KR20030023463A - Positive-type photoresist composition - Google Patents

Abstract

PURPOSE: To provide a chemical amplification type positive type photoresist composition excellent in various characteristics such as resolving power, margin for exposure, edge roughness of a pattern and density dependence. CONSTITUTION: The positive type photoresist composition contains (A) at least two photo-acid generators which are selected from sulfonates in which each of cationic moieties comprises iodonium or sulfonium and each of anionic moieties comprises an anion of the formula RFSO3¬- (where RF is a 1-20C fluorine substituted alkyl group), have a difference between the numbers of carbon atoms in the groups RF of the anionic moieties in the range of 2-15 and generate acids when irradiated with active light or radiation and (B) a resin which contains specified repeating units and is decomposed by the action of the acids to increase its alkali solubility.

Description

Positive Photoresist Composition {POSITIVE-TYPE PHOTORESIST COMPOSITION}

TECHNICAL FIELD This invention relates to the positive photoresist composition used for ultramicrolithography processes, such as manufacture of a super LSI and a high capacity | capacitance microchip, and other light manufacturing processes. More specifically, the present invention relates to a positive photoresist composition capable of forming a highly fine pattern by using an ultraviolet ray region including excimer laser light, particularly a light having a wavelength of 250 nm or less.

In recent years, the degree of integration of integrated circuits has been further increased, and the manufacture of ultra-fine patterns having a line width of less than half microns has become necessary for the manufacture of semiconductor substrates for ULSI circuits. In order to satisfy this necessity, the wavelength of use of the exposure apparatus used in photolithography becomes shorter and shorter, and now, using far wavelength excimer laser light (XeCl, KrF, ArF, etc.) has been examined. have.

There is a chemically amplified resist used for the pattern formation of lithography in this wavelength region.

As a photoresist composition for an ArF light source, a resin in which an alicyclic hydrocarbon moiety is introduced in order to impart dry etching resistance has been proposed. As such resin, resin which copolymerized the monomer which has a carboxylic acid site | part of acrylic acid or methacrylic acid, the monomer which has a hydroxyl group, or a cyano group in a molecule | numerator with the monomer which has an alicyclic hydrocarbon group is illustrated.

On the other hand, in addition to the method of introducing an alicyclic hydrocarbon moiety into the side chain of the acrylate monomer, a method of imparting dry etching resistance utilizing an alicyclic hydrocarbon moiety as a polymer main chain is also studied.

Further, Japanese Patent Laid-Open Nos. 9-73173, 9-90637 and 10-161313 disclose an alkali-soluble group protected by a structure containing an alicyclic group, and an alkali-soluble group. A resist material using an acid-sensitive compound containing a structural unit that is separated by ions and becomes alkali-soluble is described.

Moreover, the resin which introduce | transduced the hydrophilic 5- or 6-membered lactone group in order to improve the hydrophilicity with respect to alkali developing solution, or adhesiveness with respect to a board | substrate to resin which has these alicyclic groups is Unexamined-Japanese-Patent No. 9-90637, Japanese Patent Laid-Open No. Hei 10-207069, Japanese Patent Laid-Open No. Hei 10-274852, and Japanese Patent Laid-Open No. Hei 10-239846.

Even in the above technique, in the photoresist preparation (particularly, photoresist for far-ultraviolet exposure), there is still an improvement due to a resin containing an acid-decomposable group.

However, in these compositions, there existed a problem that the resolution of a pattern was inhibited by factors, such as the edge roughness of a line pattern. Here, the edge roughness means that the top and bottom edges of the line pattern of the resist fluctuate irregularly in the direction perpendicular to the line direction due to the characteristics of the resist, so that the edges appear uneven when viewed from the top. Say.

In addition, there was room for improvement in the problem of density dependency. Since various patterns are included as a trend of devices in recent years, various performances are required for resists. That is, the device has a part where the lines are dense, and conversely, a pattern having a larger space than the line, and an isolated line. For this reason, it is important to resolve various lines with high reproducibility. However, it is not always easy to reproduce various lines due to optical factors, and the solution by the resist is not clear. In particular, in the resist system containing the alicyclic group described above, the performance difference between the isolation pattern and the dense pattern is remarkable, and improvement is desired.

In addition, in the conventional resist composition, there is a problem of the exposure dose dependency in which the pattern line width changes due to a slight change in the exposure dose, and a resist composition having a smaller line width change and a wider exposure margin has been required.

It is therefore an object of the present invention to provide a chemically amplified positive photoresist composition excellent in all properties of resolution, exposure margin, pattern roughness, and roughness dependency.

The present inventors have found that the object of the present invention is achieved by using an acid-decomposable resin having a specific photoacid generator and a lactone structure as a result of intensive examination of the constituent material of a resist composition in a positive chemical amplification system. Invented.

That is, the said object is achieved by the following structures.

(1) (A) The cation portion is composed of iodonium or sulfonium, and the anion portion is composed of an anion represented by R ^F SO ₃ ⁻ (wherein R ^F is a fluorinated alkyl group having 1 to 20 carbon atoms). A photoacid generator selected from sulfonate salts and further generating an acid by irradiation of at least two actinic rays or radiations in which the difference in the carbon number of R ^{F in} the anion portion is in the range of 2 to 15, and

(B) a resin containing a repeating unit having a group represented by at least one of the following general formulas (I-1) to (I-4), which is decomposed by the action of an acid to increase its solubility in alkali; A positive photoresist composition.

In general formulas (I-1) to (I-4);

R <_1> -R <_5> may be same or different, may have a hydrogen atom and a substituent, and represents an alkyl group, a cycloalkyl group, or an alkenyl group. Two in R ₁ to R ₅ may be bonded to each other to form a ring.

(2) according to claim 1 wherein, (A) relative to component, of a carbon number of R ^F is relatively large as the anion portion mine Presentation R ^F is a straight-chain fluorine-substituted alkyl group of photo-acid generator in a range of 4 to 20 carbon atoms The photonic acid generator selected from the group and having a relatively low carbon number of R ^F is selected from the group of photoacid generators in which the anionic moiety R ^F is a linear fluorine-substituted alkyl group having 1 to 5 carbon atoms. Resist composition.

(3) The positive photoresist composition according to claim 1 or 2, wherein the cationic portion of the at least one photoacid generator is represented by the following general formulas (I), (II) or (III).

In the general formulas (I) to (III);

R ₁ to R ₃₇ may be the same or different and represent a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom or a -SR ₃₈ group. R ₃₈ represents a linear, branched or cyclic alkyl group or an aryl group. Or, R ₁ containing _{~R 15, R 16 ~R 27,} R 28 ~R by a combination of two or more of the ₃₇ different, a single bond, carbon, oxygen, sulfur, and one kind selected from nitrogen or in combination of two or more You may form a ring.

(4) The resin according to any one of claims 1 to 3, wherein the resin of (B) contains at least one of aliphatic carbon hydrogen structures represented by the following general formulas (pI) to (pVI). A positive photoresist composition comprising a repeating unit having an alkali-soluble group protected by a species group.

In general formulas (pI) to (pVI);

R ₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. Display.

R ₁₂ to R ₁₆ each independently represent a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R ₁₂ to R ₁₄ , or any of R ₁₅ and R ₁₆ One represents an alicyclic hydrocarbon group.

R ₁₇ to R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R ₁₇ to R ₂₁ represents an alicyclic hydrocarbon group . In addition, any one of R <_19> , R <_21> represents a C1-C4 linear or branched alkyl group or alicyclic hydrocarbon group.

R ₂₂ to R ₂₅ each independently represent a C1-4 straight or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R ₂₂ to R ₂₅ represents an alicyclic hydrocarbon group.

(5) The group according to any one of claims 1 to 4, wherein the group containing an alicyclic hydrocarbon structure represented by general formulas (pI) to (pVI) is a group represented by the following general formula (pIa). A positive photoresist composition.

R <_28> represents the alkyl group which may have a substituent in general formula (pIa). R ₂₉ to R ₃₁ may be the same or different and represent an hydroxy group, a halogen atom, a carboxy group or an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group or an acyl group which may have a substituent. p, q, and r respectively independently represent the integer of 0 or 1-3.

