyl group, a phenylthio phenethyl group, etc. can be mentioned. Preferably the range of carbon number of the substituent which an aralkyl group as L and L 'may have is 12 or less.

The group having at least absorption at 248 nm of Z ¹ in General Formula (I) may be any group having absorption at 248 nm, but the absorption is preferably higher.

A group having at least an absorption at 248 nm represents, for example, a group having one or more benzene rings or one or more hetero rings, but preferably a group further having a conjugated double bond (containing a carbonyl group).

For example, an arylcarbonyl group, heteroarylcarbonyl group, a cyclic aryl group, a condensed heteroaryl group, a cyclic arylcarbonyl group, a condensed heteroaryl carbonyl group, etc. are mentioned. Moreover, it does not need to be limited to aromatic rings, such as a phenyl group, Even if it is a hetero ring etc., it can be used if it is a group which has absorption of 248 nm. Moreover, also in this case, it is more preferable to have a conjugated double bond (containing a carbonyl group).

Z ¹ is preferably a group represented by -X- (Y) _n -Z ² , and a repeating unit represented by the general formula (I ') is preferable as the repeating unit represented by the general formula (I).

Specific examples of the alkyl group of 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms of X in general formula (I ′) include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group and heptylene group , Octylene group, nonylene group, decanylene group and the like. Especially, an ethylene group, a propylene group, butylene group, etc. are preferable.                     

The alkylene group may be substituted, and examples of the substituent include a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a tolyl group, a cyclohexyl group, and the like.

The hetero ring of Z ² may have a substituent, for example, tyran, cyclothiolan, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole Although, thiadiazole, thiazole, pyrrolidone, etc. are mentioned, It is not limited to these, if it is a structure (a ring formed with a carbon and a hetero atom, or a ring formed with a hetero atom) generally called a hetero ring.

Moreover, as a substituent which the said heterocyclic group in Z <^2> may have, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the said alkyl group, a methoxy group, an ethoxy group, hydroxyethoxy Alkoxy carbonyl groups, such as alkoxy groups, such as a methoxy propoxy group, a hydroxy propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, a methoxycarbonyl group, an ethoxy carbonyl group, a benzyl group, Aryl groups such as aralkyl groups such as phenethyl group and cumyl group, aralkyloxy groups, acyl groups such as formyl group, acetyl group, butyryl group, benzoyl group, cyanyl group and valeryl group, and acyloxy groups such as butyryloxy group and the above-mentioned alkenyl group Alkenyloxy groups, such as a vinyloxy group, a propenyloxy group, an aryloxy group, butenyloxy group, aryloxy groups, such as said aryl group and phenoxy group, and aryloxycarbonyl groups, such as a benzoyloxy group, are mentioned.

Examples of the divalent linking group for Y include -OC (= O)-, -O-, -S-, -SO _2- , -SO-, -Se-, an alkylene group having 1 to 4 carbon atoms, and the like. . These can be used individually or in combination of 2 or more types.

Examples of the divalent linking group of Y are preferably -OC (= 0)-, -O-, -S-, -SO _2- , -Se-, -OC (= 0) -CH ₂ .

Examples of the 5 or 6 membered ring formed by bonding of Z ¹ (or Z ² ) and L or W and L ′ to each other include tetrahydropyran ring, tetrahydrofuran ring and the like.

Resin (A1) is 5-60 mol% (preferably 5-30 mol%), and general formula of the repeating unit represented by general formula (I), Preferably general formula (I ') among all the repeating units. 5 to 60 mol% (preferably 5 to 30 mol%) of the repeating unit represented by (II), 20 to 80 mol% (preferably 40 to 80 mol%) of the repeating unit represented by General formula (III) ), And may contain other repeating units as necessary.

The content ratio ((I) :( II)) of the repeating unit represented by General Formula (I) or (I ′) and the repeating unit represented by General Formula (II) in the resin (A1) is preferably 0.10: 1-1: 0.10, More preferably, it is 0.25: 1-1: 0.25.

Resin (A1) of the present invention preferably dissolves a polymer having a phenolic hydroxyl group in an organic solvent, and dehydrates the water in the system by means of azeotropic distillation, or the like. It can be obtained by carrying out the acetalization reaction by addition and introducing a desired acetal group into the phenolic hydroxyl group.

As a polymer which has the said phenolic hydroxyl group, the polymer of hydroxy styrene is preferable, and the copolymer with acid-decomposable (meth) acrylate, such as t-butyl acrylate or t-butyl methacrylate, may be sufficient.                     

Moreover, a non-acid-decomposable group can also be introduce | transduced into the polymer which has a phenolic hydroxyl group in order to adjust the alkali solubility of resin (A1). As a method of introducing a non-acid-decomposable group, a method of copolymerizing styrenes, non-acid-decomposable (meth) acrylic acid esters and non-acid-decomposable (meth) acrylic acid amides, or protecting the hydroxyl group of hydroxystyrene with a non-acid-decomposable substituent The method is preferred.

As a substituent of the said non-acid-decomposable group, although an acetyl group, a mesyl group, a toluenesulfonyl group, etc. are preferable, it is not limited to these.

Examples of the styrenes include styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, iodine styrene, methyl styrene, dimethyl styrene, ethyl styrene, isopropyl styrene, methoxy styrene, ethoxy styrene, phenyl styrene and t Although -butyl styrene, t-butoxy styrene, etc. can be mentioned, Styrene, methyl styrene, t-butyl styrene, t-butoxy styrene is especially preferable.

As said non-acid-decomposable (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, (Meth) acrylate hydroxyethyl, etc. are mentioned.

Examples of non-acid-decomposable (meth) acrylic acid amides include (meth) acrylic acid amide, (meth) acrylic acid phenylamide, and (meth) acrylic acid isopropylamide.

Examples of the copolymerizable monomers include maleic acid derivatives, maleic anhydride derivatives, (meth) acrylonitrile, vinylpyrrolidone, vinylpyridine, vinyl acetate, and the like.                     

As mentioned above, although it is possible to introduce a copolymerization component and / or a non-acid-decomposable group into the polymer which has the said phenolic hydroxyl group in the range which adjusts the alkali solubility of resin (A1) and does not impair the alkali developability, In terms of dry etching resistance and sensitivity, it is preferable that hydroxystyrene components occupy 60 mol% or more, preferably 70 mol% or more among the components constituting the polymer having a phenolic hydroxyl group.

The weight average molecular weight of the stem polymer (polymer having a phenolic hydroxyl group) can be measured by gel permeation chromatography (GPC) as polystyrene reduced molecular weight (Mw), preferably 2000 to 200,000, and 2,500 to 30,000 This is particularly preferred. The molecular weight is 200,000 or less, so that the solubility is maintained and preferable in view of resolution.

As a vinyl ether compound used for an acetalization reaction, in order to obtain the unit represented by general formula (I), the compound represented by the following general formula (A) is obtained, and to obtain the unit represented by general formula (II), the following general formula It is preferable to use the compound represented by the following general formula (C) for obtaining the unit represented by general formula (I ') for the compound represented by (B).

(In General Formulas (A) to (C), Z ₁ , X, Y, Z ₂ , W, and n are the same as described above, respectively.)

As a specific example of a compound represented by general formula (C), ethyl vinyl ether, n- propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, n-hexyl vinyl Ether, benzyl vinyl ether, cyclohexyl ethyl vinyl ether, phenoxyethyl vinyl ether, cyclohexylphenoxyethyl vinyl ether, 4-carbonylcyclohexylphenoxyethyl vinyl ether, t-butylcyclohexylcarbonyloxyethyl vinyl ether, Cyclohexyl thioethyl vinyl ether, n-butyl cyclohexylcarbonyloxyethyl vinyl ether, etc. are mentioned, What is necessary is just to cause an acetalization reaction between the phenolic hydroxyl groups in a polymer substantially, and is not limited to the above. Among the above, ethyl vinyl ether, n-propyl ether, i-propyl ether, n-butyl ether, i-butyl ether, t-butyl ether and cyclohexyl vinyl ether are preferable.

