JP2003330202A - Method for manufacturing positive resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a positive resist composition having small changes in sensitivity with time and an excellent spreading property of a developer liquid. <P>SOLUTION: The method for manufacturing a positive resist composition containing a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure and increasing the solubility with an alkali developer liquid by the effect of an acid includes a filtration process to filter the resin having a monocyclic or polycyclic hydrocarbon structure and increasing the solubility with an alkali developer liquid by the effect of an acid through an ion exchange filter. Preferably, the method includes a filtration process to filter the resin having a monocyclic or polycyclic alicyclic hydrocarbon structure and increasing the solubility with an alkali developer liquid by the effect of an acid through a filter which removes insoluble colloid. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a positive resist composition used in the process of producing semiconductors such as ICs, the production of circuit substrates such as liquid crystals and thermal heads, and other photofabrication processes. Is. More specifically, the present invention relates to a method for producing a positive resist composition suitable when using a deep ultraviolet ray having a wavelength of 250 nm or less as an exposure light source.

[0002]

2. Description of the Related Art A chemically amplified positive resist composition produces an acid in an exposed area by irradiation with radiation such as far-ultraviolet light.
It is a pattern-forming material that forms a pattern on a substrate by changing the solubility of a portion irradiated with actinic radiation and a portion not irradiated with actinic radiation with a developer by the reaction using the acid as a catalyst.

When a KrF excimer laser is used as an exposure light source, the absorption mainly in the 248 nm region is small,
Since a resin having a basic skeleton of poly (hydroxystyrene) is used as a main component, it has a high sensitivity, high resolution, and forms a good pattern, and is a better system than the conventional naphthoquinone diazide / novolak resin system. ing.

However, when a light source with an even shorter wavelength, for example, an ArF excimer laser (193 nm) is used as an exposure light source, the compound having an aromatic group essentially exhibits large absorption in the 193 nm region, and therefore the above chemical amplification is performed. The system was not enough either. The use of poly (meth) acrylate as a polymer having small absorption in the wavelength region of 193 nm is described in J. Vac. Sci. Technol. , B9,
3357 (1991). However, this polymer has a problem that its resistance to dry etching generally performed in a semiconductor manufacturing process is lower than that of a conventional phenol resin having an aromatic group.

For this reason, an ArF excimer laser resist containing a resin having an alicyclic hydrocarbon structure has been developed, but the conventional ArF excimer laser resist has a problem that the sensitivity changes with time. Also,
The conventional ArF excimer laser resist also has a problem in developing solution developing property during development (ease of depositing the developing solution during development). That is, in the conventional ArF excimer laser resist, the resist film sometimes repelled the developing solution during development. For this reason, there is a problem that the developing solution spills from the silicon wafer during the developing solution development, and the developing solution is wasted. This problem becomes remarkable as the diameter of the silicon wafer used increases, and there is a demand for a resist that can develop a developing solution more smoothly and in a short time.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a positive resist composition in which the sensitivity is prevented from fluctuating over time and the developing solution develops at the time of development. is there.

[0007]

The present invention has the following constitution to achieve the above object of the present invention.

(1) In a method for producing a positive resist composition containing a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, the solubility of which in an alkali developing solution is increased by the action of an acid, Production of a positive resist composition comprising a filtration step of filtering a resin having a cyclic or polycyclic alicyclic hydrocarbon structure, the solubility of which in an alkali developing solution increases by the action of an acid, with an ion exchange filter. Method.

(2) A method for producing a positive resist composition containing a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, the solubility of which in an alkali developing solution is increased by the action of an acid, A resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, the solubility of which in an alkali developing solution is increased by the action of an acid, is filtered by an insoluble colloid removal filter (1) The method for producing the positive resist composition as described in 1.