(6) The positive photoresist composition according to any one of claims 1 to 5, wherein the resin of (B) contains a repeating unit represented by the following general formula (a).

In general formula (a), R represents a hydrogen atom, a halogen atom, or a C1-C4 substituted or unsubstituted alkyl group. R <_32> -R <_34> may be same or different and represents a hydrogen atom or a hydroxyl group. At least one of R ₃₂ to R ₃₄ represents a hydroxyl group.

Moreover, the following forms are also preferable.

(7) The positive photoresist composition according to any one of items 1 to 6, further comprising (C) an acid diffusion inhibitor.

Embodiment of the Invention

Hereinafter, the compound used for this invention is demonstrated in detail.

<(A) Compound which generate | occur | produces an acid by irradiation of actinic light or a radiation (it is called a photoacid generator or (A) component)>

In the present invention, as the photoacid generator, a sulfonate in which the cation portion is composed of iodonium or sulfonium, and the anion portion is represented by R ^F SO ₃ ⁻ (wherein R ^F is a fluorine-substituted alkyl group having 1 to 20 carbon atoms). At least two photoacid generators are selected from which the carbon number difference of R ^{F in} the anion portion is in the range of 2 to 15.

In addition, the carbon number of R ^F is a relatively large light image generating composition As the anion part R ^F is selected from the group consisting of a straight chain fluorine-substituted alkyl group of photo-acid generator in a range of 4 to 20 carbon atoms, the carbon number of R ^F is relatively small The photoacid generator is particularly preferably selected from the group of photoacid generators in which R ^F in the anion portion is a linear fluorine-substituted alkyl group having 1 to 5 carbon atoms.

Moreover, the photoacid generator represented with the following general formula (I), (II), or (III) is preferable for a cation part.

In the general formulas (I) to (III);

R ₁ to R ₃₇ may be the same or different and represent a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom or a -SR ₃₈ group. R ₃₈ represents a linear, branched or cyclic alkyl group or an aryl group. And a ring containing two or more selected from R ₁ to R ₁₅ , R ₁₆ to R ₂₇ , and R ₂₈ to R ₃₇ , selected from a single bond, carbon, oxygen, sulfur, and nitrogen; May be formed.

In the present invention, the cation portion is composed of iodonium or sulfonium, and the anion portion is composed of an anion represented by R ^F SO ₃ ⁻ (wherein R ^F represents a fluorinated alkyl group having 1 to 20 carbon atoms). A plurality of photoacid generators selected from the sulfonate salts are used.

The fluorine-substituted alkyl group represented by R ^F may be any of linear, branched and cyclic. Examples of preferred R ^F, is represented by _{CF 3 (CF 2) y,} y is an integer, a fluorine-substituted straight chain alkyl of 0-9.

The alkyl group as R ^F may have substituents such as a hydroxyl group and a cyano group, and further includes divalent linking groups such as -O-, -S-, -CO-, -COO-,-NHCO-, and -CONHSO _2- . You may contain it. In this case, the carbon number of R ^F also includes the carbon number of the linking group.

The alkyl group represented by R ^F may be substituted with one or more fluorine atoms, and preferably the hydrogen atom of the carbon atom at the α-position of sulfonic acid is substituted with the fluorine atom.

The composition of the present invention contains, as a photoacid generator, at least two (one pair) photoacid generators in which the difference in carbon number of R ^F is in the range of 2 to 15, preferably 3 to 7.

If for example in the carbon number of R ^F it is used 3, 4, 5, the photo-acid generator of three kinds of I, respectively, of the difference in carbon number of R ^F acid generator in a range from 2 to 15 pairs of I 1 exists and satisfying the above conditions. When three kinds of photoacid generators each having 2, 6, or 8 carbon atoms of R ^F are used, three pairs exist and the above conditions are satisfied.

It is preferable that the total amount of the photo-acid generator which forms a pair among the said photo-acid generator containing at least 2 types is 50-100 mol% with respect to all the photo-acid generators, More preferably, it is 70-100 mol%. .

The positive photoresist composition of the present invention contains a plurality of photoacid generators satisfying the above conditions together with the above-mentioned (B) specific resin (B-1) or polymer (B-2), which will be described later in detail. In the micro-light manufacturing using excimer laser light, it is excellent in all the characteristics of resolution, exposure margin, edge roughness of pattern, and density dependency.

In a preferred embodiment, among the at least one pair of photoacid generators in which the difference in the carbon number of R ^{F in} the anion portion is in the range of 2 to 15, the R ^F of the photoacid generator having a relatively high carbon number of R ^F is 4 to 20 carbon atoms. -chain fluorine-substituted alkyl group (in the following also abbreviated as a photo-acid generator "photo-acid generator A1"), and R ^F R ^F of the number of carbon atoms is relatively small in a photo-acid generating agent is a straight-chain fluorine-substituted 1 to 5 carbon atoms It is an alkyl group (Hereinafter, this photoacid generator is abbreviated as "mine generator A2.").

Moreover, it is preferable that molar ratio (A1 / A2) of photo-acid generator A1 and photo-acid generator A2 is 90/10-10/90, especially 80/20-20/80.

The cationic portion of the photoacid generator is preferably represented by the general formulas (I) to (III).

In general formula (I)-(III), as a linear, branched alkyl group of R <_1> -R <_38> , you may have a substituent, and a methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, t The C1-C4 thing like a butyl group is illustrated. As a cyclic alkyl group, you may have a substituent and a C3-C8 thing like a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group is illustrated.

As a linear, branched alkoxy group of R <_1> -R <_37> , for example, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butok The thing of 1-4 carbon atoms similar to a time is illustrated.

As a cyclic alkoxy group, a cyclopentyloxy group, for example, a cyclopentyloxy group, a cyclohexyloxy group is illustrated.

As the halogen atom of R ₁ ~R _37, there can be mentioned a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As an aryl group of R <_38>, the C6-C14 thing which may have substituents, such as a phenyl group, a tolyl group, a methoxyphenyl group, a naphthyl group, is mentioned, for example.

As these substituents, Preferably, a C1-C4 alkoxy group, a halogen atom (a fluorine atom, a chlorine atom, an iodine atom), a C6-C10 aryl group, a C2-C6 alkenyl group, a cyano group, a hydroxyl group , Carboxyl group, alkoxycarbonyl group, nitro group and the like.

Moreover, 1 type (s) or 2 or more types chosen from a single bond, carbon, oxygen, sulfur, and nitrogen which two or more of R <_1> -R <_15> , R <_16> -R <_27> and R <_28> -R <_38> couple | bond and form are formed As a ring to contain, a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, a pyrrole ring, etc. can be illustrated, for example.

Moreover, the photo-acid generator represented by the following general formula (IV) or (V) is also preferable.

The compound which has a penacylsulfonium salt structure which generate | occur | produces an acid by irradiation of actinic light or a radiation can illustrate the compound represented by the following general formula (IV), for example.

R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.

R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, or an aryl group.

Rx and Ry each independently represent an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group.

Two or more of R _1c to R _7c , and Rx and Ry may be bonded to each other to form a ring structure, and this ring structure may contain an oxygen atom, a sulfur atom, an ester bond, and an amide bond.

X ^- is, R ^F SO ₃ ^- displays. R ^F is the same as described above.

The alkyl group as R _1c to R _5c may be any of linear, branched or cyclic, for example, an alkyl group having 1 to 10 carbon atoms, preferably a linear and branched alkyl group having 1 to 5 carbon atoms (eg, a methyl group, an ethyl group, a straight chain or A branched propyl group, a linear or branched butyl group, a linear or branched pentyl group, and a C3-C8 cyclic alkyl group (for example, cyclopentyl group, cyclohexyl group) can be illustrated.

The alkoxy group as R _1c to R _{5c may} be any of linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear and branched alkoxy group having 1 to 5 carbon atoms (for example, a methoxy group and an ethoxy group). The time period, a linear or branched propoxy group, a linear or branched butoxy group, a linear or branched pentoxy group, and a C3-C8 cyclic alkoxy group (for example, a cyclopentyloxy group, a cyclohexyloxy group) can be illustrated.