As for the usage-amount of 2 or more types of vinyl ether compounds used in reaction, it is preferable to use 5 mol%-95 mol% with respect to the phenolic hydroxyl group in the polymer which has a phenolic hydroxyl group, More preferably, it is 10 mol% It is -60 mol%, More preferably, it is 15 mol%-50 mol%.

The organic solvent used for the reaction is not particularly limited as long as it is an inert solvent, but propylene glycol methyl ether acetate (PGMEA), 2-heptanone, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, tetrahydrofuran, etc. Can be enumerated. Especially, PGMEA and 2-heptanone are preferable.

As a reaction solvent, 100-1000 mass parts is normally used with respect to 100 weight part of polymers which have a phenolic hydroxyl group.

Resin (A1) can be used individually by 1 type or in combination of 2 or more types. Moreover, the combination of the acid-decomposable resin (a) synthesize | combined from the polymer which has the molecular weight and composition ratio of 2 or more types of phenolic hydroxyl groups from which a phenolic hydroxyl group differs, the combination of 2 or more types of acid-decomposable resins with different acetal protection rates, etc. are also sensitive. , Resolution, profile, and other resist properties can be selected.

Synthesis of resin (A1) dissolves the polymer which has a phenolic hydroxyl group in the organic solvent (solvent inactive to acetalization reaction) shown above, removes water in a system by distillation under reduced pressure, etc. as needed, and it is 2 or more types The vinyl ether compound is added. Two or more types of vinyl ether compounds may be added simultaneously, and may be added sequentially. Acetalization reaction advances by addition of an acidic catalyst.

The acidic catalyst may use both an inorganic acid and an organic acid. The organic acid is preferable because there is no residual metal impurity, and p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt, and the like are more preferable.

For the purpose of stopping the acetalization reaction, it is preferable to carry out neutralization with a base compound. Neutralization is preferable in view of storage stability of the resist by preventing acid from remaining. As a base compound used, what is necessary is just to neutralize the acid as an added catalyst, and to remove a salt by the water washing process, and it is not specifically limited. Among them, the organic base compound is preferable because there is no residual metal impurities, and specific examples thereof include triethylamine, trimethylamine, pyridine, aminopyridine, piperadine, imidazole and the like, and triethylamine and pyridine are particularly preferred. .

After completion of the acetalization reaction and neutralization, it is preferable to remove the salt remaining in the system using ultrapure water or the like.

Specific examples of the groups represented by -O-CH (L) -OZ ¹ in the formula (I) shown below, but are not limited to these.

The following are mentioned as a specific example of the repeating unit which comprises resin (A1) of this invention.

In the present invention, in addition to the above-mentioned resin (A1), the resin of the component (A) contains at least a repeating unit represented by the general formula (IV) and a repeating unit represented by the general formula (V). It is preferable to contain resin (A2) which decomposes | disassembles and solubility to alkali developing solution increases.

(W 'represents a group represented by the following general formula (Y) in Formula (IV)-(V); x' and y 'respectively represent 1-100. However, x' + y '<= 100.

(In formula (Y), R <^4> represents a C1-C4 lower alkyl group.))

Hereinafter, resin (A2) is explained in full detail.

In general formula (IV), W 'is group represented by the said general formula (Y), and R <^4> in general formula (Y) is a C1-C4 lower alkyl group as a methyl group, an ethyl group, n-propyl The group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, etc. are mentioned.

Although the specific example of group represented by general formula (Y) is shown below, it is not limited to these.

Although the specific structure of the structural unit represented by such a general formula (IV) is illustrated below, this invention is not limited to these.

Resin (A2) in this invention can further contain the repeating unit represented by the following general formula (VI) other than the repeating unit represented by the said general formula (IV)-(V).

In general formula (VI), R <^6> represents a hydrogen atom or a methyl group, R <^7> represents an alkyl group, an aryl group, or an aralkyl group, Z 'is 0-100 (however, x of Formula (IV), (V) x '+ y' + z '≦ 100 for', y '.

Specifically, R <^7> represents the linear, branched alkyl group and cycloalkyl group which may have a substituent, the aryl group which may have a substituent, and the aralkyl group which may have a substituent. As a linear or branched alkyl group of R <^7> , Preferably it is C1-C30, More preferably, it is C1-C20, For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i -Butyl group, t-butyl group, n-pentyl group, i-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, t-hexyl group, n-heptyl group, i-heptyl group, t -Heptyl group, n-octyl group, i-octyl group, t-octyl group, n-nonyl group, i-nonyl group, t-nonyl group, n-decanyl group, i-decanyl group, t-decanyl group, n Undecyl group, i-undecyl group, n-dodecyl group, i-dodecyl group, n-tridecyl group, i-tridecyl group, n-tetradecyl group, i-tetradecyl group, n-pentadecyl group, i Pentadecyl group, n-hexadecyl group, i-hexadecyl group, n-heptadecyl group, i-heptadecyl group, n-octadecyl group, i-octadecyl group, n-nonadecyl group, i-nona Decyl group etc. can be enumerated.

As a cycloalkyl group of R <^7> , Preferably it is 3-30, More preferably, it is C3-C20, Even when forming a ring with 20 carbon atoms, Cycloalkyl which has a substituent may be sufficient, For example, cyclopropyl group, Cyclo Butyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecanyl group, cycloundecyl group, cyclododecyl group, cyclotridecyl group, cyclotridecyl group, cyclotedecyl group, Cyclopentadecyl, cyclohexadecyl, cycloheptadecyl, cyclooctadecyl, cyclononadecyl, 4-cyclohexylcyclohexyl, 4-n-hexylcyclohexyl, heptanylcyclohexyl, A hexyloxycyclohexyl group, a fentanyloxycyclohexyl group, etc. are mentioned. Substituted cycloalkyl groups other than those listed here can also be used if they are within the above range.