(3) A method for producing a positive resist composition containing a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, the solubility of which in an alkali developing solution is increased by the action of an acid, A filtration step of filtering an organic solvent solution of a resin having a cyclic or polycyclic alicyclic hydrocarbon structure and having an increased solubility in an alkali developing solution by the action of an acid by an ion exchange filter, and then applying actinic rays or A method for producing a positive resist composition, comprising: a step of preparing a mixed solution by mixing a compound that generates an acid upon irradiation with radiation; and a filtration step of filtering the mixed solution with an insoluble colloid removal filter.

The preferred embodiments of the present invention will be further described below. (4) The method for producing a positive resist composition as described in (3), wherein a basic compound is further mixed in the step of mixing a compound that generates an acid upon irradiation with actinic rays or radiation.

(5) The boiling point of the organic solvent is 140 to 1
The method for producing a positive resist composition as described in (3) or (4), which contains at least one organic solvent at 80 ° C.

(6) The organic solvent having a boiling point of 140 to 180 ° C. is chain ketone, lactic acid alkyl ester, propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, acetic acid alkyl ester or alkyl alkoxypropionate. (5) The method for producing a positive resist composition as described in (5) above.

(7) The compound which generates an acid upon irradiation with actinic rays or radiation is a compound which generates perfluoroalkanesulfonic acid upon irradiation with actinic rays or radiation (3) to (6). 4. A method for producing the positive resist composition as described in any one of 1) to 4) above.

(8) The ion exchange filter is a cation exchange type filter (1)-
The method for producing a positive resist composition as described in any of (7).

(9) The method for producing a positive resist composition as described in any of (1) to (8), wherein the ion exchange group of the ion exchange filter is fixed to the polyethylene membrane.

(10) A positive resist composition produced by any one of the production methods described in (1) to (9).

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. << (A) Resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, the solubility of which in an alkali developing solution is increased by the action of an acid >> The positive resist composition of the present invention is a monocyclic or polycyclic alicyclic resin. It contains a resin (acid-decomposable resin) which has a cyclic hydrocarbon structure and whose solubility in an alkali developing solution is increased by the action of an acid. Examples of the resin having a monocyclic or polycyclic alicyclic hydrocarbon structure and having an increased solubility in an alkali developing solution under the action of an acid include, for example, the following general formulas (pI) to (p).
A resin containing at least one selected from the group of repeating units represented by VI) having a partial structure containing an alicyclic hydrocarbon and a repeating unit represented by formula (II-AB) is preferable.

[0019]

[Chemical 1]

(Wherein R ₁₁ is a methyl group, an ethyl group, n
Represents a propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R _{12 to} R ₁₆ each independently have 1 to 4 carbon atoms,
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R _{12 to} R ₁₄ , or either R ₁₅ or R ₁₆ 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 is Represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. R _{22 to} R ₂₅ are each independently
It represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group. Also, R ₂₃ and R
₂₄ may combine with each other to form a ring. )

[0021]

[Chemical 2]

In formula (II-AB): R ₁₁ 'and R ₁₂ ' each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent. Z'represents an atomic group for forming an alicyclic structure which contains two carbon atoms (C-C) bonded and may have a substituent.

Further, the above general formula (II-AB) is more preferably the following general formula (II-A) or general formula (II-B).

[0024]

[Chemical 3]

In formulas (II-A) and (II-B): R ₁₃ 'to R
₁₆ 'each independently represents a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR _5, group decomposable by the action of an acid, -C (= O) -X- A'-R 17', or substituted It represents an alkyl group which may have a group or a cyclic hydrocarbon group. Here, R ₅ represents an alkyl group which may have a substituent, a cyclic hydrocarbon group or the following —Y group. X
It represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-. A'represents a single bond or a divalent linking group. It is also possible to form at least two members to the ring of R _l3 '~R _16'. n represents 0 or 1.
R ₁₇ 'is —COOH, —COOR ₅ , —CN, hydroxyl group,
An alkoxy group which may have a substituent, -CO-NH
-R _6, represents a -CO-NH-SO ₂ -R ₆ or -Y group shown below. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. -Y group;

[0026]

[Chemical 4]

(In the —Y group, R ₂₁ ′ to R ₃₀ ′ each independently represents a hydrogen atom or an alkyl group which may have a substituent. A and b represent 1 or 2.)