Preferably, any one of R _1c to R _5c is a straight chain, branched, cyclic alkyl group, or a straight chain, branched or cyclic alkoxy group, and more preferably, the sum of the carbon numbers of R _1c to R _5c is 2 to 15. Solvent solubility improves more, and particle | grain generation is suppressed at the time of storage.

As an alkyl group as R <_6c> and R <_7c> , the thing similar to the alkyl group as R <_1c> -R <_5c> can be illustrated. As an aryl group, a C6-C14 aryl group (for example, a phenyl group) can be illustrated, for example.

The alkyl group as Rx and Ry can illustrate the same thing as the alkyl group as R <_1c> -R <_5c> .

2-oxoalkyl group can illustrate the group which has> C = O at the 2nd position of the alkyl group as R < _1c > -R < _5c >.

About the alkoxy group in the alkoxycarbonylmethyl group, the same thing as the alkoxy group as R <_1c> -R <_5c> can be illustrated.

As a group which Rx and Ry combine and form, a butylene group, a pentylene group, etc. can be illustrated.

By forming a ring, the compound of Formula (IV) is fixed in a three-dimensional structure, and the optical resolution is improved. For R _1c if two of the dogs with combined ~R _7c form a ring structure, in combination have one of the R _1c ~R _5c 1 and one R _6c and R _7c of being a single bond or a linking group, the case of forming a ring It is particularly preferable when R _5c and R _6c or R _7c are bonded to form a ring by a single bond or a linking group.

Examples of the linking group include an alkylene group which may have a substituent, an alkenylene group which may have a substituent, -O-, -S-, -CO-, -CONR- (R is a hydrogen atom, an alkyl group or an acyl group), and these The group combined by 2 or more can be illustrated, Moreover, you may have a substituent, The alkylene group, the alkylene group containing an oxygen atom, and the alkylene group containing a sulfur atom are preferable. As a substituent, an alkyl group (preferably C1-C15), an aryl group (preferably C6-C10, a phenyl group), an acyl group (for example, C2-C11), an acyl group (for example, C2-C11) Etc. can be illustrated.

Further, a methylene group, an ethylene group, a propylene _{group, - CH 2 - O -,} - CH 2 - S - and preferably a connection such as to form a 5 to 7-membered ring, an ethylene group, and _{- CH 2 - O -, -} CH ₂ - S - group is connected to form a 6-membered ring such as is particularly preferred. By forming the six-membered ring, the carbonyl plane and the C-S + sigma bond are closer to the vertical, and the photo resolution is improved by the orbital interaction.

Moreover, the _compound which couple | bonds through R1c- _R7c and Rx and Ry in any one position through a single bond or a linking group, and has two or more structures of Formula (IV) may be sufficient.

The sulfonium salt which does not have an aromatic ring is a salt which uses sulfonium represented by following formula (V) as a cation.

In formula, R <^1b> -R <^3b> respectively independently represents the organic group which does not contain an aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom.

X ^- is, R ^F SO ₃ ^- displays. R ^F is the same as described above.

The organic group which does not contain an aromatic ring as R ^1b to R ^3b is generally 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R ^1b to R ^3b are each independently, preferably an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, a vinyl group, and more preferably a straight chain, branched, cyclic 2-oxoalkyl group, or alkoxycarbonyl Methyl groups, most preferably straight chain, branched 2-oxoalkyl groups.

The alkyl group as R ^1b to R ^3b may be any of linear, branched or cyclic, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group) and carbon number The cyclic alkyl group (cyclopentyl group, cyclohexyl group, norbornyl group) of 3-10 can be illustrated.

The 2-oxoalkyl group as R ^1b to R ^3b may be any of straight chain, branched or cyclic, and preferably, a group having> C═O at the 2-position of the alkyl group can be exemplified.

As the alkoxy group in the alkoxycarbonylmethyl group as R ^1b to R ^3b , preferably, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, butyl group, pentyl group) can be exemplified.

R ^1b to R ^3b may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, and a nitro group.

Two of R ^1b to R ^{3b may be} bonded to each other to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by bonding two of R ^1b to R ^3b to each other include an alkylene group (for example, butylene group and pentylene group).

From the viewpoint of photoreactivity, a group in which one of R ^1b to R ^3b has a carbon-carbon double bond or a carbon-oxygen double bond is preferable.

At least one of R ^1b to R ^3b of the compound represented by General Formula (V) may have a structure in which at least one of R ^1b to R ^3b of another compound represented by General Formula (V) is bonded.

Specific examples (A1-1) to (A1-91) of the photoacid generator A1 which can be used in the present invention are shown below.

Specific examples (A2-1) to (A2-74) of the photoacid generator A2 which can be used in the present invention are shown below.

Examples Of these, a photo-acid generator _{A1, CF 3 (CF 2)} 3 SO 3 H, CF 3 (CF 2) 7 SO 3 H Examples of the compounds are preferred, and photo acid generator A2 occurring CF ₃ SO ₃ H, CF Preference is given to compounds which generate ₃ (CF ₂ ) ₃ SO ₃ H. As a preferable combination of photoacid generators A1 and A2 (photoacid generators A1 / A2, indicating generated acids), CF ₃ (CF ₂ ) ₃ SO ₃ H / CF ₃ SO ₃ H, CF ₃ (CF ₂ ) ₇ SO ₃ H / CF ₃ SO ₃ H, CF ₃ (CF ₂ ) ₇ SO ₃ H / CF ₃ (CF ₂ ) ₃ SO ₃ H.

In this invention, the addition amount of the photo-acid generator as (A) component, ie, the total amount of two or more paired photo-acid generators, is normally used in 0.001-40 weight% based on solid content in a composition, Preferably Preferably it is used in 0.01-20 weight%, More preferably, it is 0.1 to 5 weight range. If the amount of the photoacid generator is less than 0.001% by weight, the sensitivity is lowered. If the amount of the photoacid generator is more than 40% by weight, the light absorption of the resist is excessively high, so that the profile is deteriorated and the process (especially bake) margin is narrowed. not.

The sulfonium salt of the photoacid generator A1 or the photoacid generator A2 is, for example, a sulfonic acid and a salt corresponding to a triarylsulfonium halide obtained by reacting a substituted or unsubstituted phenyl sulfoxide with an aryl grignard reagent such as aryl magnesium bromide. A method of exchanging or condensing or salt-exchanging a substituted or unsubstituted phenylsulfoxide with a corresponding aromatic compound using an acid catalyst such as methanesulfonic acid / diphosphate or aluminum chloride, copper acetate of diarylionium salt and diarylsulfide It can synthesize | combine by the method of condensation, salt exchange, etc. using catalysts, such as these.

On the other hand, the iodonium salt of the photoacid generator A1 or the photoacid generator A2 can be synthesized by reacting an aromatic compound with a periodate, and salt-exchanging the obtained iodonium salt with a corresponding sulfonic acid.

In addition, the sulfonic acid or sulfonic acid salt used for salt exchange can be obtained by using a commercially available sulfonic acid as it is, or by hydrolysis of a sulfonic acid halide or the like.

The positive photoresist composition of this invention can use together photoacid generators other than the said specific compound.

As a photo-acid generator which can be used together, well-known light (400-200 nm ultraviolet-ray, far ultraviolet rays used for photoinitiator of photocationic polymerization, photoinitiator of radical photopolymerization, photochromic agent of pigment | dye, photochromic agent, or microresist etc.) And, particularly preferably, g-ray, h-ray, i-ray, KrF excimer laser light), ArF excimer laser light, electron beam, X-ray, molecular beam or ion beam, and an acid-generating compound and mixtures thereof. Can be.

As other photoacid generators that can be used in combination, for example, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenium salts, arsonium salts, onium salts, organic halogen compounds, organometallic / organohalogens The compound which produces | generates sulfonic acid by photolysis represented by a cargo, the photo-acid generator which has o-nitrobenzyl type protecting group, an imino sulfonate, etc., a disulfone compound, a diazo keto sulfone, a diazo disulfone compound, etc. can be illustrated.