As an aryl group of R <^7> , Preferably it is C6-C30, More preferably, it is C6-C20, For example, a phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3 -Ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 3-n-propylphenyl group, 2-n-propylphenyl group, 4-i-propylphenyl group, 3-i-propylphenyl group, 2-i-propylphenyl group , 4-cyclopropylphenyl group, 3-cyclopropylphenyl group, 2-cyclopropylphenyl group, 4-n-butylphenyl group, 3-n-butylphenyl group, 2-n-butylphenyl group, 4-i-butylphenyl group, 3-i -Butylphenyl group, 2-i-butylphenyl group, 4-t-butylphenyl group, 3-t-butylphenyl group, 2-t-butylphenyl group, 4-cyclobutylphenyl group, 3-cyclobutylphenyl group, 2-cyclobutylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4-cycloheptenylphenyl group, 4-cyclooctanylphenyl group, 2-cyclopentylphenyl group, 2-cyclohexylphenyl group, 2-cycloheptenylphenyl group, 2-cyclooctanyl Phenyl group, 3- Clopentylphenyl group, 3-cyclohexylphenyl group, 3-cycloheptenylphenyl group, 3-cyclooctanylphenyl group, 4-cyclopentyloxyphenyl group, 4-cyclohexyloxyphenyl group, 4-cycloheptenyloxyphenyl group, 4-cycloocta Nyloxyphenyl group, 2-cyclopentyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-cycloheptenyloxyphenyl group, 2-cyclooctanyloxyphenyl group, 3-cyclopentyloxyphenyl group, 3-cyclohexyloxyphenyl group, 3- Cycloheptenyloxyphenyl group, 3-cyclooctanyloxyphenyl group, 4-n-pentylphenyl group, 4-n-hexylphenyl group, 4-n-heptenylphenyl group, 4-n-octanylphenyl group, 2-n-pentylphenyl group , 2-n-hexylphenyl group, 2-n-heptenylphenyl group, 2-n-octanylphenyl group, 3-n-pentylphenyl group, 3-n-hexylphenyl group, 3-n-heptenylphenyl group, 3-n- Octanylphenyl, 2,6-di-isopropylphenyl group, 2,3-di-isopropylphenyl group, 2,4-di-isopropylphenyl group, 3,4-di-isopropylphenyl group, 3,6-di- t-butylphenyl group, 2,3-di-t-butylphenyl group, 2 , 4-di-t-butylphenyl group, 3,4-di-t-butylphenyl group, 2,6-di-n-butylphenyl group, 2,3-di-n-butylphenyl group, 2,4-di-n -Butylphenyl group, 3,4-di-n-butylphenyl group, 2,6-di-i-butylphenyl group, 2,3-di-i-butylphenyl group, 2,4-di-i-butylphenyl group, 3, 4-di-i-butylphenyl group, 2,6-di-t-amylphenyl group, 2,3-di-t-amylphenyl group, 2,4-di-t-amylphenyl group, 3,4-di-t- Amylphenyl group, 2,6-di-i-amylphenyl group, 2,3-di-i-amylphenyl group, 2,4-di-i-amylphenyl group, 3,4-di-i-amylphenyl group, 2,6 -Di-n-pentylphenyl group, 2,3-di-n-pentylphenyl group, 2,4-di-n-pentylphenyl group, 3,4-di-n-pentylphenyl group, 4-adamantylphenyl group, 2- Adamantylphenyl group, 4-isoboroylphenyl group, 3-isoboroylphenyl group, 2-isoboroylphenyl group, 4-cyclopentyloxyphenyl group, 4-cyclohexyloxyphenyl group, 4-cycloheptenyloxyphenyl group , 4-cyclooctanyloxyphenyl group, 2-cyclopentyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-cycloheptenyloxyphenyl group, 2-cyclooctanyloxy Phenyl group, 3-cyclopentyloxyphenyl group, 3-cyclohexyloxyphenyl group, 3-cycloheptenyloxyphenyl group, 3-cyclooctanyloxyphenyl group, 4-n-pentyloxyphenyl group, 4-n-hexyloxyphenyl group, 4 -n-heptenyloxyphenyl group, 4-n-octanyloxyphenyl group, 2-n-pentyloxyphenyl group, 2-n-hexyloxyphenyl group, 2-n-heptenyloxyphenyl group, 2-n-octanyloxyphenyl group , 3-n-pentyloxyphenyl group, 3-n-hexyloxyphenyl group, 3-n-heptenyloxyphenyl group, 3-n-octanyloxyphenyl group, 2,6-di-isopropyloxyphenyl group, 2,3- Di-isopropyloxyphenyl group, 2,4-di-isopropyloxyphenyl group, 3,4-diisopropyloxyphenyl group, 2,6-di-t-butyloxyphenyl group, 2,3-di-t-butyloxy Phenyl group, 2,4-di-t-butyloxyphenyl group, 3,4-di-t-butyloxyphenyl group, 2,6-di-n-butyloxyphenyl group, 2,3-di-n-butyloxyphenyl group, 2,4-di-n-butyloxyphenyl group, 3,4-di-n-butyloxyphenyl group, 2,6-di-i-butyloxyphenyl group, 2,3-di-i-butyloxyphenyl group, 2, 4-di-i-part Oxyphenyl group, 3,4-di-i-butyloxyphenyl group, 2,6-di-t-amyloxyphenyl group, 2,3-di-t-amyloxyphenyl group, 2,4-di-t-amyloxyphenyl group , 3,4-di-t-amyloxyphenyl group, 2,6-di-i-amyloxyphenyl group, 2,3-di-i-amyloxyphenyl group, 2,4-di-i-amyloxyphenyl group, 3 , 4-di-i-amyloxyphenyl group, 2,6-di-n-pentyloxyphenyl group, 2,3-di-n-pentyloxyphenyl group, 2,4-di-n-pentyloxyphenyl group, 3,4 -Di-n-pentyloxyphenyl group, 4-adamantyloxyphenyl group, 3-adamantyloxyphenyl group, 2-adamantyloxyphenyl group, 4-isoboroyloxyphenyl group, 3-isoboroyloxyphenyl group , 2-isoboroyloxyphenyl group, etc. are enumerated, These may further substitute, if it is in the said range, It is not limited to substituents other than the said example.

The aralkyl group of R ⁷ is preferably ⁷ to 30 carbon atoms, more preferably 7 to 20 carbon atoms, for example, a phenylethyl group, 4-methylphenylethyl group, 3-methylphenylethyl group, 2-methylphenylethyl group, 4-ethylphenylethyl group, 3-ethylphenylethyl group, 2-ethylphenylethyl group, 4-n-propylphenylethyl group, 3-n-propylphenylethyl group, 2-n-propylphenylethyl group, 4-i-propylphenylethyl group, 3-i-propylphenyl Ethyl group, 2-i-propylphenylethyl group, 4-cyclopropylphenylethyl group, 3-cyclopropylphenylethyl group, 2-cyclopropylphenylethyl group, 4-n-butylphenylethyl group, 3-n-butylphenylethyl group, 2-n -Butylphenylethyl group, 4-i-butylphenylethyl group, 3-i-butylphenylethyl group, 2-i-butylphenylethyl group, 4-t-butylphenylethyl group, 3-t-butylphenylethyl group, 2-t-butyl Phenylethyl group, 4-cyclobutylphenylethyl group, 3-cyclobutylphenylethyl group, 2-cyclobutylphenylethyl group, 4-cyclopentylphenylethyl group, 4-cyclohexylphenylethyl group, 4 -Cycloheptenylphenylethyl group, 4-cyclooctanylphenylethyl group, 2-cyclopentylphenylethyl group, 2-cyclohexylphenylethyl group, 2-cycloheptenylphenylethyl group, 2-cyclooctanylphenylethyl group, 3-cyclopentylphenyl An ethyl group, 3-cyclohexylphenylethyl group, 3-cycloheptenylphenylethyl group, 3-cyclooctanylphenylethyl group, 4-cyclopentyloxyphenylethyl group, 4-cyclohexyloxyphenylethyl group, 4-cycloheptenyloxyphenylethyl group, 4-cyclooctanyloxyphenylethyl group, 2-cyclopentyloxyphenylethyl group, 2-cyclohexyloxyphenylethyl group, 2-cycloheptenyloxyphenylethyl group, 2-cyclooctanyloxyphenylethyl group, 3-cyclopentyloxyphenylethyl group , 3-cyclohexyloxyphenylethyl group, 3-cycloheptenyloxyphenylethyl group, 3-cyclooctanyloxyphenylethyl group, 4-n-pentylphenylethyl group, 4-n-hexylphenylethyl group, 4-n-heptenylphenyl Ethyl group, 4-n-octanylphenylethyl group, 2-n-pentylphenylethyl group, 2-n- Hexylphenylethyl group, 2-n-heptenylphenylethyl group, 2-n-octanylphenylethyl group, 3-n-pentylphenylethyl group, 3-n-hexylphenylethyl group, 3-n-heptenylphenylethyl group, 3-n -Octanylphenylethyl group, 2,6-di-isopropylphenylethyl group, 2,3-di-isopropylphenylethyl group, 2,4-di-isopropylphenylethyl group, 3,4-di-isopropylphenylethyl group, 2,6-di-t-butylphenylethyl group, 2,3-di-t-butylphenylethyl group, 2,4-di-t-butylphenylethyl group, 3,4-di-t-butylphenylethyl group, 2, 6-di-n-butylphenylethyl group, 2,3-di-n-butylphenylethyl group, 2,4-di-n-butylphenylethyl group, 3,4-di-n-butylphenylethyl group, 2,6- Di-i-butylphenylethyl group, 2,3-di-i-butylphenylethyl group, 2,4-di-i-butylphenylethyl group, 3,4-di-i-butylphenylethyl group, 2,6-di- t-amylphenylethyl group, 2,3-di-t-amylphenylethyl group, 2,4-di-t-amylphenylethyl group, 3,4-di-t-amylphenylethyl group, 2,6-di-i- Amylphenylethyl group, 2,3-di-i-amylphenylethyl group, 2,4-di-i-amylphenylethyl group, 3,4-di-i-amyl Phenylethyl group, 2,6-di-n-pentylphenylethyl group, 2,3-di-n-pentylphenylethyl group, 2,4-di-n-pentylphenylethyl group, 3,4-di-n-pentylphenylethyl group , 4-adamantylphenylethyl group, 3-adamantylphenylethyl group, 2-adamantylphenylethyl group, 4-isoboroylphenylethyl group, 3-isoboroylphenylethyl group, 2-isoboroylphenyl Ethyl group, 4-cyclopentyloxyphenylethyl group, 4-cyclohexyloxyphenylethyl group, 4-cycloheptenyloxyphenylethyl group, 4-cyclooctanyloxyphenylethyl group, 2-cyclopentyloxyphenylethyl group, 2-cyclohexyloxyphenyl Ethyl group, 2-cycloheptenyloxyphenylethyl group, 2-cyclooctanyloxyphenylethyl group, 3-cyclopentyloxyphenylethyl group, 3-cyclohexyloxyphenylethyl group, 3-cycloheptenyloxyphenylethyl group, 3-cyclooctanyl Oxyphenylethyl group, 4-n-pentyloxyphenylethyl group, 4-n-hexyloxyphenylethyl group, 4-n-heptenyloxyphenylethyl group, 4-n-octanyloxyphenylethyl group, 2-n-pentyloxype Ethyl group, 2-n-hexyloxyphenylethyl group, 2-n-heptenyloxyphenylethyl group, 2-n-octanyloxyphenylethyl group, 3-n-pentyloxyphenylethyl group, 3-n-hexyloxyphenylethyl group, 3 -n-heptenyloxyphenylethyl group, 3-n-octanyloxyphenylethyl group, 2,6-di-isopropyloxyphenylethyl group, 2,3-di-isopropyloxyphenylethyl group, 2,4-di-iso Propyloxyphenylethyl group, 3,4-di-isopropyloxyphenylethyl group, 2,6-di-t-butyloxyphenylethyl group, 2,3-di-t-butyloxyphenylethyl group, 2,4-di-t -Butyloxyphenylethyl group, 3,4-di-t-butyloxyphenylethyl group, 2,6-di-n-butyloxyphenylethyl group, 2,3-di-n-butyloxyphenylethyl group, 2,4-di -n-butyloxyphenylethyl group, 3,4-di-n-butyloxyphenylethyl group, 2,6-di-i-butyloxyphenylethyl group, 2,3-di-i-butyloxyphenylethyl group, 2,4 -Di-i-butyloxyphenylethyl group, 3,4-di-i-butyloxyphenylethyl group, 2,6-di-t-amyloxyphenylethyl group, 2,3-di-t-amyloxyphenylethyl group, 2 , 4-di-t-ah Oxyphenylethyl group, 3,4-di-t-amyloxyphenylethyl group, 2,6-di-i-amyloxyphenylethyl group, 2,3-di-i-amyloxyphenylethyl group, 2,4-di-i -Amyloxyphenylethyl group, 3,4-di-i-amyloxyphenylethyl group, 2,6-di-n-pentyloxyphenylethyl group, 2,3-di-n-pentyloxyphenylethyl group, 2,4-di -n-pentyloxyphenylethyl group, 3,4-di-n-pentyloxyphenylethyl group, 4-adamantyloxyphenylethyl group, 3-adamantyloxyphenylethyl group, 2-adamantyloxyphenylethyl group, 4- And an isoboroyloxyphenylethyl group, 3-isoboroyloxyphenylethyl group, 2-isoboroyloxyphenylethyl group, or an alkyl substituted with a methyl group, propyl group, butyl group or the like.