In the general formulas (pI) to (pVI), R
The alkyl group in _{12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
Examples thereof include sec-butyl group and t-butyl group. Further, the further substituent of the above alkyl group has 1 carbon atom
To 4 alkoxy groups, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxy group, alkoxycarbonyl group, nitro group and the like.

The alicyclic hydrocarbon group for R _{11 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. Specific examples thereof include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6 to 30, and particularly preferably 7 to 25. These alicyclic hydrocarbon groups may have a substituent. Below, the structural example of an alicyclic part is shown among alicyclic hydrocarbon groups.

[0030]

[Chemical 5]

[0031]

[Chemical 6]

[0032]

[Chemical 7]

In the present invention, the alicyclic moiety is preferably adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group. , A cycloheptyl group, a cyclooctyl group,
Examples thereof include a cyclodecanyl group and a cyclododecanyl group. More preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

Examples of the substituent of these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, more preferably a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group. Represent Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group.

In the above resins, the general formulas (pI) to (pV)
The structure represented by I) can be used for protection of alkali-soluble groups. Examples of the alkali-soluble group include various groups known in this technical field. Specific examples thereof include a carboxylic acid group, a sulfonic acid group, a phenol group and a thiol group, and a carboxylic acid group and a sulfonic acid group are preferable. General formula (pI) in the above resin
The alkali-soluble group protected by the structure represented by (pVI) is preferably the following general formulas (pVII) to (pVII).
The group represented by XI) is mentioned.

[0036]

[Chemical 8]

Here, R _{11 to} R ₂₅ and Z are the same as defined above. In the above resin, the repeating unit having an alkali-soluble group protected by the structures represented by the general formulas (pI) to (pVI) is preferably a repeating unit represented by the following general formula (pA).

[0038]

[Chemical 9]

Here, R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different. A is a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group, alone or in combination of two or more. Represents a combination of groups. Ra represents any group of the above formulas (pI) to (pVI).

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (pA) are shown below.

[0041]

[Chemical 10]

[0042]

[Chemical 11]

[0043]

[Chemical 12]

[0044]

[Chemical 13]

[0045]

[Chemical 14]

[0046]

[Chemical 15]

In the above general formula (II-AB), R ₁₁ 'and R
Each ₁₂ 'independently represents a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent.
Z'represents an atomic group for forming an alicyclic structure which contains two carbon atoms (C-C) bonded and may have a substituent.

Examples of the halogen atom in R ₁₁ ′ and R ₁₂ ′ include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. Above R ₁₁ ', R ₁₂ ', R ₂₁ '~ R
The alkyl group in ₃₀ 'is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and further preferably Methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group,
a sec-butyl group and a t-butyl group.

Examples of the further substituent in the above alkyl group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like,
Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group, examples of the acyl group include formyl group, acetyl group and the like, and examples of the acyloxy group include Can include an acetoxy group and the like.

The atomic group for forming the alicyclic structure of Z'is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin, and particularly, a bridged structure. An atomic group for forming a bridged alicyclic structure forming a repeating unit of the alicyclic hydrocarbon of the formula is preferable. Examples of the alicyclic hydrocarbon skeleton to be formed include those shown by the following structures.

[0051]

[Chemical 16]

[0052]

[Chemical 17]

Preferred skeletons of bridged alicyclic hydrocarbons include (5), (6), (7),
(9), (10), (13), (14), (15),
(23), (28), (36), (37), (42),
(47) is mentioned.

The skeleton of the alicyclic hydrocarbon may have a substituent. Examples of such a substituent include R ₁₃ ′ to R ₁₆ ′ in the above general formula (II-A) or (II-B). Among the repeating units having the bridged alicyclic hydrocarbon, the repeating unit represented by the general formula (II-A) or (II-B) is more preferable.