Moreover, the compound which introduce | transduced the group which generate | occur | produces an acid by these light, or a compound in the main chain or side chain of a polymer can also be used together.

See also VNRPillai, Synthesis, (1), 1 (1980), A. Abad et al, Tetrahedron Lett., (47) 4555 (1971), DHR Barton et al, J. Chem. Soc., (C), 329 (1970). ), US Pat. No. 3,779,778, European Patent No. 126,712 and the like can also be used in combination with the acid-producing compound.

Among the compounds generating an acid by decomposition by irradiation of the actinic ray or radiation, particularly usefully used, the following general formula (PAG3), general formula (PAG4), general formula (PAG6) or general formula (PAG7) The compound displayed can be illustrated.

Ar <^1> , Ar <^2> may be same or different in general formula (PAG3) and (PAG4), and represents a substituted or unsubstituted aryl group. Preferred substituents include alkyl, haloalkyl, cycloalkyl, aryl, alkoxy, nitro, carboxyl, alkoxycarbonyl, hydroxy, mercapto and halogen atoms.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ may be the same or different and represent a substituted or unsubstituted alkyl group and an aryl group. Preferably, they are a C6-C14 aryl group, a C1-C8 alkyl group, and their substituted derivatives. Preferable substituents include an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group and a halogen atom for the aryl group, and an alkoxy group having 1 to 8 carbon atoms, a carboxyl group and an alkoxycarbonyl group for the alkyl group.

Z ^- represents a counter anion, for example _{^{BF 4 -, AsF 6 -,}} PF 6 -, SiF 6 2-, ClO 4 -, substituted and also good alkane sulfonic acid, alkane sulfonic acid as a purple, and optionally substituted benzene sulfonic acid, Naphthalene sulfonic acid, anthracene sulfonic acid, camphor sulfonic acid and the like are exemplified, but not limited thereto. Preferably, they are alkalsulfonic acid, perfluoro alkanesulfonic acid, alkyl substituted benzene sulfonic acid, and pentafluorobenzene sulfonic acid.

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

R <^206> represents a substituted or unsubstituted alkyl group and an aryl group in general formula (PAG6) and (PAG7). A represents a substituted or unsubstituted alkylene group, alkenylene group, arylene group. R represents a linear, branched or cyclic alkyl group or an aryl group which may be substituted.

Although the compound shown below is illustrated as these specific examples, It is not limited to these.

In this invention, what is represented by said formula (PAG-7) as an acid generator which can be used together is preferable.

These photoacid generators that can be used in combination are used in the range of 5% by weight or less, preferably in the range of 2% by weight or less, based on the high moisture content in the composition.

<Resin which decomposes by action of (B) acid and increases solubility to alkali>

Resin (hereinafter, simply referred to as "resin of (B)") whose solubility in alkali increases due to the action of the acid (B) used in the composition of the present invention is the above general formula (I-1) (I It contains a repeating unit which has group represented by -4).

In general formula (I-1)-(I-4), as an alkyl group in R <_1> -R <_5> , a linear and branched alkyl group may be illustrated and may have a substituent. As a linear or branched alkyl group, a C1-C12 linear or branched alkyl group is preferable, More preferably, it is a C1-C10 linear or branched alkyl group, More preferably, it is a methyl group, an ethyl group, and a propyl group. , Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.

As a cycloalkyl group in R <_1> -R <_5> , a C3-C8 thing, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, is preferable.

As an alkenyl group in R <_1> -R <_5> , a C2-C6 thing, such as a vinyl group, a propenyl group, butenyl group, and a hexenyl group, is preferable.

Moreover, as a ring formed by combining two of R <_1> -R <_5> , 3-8 membered rings, such as a cyclo propane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring, are illustrated.

In General Formulas (I-1) and (I-2), R ₁ to R ₅ may be bonded to any of seven carbon atoms constituting a cyclic skeleton.

As the other substituent of the alkyl group, cycloalkyl group and alkenyl group, alkoxy group having 1 to 4 carbon atoms, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group , Carboxyl group, alkoxycarbonyl group, nitro group and the like can be exemplified.

As a preferable repeating unit which has group represented by general formula (I-1)-(I-4), the repeating unit represented by the following general formula (AI) is illustrated.

In general formula (AI), R is the same as R in general formula (a) mentioned later. A 'represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a bivalent group combining these. B represents the group represented by either of general formulas (I-1) to (I-4). In A ', the thing of the following formula is illustrated as a bivalent group combined above, for example.

In the above formula, Ra, Rb, and r1 are the same as described later, respectively. m represents the integer of 1-3.

Although the specific example of the repeating unit represented by general formula (AI) is illustrated below, the content of this invention is not restrict | limited to these.

In the present invention, the resin of (B) further contains a repeating unit having an alkali-soluble group protected with at least one group among the groups containing an alicyclic hydrocarbon structure represented by the general formulas (pI) to (pVI). It is preferable to make the effect of this invention more remarkable.

In general formula (pI)-(pVI), as an alkyl group in R <_12> -R <_25> , any of substituted or unsubstituted may be sufficient, and the linear or branched alkyl group which has 1-4 carbon atoms is represented. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group and the like.

Further, other substituents of the alkyl group include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxyl group, alkoxycarbonyl group, Nitro group etc. can be illustrated.

As an alicyclic hydrocarbon group in R <_11> -R <_25> or the alicyclic hydrocarbon group which Z and a carbon atom form, monocyclic or polycyclic may be sufficient. Specifically, the group which has a C5 or more monocyclo, bicyclo, tricyclo, tetracyclo structure, etc. can be illustrated. 6-30 are preferable and, as for the carbon number, 7-25 are especially preferable. These alicyclic hydrocarbon groups may have a substituent.

Below, the structural example of an alicyclic part is shown among the groups containing an alicyclic hydrocarbon structure.

In this invention, as a preferable thing of the said alicyclic part, an adamantyl group, a noadamantyl group, a decalin residue group, a tricyclo decanyl group, a tetracyclo dodecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cyclo A heptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group can be illustrated. More preferably, they are an adamantyl group, a decalin residue group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

As a substituent of these alicyclic hydrocarbon groups, an alkyl group, a substituted alkyl group, a cycloalkyl group, an alkenyl group, an acyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group are illustrated. As an alkyl group, lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, isopropyl group, and a butyl group, are preferable, More preferably, they are a methyl group, an ethyl group, a propyl group, and an isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group can be illustrated.

Examples of the alkoxy group (including the alkoxy group of the alkoxycarbonyl group) include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group.

As a cycloalkyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc. are illustrated.

As an alkenyl group, a C2-C6 alkenyl group is illustrated and a vinyl group, a propenyl group, an allyl group, butenyl group, a pentenyl group, a hexenyl group, etc. are mentioned specifically ,.

As an acyl group, an acetyl group, an ethylcarbonyl group, a propyl carbonyl group, etc. are illustrated. Examples of the halogen atom include chlorine atom, bromine atom, iodine atom, fluorine atom and the like.

Among the structures represented by general formulas (pI) to (pVI), the group is preferably a general formula (pI), and more preferably a group represented by the general formula (pIa). In the general formula (pIa), an alkyl group of R ₂₈ , a halogen atom in R ₂₉ to R ₃₁ , an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group and an acyl group are exemplified in the substituent of the alicyclic hydrocarbon group. Can be mentioned.

As an alkali-soluble group protected by the structure represented by general formula (pI)-(pVI) in the said resin, various well-known groups in this technical field are illustrated. Specifically, a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol group are illustrated, Preferably they are a carboxylic acid group and a sulfonic acid group.

As an alkali-soluble group protected by the structure represented by general formula (pI)-(pVI) in the said resin, Preferably, the group represented by the following general formula (pVII)-(pXI) is illustrated.

Here, R <_11> -R <_25> and Z are the same as the said definition, respectively.