Moreover, as a substituent different from the said group, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the said alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, hydroxyprop Alkoxy groups such as alkoxy groups such as alkoxy groups, n-butoxy groups, isobutoxy groups, sec-butoxy groups, t-butoxy groups, alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups, benzyl groups, phenethyl groups and cumyl groups , Acyloxy groups such as aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanyl group, valeryl group, acyloxy group such as butyryloxy group, the alkenyl group, vinyloxy group, propenyloxy group, Alkenyloxy groups, such as an aryloxy group and butenyloxy group, aryloxy groups, such as the said aryl group and phenoxy group, and aryloxycarbonyl groups, such as a benzoyloxy group, are mentioned.

As said substituent of R <^7> , Preferably, they are a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, or a C7-20 aralkyl group. These substituents may further have a substituent.

In this invention, by containing the structural unit represented by the said General formula (VI) in resin (A2), the said resin is decomposed by the action of an acid, and the solubility in alkaline developing solution can be controlled. Moreover, by introducing this structural unit, a profile excellent in rectangularity can be achieved. Or it is effective in adjusting the quantity of the structural unit represented by general formula (IV).

Although the following are mentioned as a specific example of the repeating unit represented by such general formula (VI), It is not limited to these.

Resin containing the structural units represented by these general formula (V) and general formula (VI) is a phenol resin or its monomer, reacting with the acid anhydride in presence of a base, or reacting with the binder reacting in presence of a base. Or the like.

In the present invention, the resin (A2) having a group which is decomposed by the action of an acid and increases the solubility in the alkaline developer is used as other copolymerization components other than the structural units represented by the general formulas (IV) to (VI). You may contain the other monomeric unit.

In this invention, it is preferable that the ratio x ', y', and z 'of resin (A2) which has group which decomposes | dissolves by action of an acid, and increases the solubility in alkaline developing solution satisfies the following conditions.

for z '= O (if it does not have the structural unit of formula (VI))

0.05 <x '/ (x' + y ') <0.5, more preferably 0.1 <x' / (x '+ y') <0.45

for z> 0 (when structural unit of formula (VI))

(1) 0.10 <x '/ (x' + y '+ z') <0.50,

(2) 0.005 <z '/ (x' + y '+ z') <0.35,

(3) x '> z'

(4) 0.4 <x '/ (x' + z ') <0.95

More preferably

(1) 0.20 <x '/ (x' + y '+ z') <0.40,

(2) 0.01 <z '/ (x' + y '+ z') <0.25,

(3) x'≥z '

(4) 0.5 <x '/ (x' + y ') <0.85

When the resin (A2) satisfies the above conditions in the present invention, the rectangularity of the profile is improved, and in particular, the development defect is further improved.

In addition, x '+ y' + z '= 100.                     

Even if the repeating unit represented by general formula (IV), general formula (V), and general formula (VI), or the repeating unit from another polymerizable monomer is respectively 1 type or in combination of 2 or more types, it may exist in resin. good.

In addition, the resin contained in the positive resist composition of the present invention may contain other polymerizable monomers suitable for introducing alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups in order to maintain good developability with respect to alkaline developing solutions. It may be copolymerized.

The molecular weight of the said resin (A2) is 2,000 or more, Preferably it is 3,000-200,000, More preferably, it is 5,000-70,000 by weight average (Mw: polystyrene basis). The dispersion degree (Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 3.5, particularly preferably 1.0 to 3.0, and the smaller the dispersion degree, the more heat resistance and image formability (pattern profile, Defocus latitude, etc.) becomes favorable.

The content of the positive resist composition (excluding the coating solvent) of the resin (A2) is preferably 50 to 99% by mass, more preferably 70 to 97% by mass.

Specific examples of the repeating units of the general formulas (IV) and (V) and the repeating units of the general formulas (IV), (V) and (VI) constituting the resin (A2) are shown below. However, the present invention is not limited to these.

In the present invention, the mixing ratio of the resin (A1) and (A2), which is decomposed by the action of an acid and the solubility in the alkaline developer is increased,

0.1≤ (A1) / {(A1) + (A2)} ≤0.9 (mass ratio)

More preferably

0.2≤ (A1) / {(A1) + (A2)} ≤0.8 (mass ratio)

More preferably

0.3≤ (A1) / {(A1) + (A2)} ≤0.7 (mass ratio)

The mixing ratio is preferably 0.1 or more in terms of dry etching performance and image performance (pattern profile, defocus latitude, etc.), and the mixing ratio is preferably 0.9 or less in view of shortening performance. .