The above general formula (II-A) or (II-B)
In the formula, R ₁₃ ′ to R ₁₆ ′ each independently represent a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₅ , a group decomposable by the action of an acid, —C (═O) —X—A ′. -R
₁₇ ', or an alkyl group which may have a substituent or a cyclic hydrocarbon group. R ₅ may have a substituent, an alkyl group, cyclic hydrocarbon group or said group -Y. X is an oxygen atom, a sulfur atom, -NH-, -NH
It represents SO ₂ — or —NHSO ₂ NH—. A'represents a single bond or a divalent linking group. It is also possible to form at least two members to the ring of R _l3 '~R _16'. n is 0
Or represents 1. R ₁₇ 'is —COOH, —COOR ₅ ,
-CN, a hydroxyl group, an optionally substituted alkoxy _{group, -CO-NH-R 6,} -CO-NH-SO 2 -R 6
Alternatively, it represents the following —Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. -
In the Y group, R ₂₁ ′ to R ₃₀ ′ each independently represent a hydrogen atom or an alkyl group which may have a substituent, and
b represents 1 or 2.

In the acid-decomposable resin of the present invention, the acid-decomposable group may be contained in the above-mentioned —C (═O) —X—A′—R ₁₇ ′, or may be represented by the general formula (II-AB ) May be included as a Z'substituent. The structure of the acid-decomposable group is -C (=
O) represented by -X ₁ -R _0. In the formula, R ₀ is t
-Tert-alkyl group such as butyl group and t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-alkoxyethyl group such as 1-cyclohexyloxyethyl group , 1-methoxymethyl group, alkoxymethyl group such as 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group,
Examples thereof include a tetrahydrofuranyl group, a trialkylsilyl ester group, a 3-oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, a mevalonic lactone residue and the like. X ₁ has the same meaning as X above.

Examples of the halogen atom in R ₁₃ 'to R ₁₆ ' include chlorine atom, bromine atom, fluorine atom, iodine atom and the like.

The alkyl group for R ₅ , R ₆ , and R ₁₃ 'to R ₁₆ ' is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms.
Six linear or branched alkyl groups, more preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group.

The cyclic hydrocarbon group for R ₅ , R ₆ , and R ₁₃ 'to R ₁₆ ' is, for example, a cyclic alkyl group, a bridged hydrocarbon group, a cyclopropyl group, a cyclopentyl group,
Cyclohexyl group, adamantyl group, 2-methyl-2-
Examples thereof include an adamantyl group, a norbornyl group, a boronyl group, an isobornyl group, a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. The ring formed by combining at least two members out of R ₁₃ ′ to R ₁₆ ′ is cyclopentene,
Examples thereof include rings having 5 to 12 carbon atoms such as cyclohexene, cycloheptane, and cyclooctane.

Examples of the alkoxy group for R ₁₇ ′ include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group.

Further substituents on the above alkyl group, cyclic hydrocarbon group and alkoxy group include hydroxyl group, halogen atom, carboxyl group, alkoxy group, acyl group, cyano group, acyloxy group, alkyl group, cyclic hydrocarbon group and the like. Can be mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group, and examples of the acyl group include formyl group, acetyl group and the like, acyloxy group Examples thereof include acetoxy group and the like. Also,
Examples of the alkyl group and cyclic hydrocarbon group include those mentioned above.

The divalent linking group of A'is selected from the group consisting of alkylene group, substituted alkylene group, ether group, thioether group, carbonyl group, ester group, amide group, sulfonamide group, urethane group and urea group. These may be selected alone or in combination of two or more groups. Examples of the alkylene group and the substituted alkylene group for A ′ include groups represented by the following formula. - _{[C (R a) (R b} ) ] _r - wherein, R _a, R _b represents a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. As the substituent of the substituted alkyl group,
Examples thereof include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r represents an integer of 1 to 10.

In the acid-decomposable resin of the present invention, the group which is decomposed by the action of an acid is one of the above general formulas (pI) to (p).
VI) a repeating unit having a partial structure containing an alicyclic hydrocarbon, a repeating unit represented by the general formula (II-AB), and at least one repeating unit of the repeating units of the copolymerization component described below. Can be included.