As a repeating unit which has the alkali-soluble group protected by the structure represented by general formula (pI)-(pVI) which comprises the said resin, the repeating unit represented by the following general formula (pA) is preferable.

In general formula (pA);

R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. Some R may be same or different, respectively. The halogen atom and alkyl group of this R can illustrate the same example as R of general formula (a) mentioned later.

A 'is the same as above.

Ra represents any one of formulas (pI) to (pVI).

Hereinafter, the specific example of the monomer corresponded to the repeating unit represented by general formula (pA) is shown.

The resin (B) may further contain other repeating units.

It is preferable that (B) resin in this invention contains the repeating unit represented by said general formula (a) as another copolymerization component. Thereby, developability and adhesiveness with a board | substrate improve. As alkyl which may have a substituent of R in general formula (a), the example similar to R1 in said general formula (I-1)-(I-4) is mentioned. As a halogen atom of R, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be illustrated. At least 1 of R <_32> -R <_34> of general formula (a) is a hydroxyl group, Preferably it is a dihydroxy body and a monohydroxy body, More preferably, it is a monohydroxy body.

Moreover, it is preferable that (B) resin in this invention contains the repeating unit represented by the following general formula (III-a) (III-d) as another copolymerization component. This improves the resolution of the contact hole pattern.

In said formula, R <_1> is the same as said R. R ₅ to R ₁₂ each independently represent a hydrogen atom or an alkyl group which may have a substituent. R represents a hydrogen atom or an alkyl group, a cyclic alkyl group, an aryl group or an aralkyl group which may have a substituent. m represents the integer of 1-10. X is a group consisting of an alkylene group, a cyclic alkylene group, an arylene group or an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group which may have a single bond or a substituent. At least two or more of these groups selected alone or in combination are combined to represent a divalent group which does not decompose by the action of an acid.

Z represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or the bivalent group which combined these. R <_13> represents a single bond, an alkylene group, an arylene group, or the bivalent group which combined these. R <_15> represents an alkylene group, an arylene group, or the bivalent group which combined these. R <_14> represents the alkyl group, cyclic alkyl group, aryl group, or aralkyl group which may have a substituent. R <_16> represents a hydrogen atom or the alkyl group, cyclic alkyl group, alkenyl group, aryl group, or aralkyl group which may have a substituent.

A represents either of the functional groups shown below.

As an alkyl group of R <_5> -R <_12> , R, R <_14> , R <_16> , a linear and branched alkyl group may be illustrated and may have a substituent. As a linear or branched alkyl group, a C1-C12 linear or branched alkyl group is preferable, More preferably, it is a C1-C10 linear or branched alkyl group, More preferably, it is a methyl group, an ethyl group, and a propyl group. , Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.

Examples of cyclic alkyl groups of R, R _14, R _16, and examples 3 to 30 carbon atoms is, specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, Boro group, a tricyclo Decanyl group, dicyclopentenyl group, norbornane epoxy group, menthyl group, isomentyl group, neomentyl group, tetracyclododecanyl group, steroid residue and the like can be exemplified.

R, R _14, of R ₁₆ and the aryl group, and examples of 6 to 20 carbon atoms is, may have a substituent. Specifically, a phenyl group, tolyl group, naphthyl group, etc. are illustrated.

As the aralkyl group of R, R _14, R _16, and illustrated that 7 to 20 carbon atoms, which may optionally have a substituent such as a good, a benzyl group, a phenethyl group, a cumyl group and the like. As an alkenyl group of R <_16> , a C2-C6 alkenyl group is illustrated, Specifically, a vinyl group, a propenyl group, an allyl group, butenyl group, a pentenyl group, a hexenyl group, a cyclopentenyl group, a cyclohexenyl group, 3 -Oxocyclohexenyl group, 3-oxocyclopentenyl group, 3-oxoisodenyl group, etc. are illustrated. Of these, the cyclic alkenyl group may contain an oxygen atom.

The linking group X is selected from the group consisting of an alkylene group, a cyclic alkylene group, an arylene group, which may have a substituent, or an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group. Divalent groups, alone or in combination of at least two or more of these groups, which are not decomposed by the action of an acid are exemplified.

Z represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or the bivalent group which combined these. R <_13> represents a single bond, an alkylene group, an arylene group, or the bivalent group which combined these. R <_15> represents an alkylene group, an arylene group, or the bivalent group which combined these.

As an arylene group in X, R <_13> , R <_15> , a C6-C10 thing is illustrated and may have a substituent. Specifically, a phenylene group, a trylene group, a naphthylene group, etc. are illustrated.

As X cyclic alkylene group, what the above-mentioned cyclic alkyl group becomes bivalent is illustrated.

As an alkylene group in X, Z, R <_13> , R <_15> , group represented by a following formula can be illustrated.

= [C (Ra) (Rb)] r1-

In formula, Ra and Rb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, and both may be same or different. As an alkyl group, lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, are preferable, More preferably, they are selected from a methyl group, an ethyl group, a propyl group, and an isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group can be illustrated. As an alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be illustrated. As a halogen atom, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. can be illustrated. r1 represents the integer of 1-10.

Although the specific example of linking group X is shown below, the content of this invention is not limited to these.

Examples of other substituents in the alkyl group, cyclic alkyl group, alkenyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group and arylene group include a carboxyl group, acyloxy group, cyano group, alkyl group, substituted alkyl group, halogen atom, hydroxyl group, An alkoxy group, an acetylamide group, an alkoxycarbonyl group, and an acyl group are illustrated. Here, as an alkyl group, lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, an isopropy group, a butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group, can be illustrated. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group can be illustrated. As alkoxy, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be illustrated. As acyloxy, an acetoxy group etc. are illustrated. As a halogen atom, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. can be illustrated.

Hereinafter, although the specific example of the structure of the terminal remove | excluding X is shown as a specific example of the structure of the side chain in general formula (III-b), the content of this invention is not limited to these.

Hereinafter, although the specific example of the monomer corresponded to the repeating structural unit represented by general formula (III-c) is shown, the content of this invention is not restrict | limited to these.

Hereinafter, although the specific example of the monomer corresponded to the repeating structural unit represented by general formula ((III-d) is shown, the content of this invention is not limited to these.

In general formula (III-b), as R <_5> -R <_12> , a hydrogen atom and a methyl group are preferable. As R, a hydrogen atom and a C1-C4 alkyl group are preferable. 1-6 of m are preferable.

In general formula (III-c), as R <_13> , alkylene groups, such as a single bond, a methylene group, ethylene group, a propylene group, butylene group, are preferable, and as R <_14> , C1-C10, such as a methyl group and an ethyl group, is preferable. Preference is given to cyclic alkyl groups such as alkyl groups, cyclopropyl groups, cyclohexyl groups and camphor residues, naphthyl groups and naphthylmethyl groups. Z is preferably a single bond, an ether bond, an ester bond, an alkylene group having 1 to 6 carbon atoms, or a combination thereof, and more preferably a single bond or an ester bond.

In general formula (III-d), as R <_15> , a C1-C4 alkylene group is preferable. As R <_16> , a C1-C8 alkyl group, cyclohexyl group, adamantyl group, norbornyl group, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, neopentyl group, and octyl group which may have a substituent Phenyl group, toluyl group, mesityl group, naphthyl group, camphor residue which may have a substituent, a boronyl group, an isoboroyl group, a menthyl group, a morpholino group, 4-oxocyclohexyl group, and a substituent are preferable. As these other substituents, halogen atoms, such as a fluorine atom, a C1-C4 alkoxy group etc. are preferable.

In this invention, the repeating unit represented by general formula (III-b) and general formula (III-d) is preferable also among general formula (III-a)-general formula (III-d).

In addition to the above, the resin of (B) is used in combination with various monomer repeating units for the purpose of controlling dry etching resistance, standard developer aptitude, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc. which are general requirements of resist. It can be used as coalescing.

As such a repeating unit, although the repeating unit corresponded to the following monomers can be illustrated, it is not limited to these.