As content in the composition of acid-decomposable resin (A), it is 70-98 mass% normally with respect to the mass of the total solid of the said composition, Preferably it is 75-96 mass%, More preferably, it is 80-96 mass%.

<< compound (B) >> which produces | generates an acid by irradiation of actinic light or radiation >>

The compound which generate | occur | produces an acid by irradiation of actinic light or radiation used by this invention (henceforth a "acid generator" and a "component B") is demonstrated below.

Examples of the acid generator usable in the present invention include a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photochromic agent for dyes, a photochromic agent, a known photopolymer for generating an acid by irradiation with radiation used in a micro resist, or the like. The compound and mixtures thereof may be appropriately selected and used.

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 / organohalides, and acids having o-nitrobenzyl-type protecting groups The compound and the disulfone compound which photodecomposes and generate a sulfonic acid represented by a generator, an imino sulfonate, etc. can be mentioned.

Moreover, the compound which introduce | transduced the group which generate | occur | produces an acid by irradiation of these actinic rays or radiation, or the compound in the main chain or side chain of a polymer, for example, US Patent No. 3,849,137 specification, German Patent No. 3,914,407 specification, Japan Japanese Patent Application Laid-Open No. 63-26653, Japanese Patent Application Laid-Open No. 55-164824, Japanese Patent Application Laid-Open No. 62-69263, Japanese Patent Application Laid-Open No. 63-146038, Japanese Patent Publication No. 63-163452, Japan The compound described in Unexamined-Japanese-Patent No. 62-153853, Unexamined-Japanese-Patent No. 63-146029, etc. can be used.

In addition, a compound which generates an acid by light described in U.S. Patent No. 3,779,778, European Patent No. 126,712, or the like can also be used.

Among the compounds which are decomposed by irradiation of the above usable actinic rays or radiation to generate an acid, those which are particularly effectively used will be described below.

(1) Iodonium salt represented by the following general formula (PAG3), or sulfonium salt represented by general formula (PAG4).

Here, formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include alkyl, cycloalkyl, aryl, alkoxy, nitro, carboxyl, alkoxycarbonyl, hydroxy, mercapto and halogen atoms.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each 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.

Preferred substituents 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 with respect to aryl groups, and alkoxy groups having 1 to 8 carbon atoms, carboxyl groups and alkoxycarbonyl groups for alkyl groups.

Z ^- represents a counter anion, for _{^{example, BF 4 -, AsF 6 -}} , PF 6 -, SbF 6 -, SiF 6 2 -, ClO 4 -, CF 3 SO 3 - , such as perfluoro alkane sulfonic acid anion, Penta Condensed polynuclear aromatic sulfonic anions, anthraquinone sulfonic anion, sulfonic acid group-containing dyes such as fluorobenzene sulfonic acid anion and naphthalene-1-sulfonic acid anion, and the like, and the like can be listed, but are not limited thereto.

In addition, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded to each other through a single bond or a substituent.

Although the compound shown below is mentioned as a specific example, It is not limited to these.

The onium salts represented by the formulas (PAG3) and (PAG4) are known and can be synthesized by the methods described in, for example, US Pat. Nos. 2,807,648 and 4,247,473, Japanese Patent Application Laid-Open No. 53-101,331. have.

(2) The disulfone derivative represented by the following general formula (PAG5) or the iminosulfonate derivative represented by the general formula (PAG6).

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group.

R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, arylene group.

Although the compound shown below is mentioned as a specific example, It is not limited to these.

(3) Diazodisulfone derivatives represented by the following general formula (PAG7).

Here, R represents a linear, branched or cyclic alkyl group or an aryl group which may be substituted.

Although the compound shown below is mentioned as a specific example, It is not limited to these.

(4) As the acid generator (A), phenacylsulfonium derivatives represented by the following general formula (I) can also be used.

In general formula (I),

R ₁ to R ₅ may represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a halogen atom, an alkyloxycarbonyl group or an aryl group, and two or more of R ₁ to R ₅ may be bonded to form a ring structure.

R ₆ and R ₇ represent a hydrogen atom, an alkyl group, a cyano group, or an aryl group.

Y ₁ and Y ₂ represent an aromatic group containing an alkyl group, an aryl group, an aralkyl group or a hetero atom, and Y ₁ and Y ₂ may be bonded to form a ring.

Y ₃ represents a polybond or a divalent linking group.

X ⁻ represents a nonnucleophilic anion.

R ₁ ~R may be the at least one of Y ₁ or Y ₅ and at least one of the _two combined to form a ring, R ₁ ~R least one of R ₅ and R ₆ or at least one of the coupling ₇ You may form a ring.

Any of R ₁ to R ₇ may be bonded via a linking group at any one of Y ₁ or Y ₂ , and may have two or more structures of formula (I).

Although the specific example of a compound represented by said Formula (I) is listed below, this invention is not limited to these.

Among the above compounds which decompose upon irradiation with actinic light or radiation to generate an acid, examples of particularly preferred ones are listed below.

The compound of (B) component can be used individually by 1 type or in combination of 2 or more types.                     

As for content in the positive resist composition of this invention of the compound of (B) component, 0.1-20 mass% is preferable on the basis of solid content of a composition, More preferably, it is 0.5-10 mass%, More preferably, it is 1- 7 mass%.

<< solvent (C) >>

The composition of this invention is melt | dissolved in the base solvent which melt | dissolves each said component and arbitrary components mentioned later, and is apply | coated on a support body. As a solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, (gamma) -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, pyrubin Ethyl acid, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

Among the above, preferred organic solvents include 2-heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, methyl methoxy propionate, ethyl ethoxy propionate, N-methylpyrrolidone and tetrahydrofuran.                     

<< (other components used in the present invention) >>

The positive resist composition of this invention can mix | blend alkali-soluble resin which does not contain an acid-decomposable group other than the said acid-decomposable resin (a) as a resin component, and sensitivity improves by these.

Alkali-soluble resins which do not contain an acid-decomposable group (hereinafter only referred to as "alkali-soluble resins") are resins soluble in alkali, and polyhydroxystyrene, novolak resins and derivatives thereof can be preferably listed. . Moreover, the copolymerization resin containing a p-hydroxy styrene unit can also be used if it is alkali-soluble.

Among these, poly (p-hydroxy styrene), poly (p- / m-hydroxy styrene) copolymer, poly (p- / o-hydroxy styrene) copolymer, poly (p-hydroxy styrene / styrene) Copolymers are preferably used. In addition, poly (4-hydroxy-3-methylstyrene), poly (alkyl-substituted hydroxystyrene) resins such as poly (4-hydroxy-3,5-dimethylstyrene), and a part of the phenolic hydroxyl group of the resin Alkylated or acetylated resins are also preferably used if they are alkali soluble.

Moreover, when a part (30 mol% or less of all phenol nucleus) of the said resin is hydrogenated, transparency of resin improves and it is preferable at the point of the sensitivity, the resolution, and the rectangular formation of a profile.

In this invention, as addition amount in the composition of alkali-soluble resin which does not contain the said acid-decomposable group, Preferably it is 2-60 mass% with respect to the total mass of solid content of a composition, More preferably, it is 5-30 mass%. .                     

The positive resist composition of the present invention may contain an acid decomposable dissolution promoting compound, a dye, a plasticizer, a surfactant, a photosensitizer, a basic compound, a compound for promoting solubility in a developer, and the like, as necessary.

(d) fluorine-based and / or silicone-based surfactants

In the positive resist composition of the present invention, any one or two or more of (d) a fluorine-based and / or silicon-based surfactant (a fluorine-based surfactant and a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom) can be used. It is preferable to contain.

When the positive resist composition of the present invention contains the surfactant (d), a resist pattern with less adhesion and development defects can be provided with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. have.