The above general formula (II-A) or the general formula (II
The various substituents of R ₁₃ ′ to R ₁₆ ′ in —B) are an atomic group for forming the alicyclic structure in formula (II-AB) or a bridged alicyclic structure for forming an alicyclic structure. It also serves as a substituent of the atomic group Z.

The above general formula (II-A) or general formula (II
As specific examples of the repeating unit represented by -B), the following [II
-1] to [II-175], but the present invention is not limited to these specific examples.

[0066]

[Chemical 18]

[0067]

[Chemical 19]

[0068]

[Chemical 20]

[0069]

[Chemical 21]

[0070]

[Chemical formula 22]

[0071]

[Chemical formula 23]

[0072]

[Chemical formula 24]

[0073]

[Chemical 25]

[0074]

[Chemical formula 26]

[0075]

[Chemical 27]

[0076]

[Chemical 28]

The acid-decomposable resin of the present invention may further contain a repeating unit having a lactone structure represented by the following general formula (IV).

[0078]

[Chemical 29]

In formula (IV), R ₁ a represents a hydrogen atom or a methyl group. W ₁ represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, or a combination of two or more groups selected from the group consisting of. Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ and Re ₁ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3, m + n
Is 2 or more and 6 or less.

Examples of the alkyl group having 1 to 4 carbon atoms represented by Ra _{1 to} Re ₁ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group and the like. Can be mentioned.

In the general formula (IV), examples of the alkylene group for W ₁ include groups represented by the following formula. — [C (Rf) (Rg)] r ₁ — In the above formula, Rf and Rg represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, which may be the same or different. Good. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r ₁ is an integer of ₁ to 10.

Further substituents on the alkyl group include a carboxyl group, an acyloxy group, a cyano group, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a substituted alkoxy group, an acetylamide group, an alkoxycarbonyl group, An acyl group can be mentioned. Examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group and a cyclopentyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the substituent of the substituted alkoxy group include an alkoxy group and the like. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. An acetoxy group etc. are mentioned as an acyloxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like.

Specific examples of the monomer corresponding to the repeating structural unit represented by the general formula (IV) are shown below, but the present invention is not limited thereto.

[0084]

[Chemical 30]

[0085]

[Chemical 31]

[0086]

[Chemical 32]

In the specific example of the above general formula (IV), from the viewpoint that the exposure margin becomes better (IV-17) to
(IV-36) is preferred. Further, as the structure of the general formula (IV), a structure having an acrylate structure is preferable from the viewpoint of good edge roughness.

Further, the following general formulas (V-1) to (V-5)
You may contain the repeating unit which has the group represented by either of these.

[0089]

[Chemical 33]

In the general formulas (V-1) to (V-5),
R _{1b to} R _5b each independently represent a hydrogen atom or an optionally substituted alkyl group, cycloalkyl group, alkoxy group, alkoxycarbonyl group, alkylsulfonylimino group or alkenyl group. Two of R _{1b to} R _5b may combine with each other to form a ring.

In the general formulas (V-1) to (V-5),
Examples of the alkyl group in R _{1b to} R _5b , the alkoxy group, the alkoxycarbonyl group, and the alkylsulfonylimino group include linear and branched alkyl groups, which may have a substituent. The linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, more preferably 1 to 12 carbon atoms.
10 linear or branched alkyl groups, more preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, A hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. R _1b ~ R
_As the cycloalkyl group in _5b , those having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group are preferable. As the alkenyl group for R _{1b to} R _5b ,
Those having 2 to 6 carbon atoms such as vinyl group, propenyl group, butenyl group and hexenyl group are preferable. Also, R _{1b to} R _5b
Examples of the ring formed by combining two of the above include a 3- to 8-membered ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring. R _1b in the general formulas (V-1) to (V-5)
~ R _5b may be linked to any of the carbon atoms constituting the cyclic skeleton.