Thus, the performance required for the resin, in particular, (1) solubility in the coating solvent, (2) film forming property (glass transition point), (3) alkali developability, and (4) film loss (hydrophilicity, alkali soluble group selection) ), (5) adhesion to the substrate of the non-exposed part, and (6) fine adjustment of dry etching resistance.

Examples of such copolymerized monomers include compounds having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Can be mentioned.

Specifically, for example, acrylic esters, for example alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) acrylate (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate , Octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, penta Erythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate and tetrahydrofurfuryl acrylate, etc.);

Methacrylic acid esters, for example alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) methacrylate (eg methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate) Acrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5- Hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate and tetrahydrofurfuryl methacrylate Rate, etc.);

Acrylamides, for example acrylamide, N-alkyl acrylamides (as alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohex Real groups, hydroxyethyl groups, etc.), N, N-dialkylacrylamides (as alkyl groups having from 1 to 10 carbon atoms, for example, methyl, ethyl, butyl, isobutyl, ethylhexyl and cyclohexyl groups); N-hydroxyethyl-N-methylacrylamide and N-2-acetamideethyl-N-acetylacrylamide and the like;

Methacrylamides, such as methacrylamide, N-alkyl methacrylamide (as alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group, cyclohexyl group Etc.), N, N-dialkyl methacrylamide (as alkyl group, ethyl group, propyl group, butyl group, etc.), N-hydroxyethyl-N-methyl acrylamide, etc .;

Allyl compounds such as allyl esters (for example, allyl acetate, allyl capronate, allyl caprylic acid, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetic acid and allyl lactate), and allyloxyethanol;

Vinyl ethers, such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-); 2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether , Tetrahydrofurfuryl vinyl ether, etc.);

Vinyl esters, such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl acetate Vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, and the like;

Dialkyl itaconic acid (for example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); Dialkyl esters of fumaric acid (for example, dibutyl fumarate and the like) or monoalkyl esters;

In addition, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleonitrile, etc. can be illustrated. In addition, the addition-polymerizable unsaturated compound copolymerizable with the above various repeating structural units may be sufficient.

In the resin of (B), the molar ratio of each repeating unit structure includes acid value, dry etching resistance of resist, standard developer suitability, substrate adhesion, dense dependency of resist profile, or resolution, heat resistance, and sensitivity generally required for resist. It is appropriately set to adjust the back.

Content of the repeating unit which has group represented by General Formula (I-1)-(I-4) in resin of (B) is 30-70 mol% in all the repeating units, Preferably it is 35-65 mol% More preferably, it is 40-60 mol%.

Moreover, content of the repeating unit which has group represented by General Formula (pI)-(pVI) is 20-75 mol% normally in all the repeating units, Preferably it is 25-70 mol%, More preferably, it is 30- 65 mol%.

Content of the repeating unit represented by general formula (a) in resin of (B) is 0 mol%-70 mol% normally in all the monomer repeating units, Preferably it is 10-40 mol%, More preferably, it is 15 It is-30 mol%.

Moreover, content of the repeating unit represented by general formula (III-a)-general formula (III-d) in resin of (B) is 0.1-30 mol% normally in all the monomer repeating units, Preferably Is 0.5 to 25 mol%, more preferably 1 to 20 mol%.

Moreover, based on the monomer of the said other copolymerization component, content in resin of a repeating unit can also be set suitably according to the performance of a desired resist, Generally, in general formula (I-1)-(I-4), 99 mol% or less is preferable with respect to the total mole number which totaled the repeating unit containing group represented by either, and the repeating unit which has group represented by general formula (pI)-(pVI), More preferably, 90 mol% or less, More preferably, it is 80 mol% or less.

The weight average molecular weight Mw of the resin of (B) is polystyrene standard by gel permeation chromatography (GPC) method, Preferably it is 1,000-1,000,000. More preferably, it is 1,500-500,000, More preferably, it is 2,000-200,000, Especially preferably, it is the range of 2,500-100,000, The larger the weight average molecular weight, the more heat resistance etc. improve, while developability etc. fall, It adjusts to a preferable range by balance.

Resin of (B) used for this invention can be synthesize | combined by the radical polymerization method according to a conventional method, for example.

Hereinafter, although the specific example of resin of (B) of this invention is illustrated, the content of this invention is not limited to these.

In said formula, m, n, p, or n1, n2, n3 all show the molar ratio of repeating number. The repeating unit which has group represented by either of (I-1)-(I-4) was represented by n, and the case where two or more types are combined was distinguished by n1, n2, etc. The repeating unit having a group containing an alicyclic hydrocarbon structure represented by (pI) to (pVI) was represented by m. The repeating unit represented by general formulas (III-a) to (III-d) was represented by p.

When it contains the repeating unit represented by general formula (III-a)-(III-d), m / n / p is (25-70) / (25-65) / (3-40). When it does not contain the repeating unit represented by general formula (III-a)-(III-d), m / n is (30-70) / (70-30). It may be a block copolymer or a random copolymer. It may be a regular polymer or an irregular polymer.

In the positive photoresist composition for far ultraviolet exposure of the present invention, the amount of the resin added in the whole composition of the resin of (B) is preferably 40 to 99.99% by weight in the total resist solid content, and more preferably 50 to 99.97% by weight.

The positive photoresist composition of the present invention may further contain, if necessary, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a surfactant, a photosensitizer, an organic base compound, a compound for promoting solubility in a developing solution, and the like.

It is preferable that the positive resist composition of this invention contains surfactant, and it is especially preferable that it contains a fluorine and / or silicone surfactant.

That is, it is especially preferable to contain any one, or 2 or more types of fluorine-type surfactant, silicone type surfactant, and surfactant containing both a fluorine atom and a silicon atom.

As these surfactants, for example, Japanese Patent Laid-Open No. 62-36663, Japanese Patent Laid-Open No. 61-226746, Japanese Patent Laid-Open No. 61-226745, Japanese Patent Laid-Open No. 62-170950, Japanese Patent Laid-Open No. 63-34540 , Surfactants described in JP-A-7-230165, JP-A-8-62834, JP-A-9-54432 and JP-A-9-5988, and the following commercially available interfaces The active agent can be used as it is.

Commercially available surfactants include, for example, Eftop EF301, EF303 (manufactured by New Akita Kasei Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitom 3M), Megafack F171, F173, F176, F189, R08 (Dainippon Ink Company And fluorine-based surfactants or silicone-based surfactants such as Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.). Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone type surfactant.

The compounding quantity of surfactant is 0.001 weight%-2 weight% normally, based on solid content in the composition of this invention, Preferably they are 0.01 weight%-1 weight%. These surfactants may be added alone, or may be added in any combination.

As surfactant which can be used for that excepting the above, Specifically, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether; Polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; Polyoxyethylene polyoxypropylene block copolymer; Sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate and sorbitan tristearate; Polyoxyethylene sorbitan such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Nonionic surfactants, such as nonfatty acid ester, are mentioned.

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

The acid diffusion inhibitor (C) which can be used in the present invention is preferably added in view of suppressing fluctuations in sensitivity and resolution during the time elapsed from post-exposure heating and development, and are preferably organic basic compounds. . Examples of the organic basic compound include a nitrogen-containing basic compound having the following structure.

Here, R ²⁵⁰ , R ^251, and R ²⁵² may be the same or different and are a hydrogen atom, a C 1-6 alkyl group, a C 1-6 aminoalkyl group, a C 1-6 hydroxyalkyl group, or a C 6-20 substituent Or an unsubstituted aryl group, wherein R ²⁵¹ and R ²⁵² may combine with each other to form a ring.

(Wherein, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ may be the same or different and represent an alkyl group having 1 to 6 carbon atoms)

A more preferable compound is a nitrogen-containing basic compound having two or more nitrogen atoms in different chemical environments in one molecule, particularly preferably a compound having both a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom, or It is a compound which has an alkylamino group. Preferred embodiments include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or unsubstituted pyrazole, substituted or Unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted aminomorpholine and substituted or unsubstituted Substituted aminoalkyl morpholine etc. are mentioned. Preferred substituents include amino groups, aminoalkyl groups, alkylamino groups, aminoaryl groups, arylamino groups, alkyl groups, alkoxyl groups, acyl groups, acyloxy groups, aryl groups, aryloxy groups, nitro groups, hydroxyl groups and cyano groups.