As these (d) surfactants, Unexamined-Japanese-Patent No. 62-36663, Unexamined-Japanese-Patent No. 61-226746, Unexamined-Japanese-Patent No. 61-226745, and Unexamined-Japanese-Patent No. 62-170950 are mentioned, for example. JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988 No. 2002-277862, US Patent No. 5,405,720, US 5,360,692, US 5,529,881, US 5,296,330, US 5,436,098, US 5,576,143, US 5,294,511, US 5,824,451 The surfactant described in the above can be enumerated, and the following commercially available surfactant can also be used as it is.                     

As a commercially available surfactant which can be used, For example, F-Top EF301, EF303 (made by Shin-Akiga Chemical Co., Ltd.), Floroid FC430, 431 (made by Sumitomo 3M Corporation), Megapack F171, F173, F176, F189, R08 (manufactured by Dainippon Ink, Co., Ltd.), Supron S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.) Fluorine-based surfactants such as products) or silicone surfactants. Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone type surfactant.

Moreover, as surfactant, in addition to the well-known thing mentioned above, the fluorine introduced from the fluoro aliphatic compound manufactured by the telomerization method (also called telomer method) or the oligomerization method (also called oligomer method) As the surfactant, a surfactant using a polymer having an aliphatic group can be used. A fluoro aliphatic compound can be synthesize | combined by the method of Unexamined-Japanese-Patent No. 2002-90991.

As the polymer having a fluoro aliphatic group, a copolymer of a monomer having a fluoro aliphatic group with (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and is distributed irregularly. It may be present or may be block copolymerized. Examples of the poly (oxyalkylene) group include poly (oxyethylene) groups, poly (oxypropylene) groups, poly (oxybutylene) groups and the like, and poly (oxyethylene, oxypropylene and oxyethylene It may be a unit having alkylene having a different chain length in the chain length such as a block linker) or a poly (block linker of oxyethylene and oxypropylene) group. The copolymer of a monomer having a fluoro aliphatic group and a (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer or another monomer having two or more different fluoro aliphatic groups. A ternary or higher copolymer obtained by simultaneously copolymerizing two or more kinds of (poly (oxyalkylene)) acrylates (or methacrylates) may be used.

For example, as a commercially available surfactant, Megapack F178, F-470, F-473, F-475, F-476, and F-472 (made by Dainippon Ink & Chemicals Co., Ltd.) can be mentioned. Further, copolymers of acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate having a C ₆ F ₁₃ group) ) And a copolymer of (poly (oxyethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate), an acrylate (or methacrylate having a C ₈ F ₁₇ group) ) And (poly (oxyalkylene)) acrylates (or methacrylates), acrylates (or methacrylates) and (poly (oxyethylene)) acrylates (or methacrylates) having C ₈ F ₁₇ groups And copolymers of (poly (oxypropylene)) acrylate (or methacrylate) and the like.

The amount of the surfactant (d) used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the positive resist composition (excluding the solvent).

These surfactant can be used individually by 1 type or in combination of 2 or more type.

(E) A basic compound, More preferably, an organic basic compound can be used for the positive resist composition of this invention. This is preferable because it improves stability at the time of storage and changes the line width due to PED (Post Exposure Delay).

Preferred organic basic compounds which can be used in the present invention are compounds which are more basic than phenol. Among these, nitrogen-containing basic compounds are preferable.

As a preferable chemical environment, the following formula (A)-(E) structure can be mentioned.

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵¹ and R ²⁵² are each other You may combine and form a ring.

In the formula, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ are the same or different and represent an alkyl group having 1 to 20 carbon atoms.

Other preferred compounds are nitrogen-containing cyclic compounds or nitrogen-containing basic compounds having two or more nitrogen atoms in different chemical environments in one molecule.

As the nitrogen-containing cyclic compound, a polycyclic structure is more preferable. As a preferable specific example of a nitrogen-containing polycyclic cyclic compound, the compound represented by the following general formula (F) is mentioned.

In formula (F), Y and Z respectively independently represent the linear, branched, and cyclic alkylene group which may contain the hetero atom and may be substituted.

Here, as a hetero atom, a nitrogen atom, a sulfur atom, and an oxygen atom are mentioned. As an alkylene group, C2-C10 is preferable, More preferably, it is a 2-5 thing. As a substituent of an alkylene group, halogen atoms other than a C1-C6 alkyl group, an aryl group, an alkenyl group, and a halogen substituted alkyl group are mentioned. Moreover, the compound shown below is mentioned as a specific example of a compound represented by general formula (F).

Among these, 1,8- diazabicyclo [5.4.0] undeca-7-ene and 1, 5- diazabicyclo [4.3.0] nona-5-ene are especially preferable.

As the nitrogen-containing basic compound having two or more nitrogen atoms in different chemical environments in one molecule, particularly preferably, a compound containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom or a compound having an alkylamino group to be. Particularly preferred compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethyl Aminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6 -Methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4 -Amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3- Amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, trimethylimidazole, triphenylimidazole, methyldiphenylimidazole and the like are listed, but are not limited to these.

These basic compounds are used individually or in combination of 2 or more types. The usage-amount of a basic compound is 0.001-10 mass parts normally with respect to 100 mass parts of compositions (solid content), Preferably it is 0.01-5 mass parts. By setting it as 0.001 mass part or more, the said effect is acquired. Moreover, if it is 10 mass parts or less, favorable sensitivity and developability will be obtained.

As a dissolution promoting compound with respect to the developing solution which can be used by this invention, it is a low molecular weight compound of 1,000 or less molecular weight which has two or more phenolic hydroxyl groups or one or more carboxyl groups. In the case of having a carboxyl group, an alicyclic or aliphatic compound is preferable for the same reasons as described above.

The preferable addition amount of these dissolution promoting compounds is 2-50 mass% with respect to the polymer in this invention, More preferably, it is 5-30 mass%. From the viewpoint of the development residue and the prevention of pattern deformation during development, the addition amount of the dissolution-accelerating compound is preferably at most 50 mass%.

For such phenolic compounds having a molecular weight of 1000 or less, see, for example, the methods described in Japanese Patent Application Laid-Open No. Hei 4-122938, Japanese Patent Application Laid-Open No. 2-28531, US Patent No. 4916210, European Patent No. 219294, and the like. Thus, it can be easily synthesized by those skilled in the art.

Although the specific example of a phenol compound is shown below, the compound which can be used by this invention is not limited to these.                     

Resorcin, phloroglucin, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,3 ', 4', 5'- Hexahydroxybenzophenone, acetone pyrogallol condensation resin, phloglucoside, 2,4,2 ', 4'-biphenylterol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2 ', 4,4'-tetrahydroxydiphenylether, 2,2', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2 ', 4,4'-tetrahydroxydiphenyl Sulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4- (α-methylbenzylidene) bisphenol, α, α ', α "-tris ( 4-hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α ', α "-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,2,2 -Tris (hydroxyphenyl) propane, 1,1,2-tris (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) butane, para [ , Α, α ', α'- tetrakis (4-hydroxyphenyl)] - xylene and the like can be exemplified.

Preferred dyes are oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (above, Orient Kagaku High school), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI52015), and the like.

In order to improve the acid generation rate by exposure, photosensitizers such as those listed below can also be added. Specific examples of the preferred photosensitizer include benzophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylethylamizobenzophenone, 2-chlorothioxanthone, anthrone and 9-ethoxy Anthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2 Nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, Picramid, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone , 1,2-naphthoquinone, 3,3'-carbonyl-bis (5,7-dimethoxycarbonylcoumarin), coronene, and the like, but are not limited thereto.

In addition, these photosensitizers can also be used as a light absorber of far ultraviolet light of a light source. In this case, the light absorber can reduce the reflected light from the substrate and reduce the influence of multiple reflections in the resist film, and exhibits the effect of improving the standing wave.

In this invention, surfactant other than the said fluorine type and / or silicone type surfactant can also be added. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol Polyoxyethylene alkyl allyl ethers such as ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan triol Sorbitan fatty acid esters such as late, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate Polyoxy such as polyoxyethylene sorbitan tristearate Such as ethylene sorbitan fatty acid non-ionic surfactants such as esters can be exemplified.