Preferred specific 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-methyl-pyridine, 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-tolyl-pyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyri Midine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpho , N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4,3,0] nona-5-ene, 1,8-diazabicyclo [5,4,0] undeca-7 -Ene, 2,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMETU Although tertiary morpholine derivatives, such as) and interference amines (for example, what is described in the paragraph of this publication) of Unexamined-Japanese-Patent No. 11-52575 are mentioned, It is not limited to these.

As a particularly preferred embodiment, 1,5-diazabicyclo [4,3,0] nona-5-ene, 1,8-diazabicyclo [5,4,0] undeca-7-ene, 1,4- Diazibicyclo [2,2,2] octane, 4-dimethylaminopyridine, hexamethylenetetraamine, 4,4-di-methylimidazoline, pyrrole, pyrazole, imidazole, pyridazine, pyrimidine, CHMETU, etc. And interfering amines such as tertiary morpholines and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

Among them, 1,5-diazabicyclo [4,3,0] nona-5-ene, 1,8-diazabicyclo [5,4,0] undeca-7-ene, 1,4-diazabi Cyclo [2,2,2] octane, 4-dimethylaminopyridine, hexamethylenetetraamine, CHMETU and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate are preferred.

These nitrogen-containing basic compounds are used alone or in combination of two or more thereof. The amount of the nitrogen-containing basic compound is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solids of the entire composition of the photosensitive resin composition. Weight percent. If it is less than 0.001% by weight, the effect of adding the nitrogen-containing basic compound is not obtained. On the other hand, when it exceeds 10 weight%, there exists a tendency for the fall of a sensitivity and the developability of a non-exposed part to deteriorate.

The positive resist composition of this invention is melt | dissolved in the solvent which melt | dissolves each said component, and apply | coats on a support body. Examples of the solvent used herein include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 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 preferred. These solvents are used individually or in mixture of them.

Especially, as a preferable solvent, 2-heptanone, (gamma) -butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol monomethyl ether acetate, methyl lactate, ethyl lactate, methyl methoxy propionate, ethyl ethoxy propionate, N-methylpyrrolidone and tetrahydrofuran.

It is also preferable to mix 2 or more types of solvents, Especially preferably, it is a mixed solvent of the solvent which does not contain a hydroxyl group, and the solvent containing a hydroxyl group.

This positive resist composition of the present invention is applied onto a substrate to form a thin film. As for the thickness of this coating film, 0.2-1.2 micrometer is preferable. In the present invention, a commercially available inorganic or organic antireflection film can be used.

As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon, and an organic film type made of a light absorber and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, a sputtering apparatus, etc. to form the film. As the organic antireflection film, for example, a condensation product of a diphenylamine derivative described in Japanese Patent Publication No. Hei 7-69611 with a formaldehyde-modified melamine resin, an alkali-soluble resin and a light absorber, or maleic anhydride described in US Patent No. 5294680 A reaction product of a copolymer with a diamine type light absorber, the resin binder described in JP-A-6-118631 and the methylolmelamine-based crosslinking agent, and the carboxylic acid group and the epoxy group-absorption described in JP-A-6-118656. Acryl resin antireflection film having a group in the same molecule, consisting of methylol melamine and benzophenone light absorbing agent described in Japanese Patent Application Laid-open No. Hei 8-87115, low molecular absorption in polyvinyl alcohol resin of Japanese Patent Application Laid-open No. Hei 8-179509 Addition of the agent, etc. are illustrated.

In addition, as the organic antireflection film, DUV-30 series, DUV-40 series, AC-2, AC-3, etc., manufactured by Brae Science, Inc. may be used.

The resist solution is applied on a substrate (e.g., silicon / silicon dioxide coating) by a suitable coating method such as spinner, coater, etc. to be used in the manufacture of precision integrated circuit elements After that, a good resist pattern can be obtained by exposing, baking, and developing through a predetermined mask. The exposure light is preferably light having a wavelength of 150 nm to 250 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), an X-ray, an electron beam, etc. are mentioned.

As a developing solution, Inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-butylamine; Tertiary amines such as triethylamine and methyldiethylamine; Alcohol amines such as dimethylethanolamine and triethanolamine; Quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; Alkaline aqueous solutions, such as cyclic amines, such as a pyrrole and a 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 of Photoacid Generator as (A) Component]

Hereinafter, although the synthesis example of the photo-acid generator which is (A) component is shown, the other photo-acid generator used below was synthesize | combined by the same method or the said general method, or what was marketed was used.

The following photo-acid generator used what was produced by Midorikagaku Corporation.

Triphenylsulfonium perfluoro-n-butanesulfonate:

(A1-1), (A2-4)

Triphenylsulfonium trifluoromethanesulfonate: (A2-1)

Bis (t-butylphenyl iodonium) perfluoro-n-butanesulfonate: (A1-49)

[Synthesis of triphenylsulfonium perfluoro-n-octanesulfonate (A1-3)]

50 g of diphenyl sulfoxide was dissolved in 800 ml of benzene, and 200 g of aluminum chloride was added thereto, and the mixture was refluxed for 24 hours. The reaction solution was slowly poured into 2 L of water, and 400 ml of strong hydrochloric acid was added thereto, followed by heating at 70 ° C for 10 minutes. This aqueous solution was washed with 500 ml of ethyl acetate, and after filtering, 200 g of ammonium iodide dissolved in 400 ml of water was added. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate and dried to obtain 70 g of triphenylsulfonium iodine.

17.6 g of triphenylsulfonium yodine was dissolved in 1000 ml of methanol, 12.5 g of silver oxide was added to the solution, and the mixture was stirred at room temperature for 4 hours. The solution was filtered and 25 g of perfluoro-n-octanesulfonic acid methanol solution was added thereto. The reaction solution was concentrated, and the precipitated oily substance was dissolved in ethyl acetate, washed with water, dried and concentrated to give 20.5 g of the target product.

[Synthesis of tri (t-butylphenyl) sulfonium perfluoro-n-butanesulfonate (A1-5) and (A2-8)]

A mixture of di (t-butylphenyl) sulfide (80 mmol), di (t-butylphenyl) iodium perfluoro-n-butanesulfonate (20 mmol) and silver benzoic acid (4 mmol) was carried out at room temperature. It stirred at 4 degreeC for 4 hours. The reaction solution was left to cool, 100 ml of ethanol was added thereto, and the precipitate was removed. The filtrate was concentrated, and when 200 ml of ether was added thereto, the powder was precipitated, which was collected by filtration, washed with ether and dried to obtain the target product.

[Synthesis of Resin Example (1) of the Present Invention]

Molar ratio of 2-methyl-2-adamantyl methacrylate and 5-exo-methacrylate of 6-endo-hydroxybicyclo [2.2.1] heptane-2-endo-carboxylic acid-γ-lactone It put in the ratio of 50/50, melt | dissolved in N, N- dimethylacetamide / tetrahydrofuran = 5/5, and adjusted 100 ml of the solution of 20% of solid content concentration.

5-exo-methacrylate of 6-endo-hydroxybicyclo [2.2.1] heptane-2-endo-carboxylic acid-γ-lactone is 6-endo-hydroxybicyclo [2.2.1] heptane After acetoxy-lactoneization of 2-endo-carboxylic acid, a compound synthesized by alkali hydrolysis of the acetoxy group to the hydroxy group and esterification with methacrylic acid chloride was used. J. Chem. Soc., 227 (1959), Tetrahedron, 21., 1501 (1965).

3 mol% of Wako Junyaku Kogyo Co., Ltd. product V-65 was added to this solution, and it was dripped at 10 ml of N, N- dimethylacetamide heated to 60 degreeC over 3 hours under nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated for 3 hours, 1 mol% of V-65 was added again, and stirred for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and the white powder was crystallized and precipitated in 3 L of distilled water. The polymer composition determined from C ¹³ NMR was 51/49. In addition, the weight average molecular weight of the standard polystyrene conversion calculated | required by GPC measurement was 7,200.