The compounding quantity of these surfactant is 2 mass% or less normally per 100 mass% of solid content in the composition of this invention, Preferably it is 1 mass% or less.

These surfactants may be added alone, or may be added in any combination.

The positive resist composition according to the present invention is applied onto a substrate (e.g., silicon / silicon dioxide substrate) by a suitable coating method such as spinner, coater, etc. to be used for the manufacture of precision integrated circuit devices, and then prebaking is performed. A good resist pattern can be obtained by exposing through a predetermined mask and performing post-baking to develop. Here, as exposure light, Preferably it is far ultraviolet of the wavelength of 250 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 mentioned.

Examples of the developer of the positive resist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, first amines such as ethylamine and n-propylamine, diethylamine, Second amines such as di-n-butylamine, third amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide Alkaline aqueous solutions (usually 0.1-10 mass%), such as cyclic amines, such as quaternary ammonium salts, pyrrole, and piperidine, can be used.

Moreover, alcohol and surfactant can be added to the alkaline aqueous solution in an appropriate amount.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

Synthesis Example X1

<Synthesis of 2-thienylmethylcarbonyloxyethyl vinyl ether (X-1)>

100 g of thiophene-2-acetic acid was dissolved in 500 ml of DMAc (N, N-dimethylacetamide), 31 g of sodium hydroxide was added, and the mixture was stirred at room temperature for 10 minutes. 112 g of 2-chloroethyl vinyl ether were added there, and it stirred at 120 degreeC for 2 hours (precipitation of salt). Water and ethyl acetate were added to the reaction mixture, the separation operation was performed, and water washing was performed three times. After drying the obtained organic phase, it concentrated and distillation under reduced pressure obtained the target object (X-1). The target product was confirmed by NMR.

Synthesis Example X2

<Synthesis of thienylcarbonyloxyethyl vinyl ether (X-2)>

The target object (X-2) was obtained by the same operation as Synthesis Example X1 except that tenenoic acid was used as the raw material.

Synthesis Example X3                     

<Synthesis of vinyloxyethyloxycarbonyl naphthalene (X-3)>

The target object (X-3) was obtained in the same manner as in Synthesis Example X1 except that α-naphthalenecarboxylic acid was used as the starting material.

Synthesis Example X4

<Synthesis of 2-thienylethyl vinyl ether (X-4)>

The target product (X-4) was obtained in the same manner as in Synthesis Example X1 except that 2-thienyl lithium or 2-thienyl magnesium bromide was used as the starting material.

Synthesis Example X5

<Synthesis of 2-furylcarbonyloxyethyl vinyl ether (X-5)>

Except having used 2-furyl carboxylic acid as a raw material, the target object (X-5) was obtained by operation similar to the synthesis example X1.

Synthesis Example X6

<Synthesis of 2-thienylthioethyl vinyl ether (X-6)>

Except having used 2-thienyl thiol as a raw material, the target object (X-6) was obtained by operation similar to the synthesis example X1.

The structures of the vinyl ethers (X-1) to (X-6) synthesized above are shown below.

Synthesis Example 1 (polymer having phenolic hydroxyl group: synthesis of resin R-1)

32.4 g (0.2 mol) of p-acetoxystyrene was dissolved in 120 ml of methanol, stirred under a stream of nitrogen, and 0.033 g of azobisisobutylnitrile (AIBN) was added at 60 ° C, and stirring was continued for 12 hours. Was performed. Dilute hydrochloric acid was added to the reaction solution to break the acetoxy group, and then the volatiles were removed by distillation under reduced pressure. The obtained resin was dissolved in 150 ml of methanol again and added to a large amount of water to obtain a white polymer. The procedure of dissolving the polymer again in methanol and adding to a large amount of water was repeated three times. The resultant resin was dried in a vacuum dryer at 60 ° C. for 24 hours, and poly (p-hydroxystyrene) (resin R-1) Got. The weight average molecular weight of the obtained resin was 15,000.

Synthesis Example 2 (polymer having a phenolic hydroxyl group: synthesis of resin R-2)

According to the method, 35.25 g (0.2 mol) of dehydrated, distilled and purified p-tert-butoxystyrene monomer and 2.42 g (0.0151 mol) of p-tert-butylstyrene were dissolved in 100 ml of tetrahydrofuran. Under nitrogen stream and stirring, 0.033 g of azobisisobutylnitrile (AIBN) was added three times every three hours at 83 ° C, and the polymerization reaction was carried out by continuing stirring for six more hours. The reaction solution was poured into 1200 ml of hexane to precipitate white resin. The obtained resin was dissolved in 150 ml of tetrahydrofuran after drying. 4N hydrochloric acid was added to this, and it heated and refluxed for 6 hours, and after hydrolyzing, it was reprecipitated in 5L of ultrapure water, this resin was filtered and filtered, and it washed with water and dried. In addition, it was dissolved in 200 ml of tetrahydrofuran, and dripped and reprecipitation was performed with vigorous stirring with 5 L of ultrapure water. This reprecipitating operation was repeated three times. The obtained resin was dried in a vacuum dryer at 60 ° C. for 24 hours to obtain a poly (p-hydroxystyrene / p-tert-butylstyrene) copolymer (resin R-2). The weight average molecular weight of obtained resin was 10,000.

Synthesis Example 3 (polymer having a phenolic hydroxyl group: synthesis of resin R-3)

40 g (0.33 mol) of p-hydroxystyrene and 10.7 g (0.08 mol) of tert-butyl acrylate were dissolved in 50 g of dioxane, and 8 g of azobisisobutylnitrile (AIBN) was added thereto, followed by 8 hours at 60 ° C. under a nitrogen stream. Heat stirring was performed. The reaction solution was poured into 1200 ml of hexane to precipitate white resin. The obtained resin was dried, dissolved in acetone, and dripped in 5 L of ultrapure water with vigorous stirring, followed by reprecipitation. This re-immersion operation was repeated three times. The obtained resin was dried at 60 ° C. for 24 hours in a vacuum dryer to obtain a poly (p-hydroxystyrene / tert-butylacrylate) copolymer (resin R-3). The weight average molecular weight of obtained resin was 21,000.

Synthesis Example 4 (acid-decomposable resin (a): synthesis of polymer A'-1)

150 g of poly (p-hydroxystyrene) (resin R-4) (molecular weight 10000) from Nippon Sodachi Co., Ltd. was dissolved in 700 g of propylene glycol monomethyl ether acetate (PGMEA), and the solution was heated to 60 ° C and 20 mmHg. It reduced pressure and removed about 40g of solvent with water which remain | survived in the system. After cooling to 20 ° C, 24 g of a 1% PGMEA solution of paratoluenesulfonic acid was added, 9.0 g of ethyl vinyl ether was added, and the mixture was stirred at room temperature for 1 hour. Subsequently, 49 g of 2-thienylcarbonyloxyethyl vinyl ether (X-2) synthesize | combined separately was added to this reaction liquid, and it stirred at room temperature for 1 hour. Thereafter, 25 g of 1% triethylamine PGMEA solution was added to neutralize the solution, precipitated with 600 ml of ethyl acetate, and washed three times with 300 ml of water to obtain A'-1.

Synthesis Examples 5 to 13 (acid-decomposable resin (a): synthesis of polymers A'-2 to A'-10)

Acid-decomposable resins were synthesized in the same manner as in Synthesis Example 4 except that a polymer (stem polymer) having two phenolic hydroxyl groups and two vinyl ethers shown in Table 1 were used, and the obtained polymers were A'-2 to A '. It was set to -12.

In addition, it synthesize | combined in the same manner to the above except using only 1 type of vinyl ether as resin (C-1) for a comparative example (ethyl vinyl ether: 27 g, stem polymer R-1).