In the same manner as in the synthesis example, the resin examples (2) to (59) shown above were synthesized. Table 1 shows the molar ratio of the repeating units (the order from the left of the repeating units shown in each resin example) and the weight average molecular weight.

Examples 1 to 59 and Comparative Examples 1 to 5

[Adjustment and Evaluation of Photosensitive Composition]

The resin synthesized in the above synthesis example and each component shown in Table 2 were dissolved in the solvent shown in Table 2 at a ratio of 12% by weight of solid content, and then filtered through a 0.1 μm microprofile, and Examples 1 to 59 and Comparative Examples. Positive resists of 1 to 5 were adjusted.

Table 2 shows each component of the composition of the present invention used.

Each symbol in Table 2 shows the following.

Resin Z: 2-Methyl-2-adamantyl methacrylate mechatronic lactone methacrylate (50/50), weight average molecular weight 6900

Acid Diffusion Inhibitor

B1: DBN; 1,5-diazabicyclo [4.3.0] nona-5-ene

B2: TPI; 2,4,5-triphenylimidazole

B3: DCMA; dicyclohexylmethylamine

B4: 2,6-diisopropylaniline

B5: TPSA; triphenylsulfonium acetate

[Surfactants]

W1: Mega pack F176 (product made by Dainippon Ink Corporation) (fluorine system)

W2: Mega pack R08 (product of Dainippon Ink Corporation) (fluorine and silicon type)

W3: polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) (silicone type)

W4: Toroazole S-366 (Toro Chemical Co., Ltd.)

[solvent]

PGMEA: Propylene glycol monomethyl ether acetate

PGME: Propylene glycol monomethyl ether

CH: cyclohexanone

BL: γ-butyrolactone

<Image evaluation method>

(1) Evaluation of resolution, exposure margin, roughness dependence and line edge roughness

On a silicon substrate treated with hexamethyldisilazane with a spin coater, an anti-reflection film DUV-42 manufactured by Bluwa Science Co., Ltd. was uniformly coated with 600 ohms, dried on a photoresist at 100 ° C. for 90 seconds, and then 240 ° C. at 190 ° C. for 240 seconds. Heat drying was performed. Then, each photosensitive resin composition was apply | coated with a spin coater, it dried for 90 second at 120 degreeC, and the resist film of 0.3 micrometer was formed. The resist film was exposed through an mask with an ArF excimer laser stepper (NA = 0.6 manufactured by ISI) and heated on a photoresist at 120 ° C for 90 seconds immediately after the exposure. Further, the solution was developed at 23 ° C. for 60 seconds in an aqueous 2.38% tetramethylantimonium hydroxide solution, rinsed with pure water for 30 seconds, and dried to obtain a resist line pattern.

RESOLUTION: The resolution represents the limit resolution in the exposure amount which reproduces the mask pattern of 0.13 micrometer.

[Exposure Margin]: The exposure dose for reproducing the mask pattern of the line end space (1/1) of 0.13 mu m is the optimal exposure dose, and the exposure dose width for the line width of 0.13 mu m ± 10% divided by the optimum exposure dose is 100%. It is expressed as (%). The larger the number, the smaller the change in line width with respect to the change in exposure dose.

Roughness dependency

Overlapping depths of focus allowing 0.13 µm ± 10% in line end space patterns (dense pattern: line end space 1/1) and isolated line patterns (coarse pattern: line end space 1/5) having a line width of 0.13 µm, respectively. The range was obtained. The larger this range, the better the density dependency.

[Line Edge Roughness]

For a range of 5 μm in the longitudinal edge of the isolated line pattern, the distance from the appropriate baseline with the edge was measured by 50 points by measuring SEM (S-8840, manufactured by Nichiritsu Seisakusho Co., Ltd.), and the standard deviation was determined. 3σ was calculated. Smaller values indicate better performance.

Table 3 shows the results.

As will be apparent from the results in Table 3, the positive resist composition of the present invention is at a satisfactory level for all of them. That is, it is suitable for lithography using far ultraviolet rays starting with ArF excimer laser exposure.

The present invention is capable of providing a positive resist composition which is preferable for far ultraviolet light, especially ArF excimer light, and which is excellent in terms of resolution, exposure margin, density dependency, and line edge roughness.

Claims (6)

(A) is composed of a cation portion iodonium or sulfonium, the anion portion R ^F SO ₃ ^- (wherein, R ^F is a fluorine-substituted alkyl group of 1 to 20 carbon atoms) in the acid salts that are composed of anions represented by A photoacid generator which is selected and further generates an acid by irradiation of two or more actinic rays or radiations in which the difference in the carbon number of R ^{F in} the anion portion is in the range of 2 to 15; and (B) containing a repeating unit having a group represented by at least one of the following general formulas (I-1) to (I-4), and containing a resin which is decomposed by the action of an acid and has increased solubility in alkali A positive photoresist composition. (In General Formula (I-1)-(I-4); R ₁ to R ₅ may be the same or different and represent an alkyl group, a cycloalkyl group or an alkenyl group which may have a hydrogen atom or a substituent. Two of R ₁ to R ₅ may be bonded to each other to form a ring.) Claim 1 wherein, (A) for the components, the carbon number of R ^F is relatively large as the anion portion mine Presentation R ^F is selected from straight-chain fluorine-substituted alkyl group of the photo-acid generator in a range of 4 to 20 carbon atoms in and, a positive photoresist composition, wherein the carbon number of R ^F is relatively small as the photoacid generating the anion portion R ^F is selected from the group of straight-chain fluorine-substituted alkyl group of photo-acid generator in a range of 1 to 5 carbon atoms. The positive photoresist composition according to claim 1 or 2, wherein the cation part of at least one photoacid generator is represented by the following general formulas (I), (II) or (III). (In said general formula (I)-(III); R ₁ to R ₃₇ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom or a -SR ₃₈ group. R ₃₈ represents a linear, branched or cyclic alkyl group or an aryl group. Moreover, two or more of R <_1> -R <_15> , R <_16> -R <_27> and R <_28> -R <_37> couple | bonds, and contains 1 type (s) or 2 or more types chosen from a single bond, carbon, oxygen, sulfur, and nitrogen. You may form a ring.) The resin of (B) according to any one of claims 1 to 3, wherein the resin of (B) is protected with at least one group among groups containing an alicyclic carbon structure represented by the following general formulas (pI) to (pVI). A positive photoresist composition, further comprising a repeating unit having an alkali-soluble group. (In the general formulas (pI) to (pVI); R ₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, and Z is an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom Is displayed. R ₁₂ to R ₁₆ each independently represent a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R ₁₂ to R ₁₄ or any of R ₁₅ and R ₁₆ One represents an alicyclic hydrocarbon group. R ₁₇ to R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R ₁₇ to R ₂₁ represents an alicyclic hydrocarbon group. . In addition, any one of R <_19> , R <_21> represents a C1-C4 linear or branched alkyl group or alicyclic hydrocarbon group. R ₂₂ to R ₂₅ each independently represent a C1-C4 linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R ₂₂ to R ₂₅ represents an alicyclic hydrocarbon group.) The group containing the alicyclic hydrocarbon structure represented by the said general formula (pI)-(pVI) is group represented by the following general formula (pIa) in any one of Claims 1-4. Positive photoresist composition. (In General Formula (pIa), R ₂₈ represents an alkyl group which may have a substituent. R ₂₉ to R ₃₁ may be the same or different, and an alkyl group which may have a hydroxy group, a halogen atom, a carboxy group or a substituent, A cycloalkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group or an acyl group is represented, and p, q, and r each independently represent an integer of 0 or 1 to 3.) The positive photoresist composition according to any one of claims 1 to 5, wherein the resin of (B) contains a repeating unit represented by the following general formula (a). (In formula (a), R represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. R ₃₂ to R ₃₄ may be the same or different and represent a hydrogen atom or a hydroxyl group. At least one of R ₃₂ to R ₃₄ represents a hydroxyl group.)