Synthesis Example 14 (Synthesis of Resin B'-1)

VP15000 (100 g) from Nippon Sodachi and propylene glycol monomethyl ether acetate (PGMEA) (400 g) were dissolved in a flask, distilled under reduced pressure, and azeotropically removed water and PGMEA.

After confirming that the water content was sufficiently lowered, ethyl vinyl ether (25.0 g) and p-toluenesulfonic acid (0.02 g) were added and stirred at room temperature for 1 hour. Triethylamine (0.03 g) was added to the reaction solution to stop the reaction, water (400 ml) and ethyl acetate (800 ml) were added and separated, and the mixture was washed with water, and then ethyl acetate, water and azeotrope were removed under reduced pressure. Minute PGMEA was removed to obtain alkali-soluble resin B'-1 (30% PGMEA solution) having a substituent according to the present invention.

Synthesis Example-15 (Synthesis of Resin B'-2)

de-protection by polymerization or hydrochloric acid using p-acetoxystyrene monomer (or pt-butoxystyrene monomer) and cyclohexyl acrylate monomer as 2,2'-azobisisobutyrate dimethyl (AIBN) as an initiator, p-hydroxystyrene / cyclohexylacrylate copolymer (90/10) R-4 was obtained.

Resin R-4 (100 g) and propylene glycol monomethyl ether acetate (PGMEA) (400 g) were dissolved in a flask, and distillation under reduced pressure was carried out to azeotropically remove water and PGMEA. After confirming that the water content was sufficiently lowered, ethyl vinyl ether (25.0 g) and p-toluenesulfonic acid (0.02 g) were added and stirred at room temperature for 1 hour.

Triethylamine (0.03 g) was added to the reaction solution to stop the reaction, water (400 ml) and ethyl acetate (800 ml) were added and separated, and the mixture was washed with water, and then ethyl acetate, water and azeotrope were removed under reduced pressure. Minute PGMEA was removed to obtain alkali-soluble resin B'-2 (30% PGMEA solution) with a substituent according to the invention.

Synthesis Example-16 (Synthesis of Resin B'-3)

Resin B'-3 was obtained by the same method as the synthesis example 14 except having changed the ethyl vinyl ether of the synthesis example 14 into isobutyl vinyl ether.

Synthesis Example-17 (Synthesis of Resin B'-4)

Resin B'-4 was obtained by the same method as the synthesis example 14 except having changed the ethyl vinyl ether of the synthesis example-14 into t-butyl vinyl ether.

Each solution of the said acid-decomposable resin was adjusted so that solid content concentration in PGMEA might be 20 mass%, and it used for the following example and the comparative example.

Examples 1 to 27 and Comparative Examples 1 and 2 (Preparation and Evaluation of Positive Resist Composition)                     

Each component shown in Table 2 was dissolved in 8.4 g of a solvent (PGMEA), and filtered through a 0.1 μm filter to prepare a positive resist composition. All acid-decomposable resins used 7.66g of PGMEA 30% solution, respectively. 100 ppm of surfactant was added with respect to the resist solution.

The positive resist composition was uniformly coated on a hexamethyldisilazane-treated silicon wafer using a spin coater, and heated and dried on a hot plate at 120 ° C. for 90 seconds to form a 0.4 μm resist film. I was. This resist film was subjected to pattern exposure using a KrF excimer laser stepper (NA: 0.63) using a halftone mask having a transmittance of 6%, and immediately after exposure, it was heated on a hot plate at 90 ° C for 90 seconds. Furthermore, it developed at 23 degreeC with the 2.38% tetramethylammonium hydroxide aqueous solution for 60 second, wash | cleaned with pure water for 30 second, and dried.

The obtained pattern was observed with the scanning electron microscope, and the resist performance was evaluated as follows. The results are shown in Table 2.

[Remaining standing waves]: The sidewalls of the resist pattern obtained by the mask pattern of 0.30 탆 line and space were observed with a scanning electron microscope, and the following five-step evaluation was performed.

A: No standing waves at all and the pattern sidewalls are very clean

B: Slight standing waves or irregularities on the pattern sidewalls

C: When standing waves can be surely confirmed (not applicable in this embodiment)

D: When standing waves can be confirmed slightly stronger                     

E: When standing waves can be identified very strongly

[profile]

The profile of the pattern obtained above was observed by cross-sectional SEM, and the following three stages of evaluation were performed.

1: for rectangle

2: the taper is hardly checked and is generally rectangular

3: clearly tapered

As a surfactant,

W-1: Mega Pack F176 (Dai Nippon Ink Chemical Industries, Ltd.) (Fluoride)

W-2: Mega Pack R08 (Dai Nippon Ink Chemical Industries, Ltd.) (fluorine and silicone)

W-3: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

W-4: Polyoxyethylene nonyl phenyl ether

W-5: Troisol S-366 (Troy Chemical Co., Ltd.)

W-6: Mega Pack F-475 (Dai Nippon Ink Chemical Industries, Ltd.)

W-7: Copolymer of an acrylate having a C ₆ F ₁₃ group, a (poly (oxypropylene)) acrylate, and a (poly (oxypropylene)) methacrylate

W-8: Copolymer of an acrylate having a C ₆ F ₁₃ group with a (poly (block of ethyleneoxy, propyleneoxy and ethyleneoxy)) acrylate

As a basic compound (amine)

DBN: 1,5-diazabicyclo [4.3.0] nona-5-ene

DMAP: 4-N, N-dimethylaminopyridine

TPI: 2,4,5-triphenylimidazole

TBA: tri-n-butylamine

TOA: tri-n-octylamine

DCMA: Dicyclohexylmethylamine

DCEA: Dicyclohexylethylamine

.

As is apparent from the results in Table 2, the positive resist composition of each example had a satisfactory result in each of standing waves and profiles. However, the resist composition of the comparative example remained standing waves and had a poor profile.

The positive resist composition of the present invention contains a specific acid-decomposable resin, whereby substantially no generation of standing waves occurs, and an excellent profile also exhibits excellent effects.

Claims (6)

It contains a repeating unit represented by the following general formula (I), a repeating unit represented by the general formula (II), and a repeating unit represented by the general formula (III), and decomposed by the action of an acid to dissolve in an alkaline developer. A positive resist composition comprising the resin (A1) which increases, the compound (B) which generate | occur | produces an acid by irradiation of actinic light, or a radiation, and a solvent (C).

(In Formulas (I) to (III), L and L 'each independently represent a hydrogen atom, an alkyl group, or an aralkyl group; Z ¹ represents an arylcarbonyl group, a cyclic aryl group, a cyclic arylcarbonyl group, or a group having a heterocycle. W represents an alkyl group; Z ¹ and L, W and L 'may combine with each other to form a 5- or 6-membered ring. The resin (A1) according to claim 1, wherein the resin (A1) contains a repeating unit represented by the following general formula (I '), a repeating unit represented by the general formula (II), and a repeating unit represented by the general formula (III). A positive resist composition characterized by the above.

(Formula (I '), (II) , (III) of the, L and L' each independently represents a hydrogen atom, an alkyl group, or aralkyl group; Z ² represents a heterocyclic group; X is a carbon number of 1 to 20 An alkylene group; Y represents a divalent linking group; n represents 0 or 1; W represents an alkyl group; Z ² and L, W, and L 'may combine with each other to form a 5- or 6-membered ring. ) The resin (A2) according to claim 1 or 2, further comprising a resin (A2) having a repeating unit represented by the following general formulas (IV) and (V), which is decomposed by the action of an acid and has increased solubility in an alkaline developing solution. A positive resist composition, characterized in that.

(W 'represents a group represented by the following general formula (Y) in Formula (IV)-(V); x' and y 'represent 1-100, respectively, provided that x' + y '<= 100;

In formula (Y), R <^4> represents a C1-C4 lower alkyl group.) The pattern formation method characterized by forming a resist film with the resist composition of Claim 1 or 2, exposing and developing the said resist film. delete A positive resist according to claim 2, wherein Y in formula (I ') represents -OC (= 0)-, -O-, -S-, or -OC (= 0) -CH _2-. Composition.