The preferred substituents which the alkyl group, cycloalkyl group, alkoxy group, alkoxycarbonyl group, alkylsulfonylimino group and alkenyl group represented by R _{1b to} R _5b may have are 1 to 4 carbon atoms. Alkoxy group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group having 2 to 5 carbon atoms, 2 carbon atoms
Examples thereof include an acyloxy group having 5 to 5, a cyano group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group having 2 to 5 carbon atoms, and a nitro group.

The repeating unit having a group represented by any one of the general formulas (V-1) to (V-5) is represented by the above general formula (II-
A) or (II-B) in which at least one of R ₁₃ 'to R ₁₆ ' has a group represented by the above general formulas (V-1) to (V-5) (for example, -COOR ₅ R ₅ is a general formula (V-
1) to (V-5)) or a repeating unit represented by the following general formula (AI).

[0094]

[Chemical 34]

In the general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group represented by R _b0 may have include those represented by the general formula (V-1) to
Examples of the preferable substituent which the alkyl group as R _1b in (V-5) may have include those exemplified above. Examples of the halogen atom of R _b0 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R
_b0 is preferably a hydrogen atom. A'represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group combining these. B ₂ represents a group represented by any one of formulas (V-1) to (V-5). In A ′, examples of the combined divalent group include those represented by the following formulas.

[0096]

[Chemical 35]

In the above formula, R _ab and R _bb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group or an alkoxy group, and they may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r
1 represents an integer of 1 to 10, preferably an integer of 1 to 4.
m represents an integer of 1 to 3, preferably 1 or 2.

Specific examples of the repeating unit represented by formula (AI) are shown below, but the contents of the present invention are not limited to these.

[0099]

[Chemical 36]

[0100]

[Chemical 37]

[0101]

[Chemical 38]

[0102]

[Chemical Formula 39]

[0103]

[Chemical 40]

[0104]

[Chemical 41]

[0105]

[Chemical 42]

Further, it may contain a repeating unit having a group represented by the following general formula (VII).

[0107]

[Chemical 43]

In formula (VII), R ₂ c to R ₄ c each independently represent a hydrogen atom or a hydroxyl group. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group.

The group represented by the general formula (VII) is preferably a dihydroxy body or a monohydroxy body, more preferably a dihydroxy body.

As the repeating unit having a group represented by the general formula (VII), the above general formula (II-A) or (II-
At least one of R ₁₃ 'to R ₁₆ ' in B) has a group represented by the above general formula (VII) (for example, -COO).
R ₅ of R ₅ represents a group represented by general formulas (V-1) to (V-4), or a repeating unit represented by the following general formula (AII).

[0111]

[Chemical 44]

In formula (AII), R ₁ c represents a hydrogen atom or a methyl group. R ₂ c to R ₄ c represents a hydrogen atom or a hydroxyl group independently. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group.

The specific examples of the repeating units having the structure represented by formula (AII) are shown below, but the invention is not limited thereto.

[0114]

[Chemical formula 45]

Further, it may contain a repeating unit having a group represented by the following general formula (VIII).

[0116]

[Chemical formula 46]

In the general formula (VIII): Z ₂ is —O— or —
Represents N (R ₄₁ ) −. Here, R ₄₁ is a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO ₂ —R.
Represents ₄₂ . R ₄₂ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

In the general formula (VIII), Z ₂ is-
Represents O- or -N (R ₄₁ )-. Here, R ₄₁ is a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OS.
Representing the O ₂ -R _42. R ₄₂ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

The alkyl group for R ₄₁ and R ₄₂ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Groups, more preferably methyl group, ethyl group, propyl group, isopropyl group, n-
A butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Examples of the haloalkyl group for R ₄₁ and R ₄₂ include a trifluoromethyl group, a nanofluorobutyl group, a pentadecafluorooctyl group and a trichloromethyl group. Examples of the cycloalkyl group for R ₄₂ include a cyclopentyl group, a cyclohexyl group and a cyclooctyl group.

The alkyl group and haloalkyl group as R ₄₁ and R ₄₂ , the cycloalkyl group as R ₄₂ or the camphor residue may have a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom and an iodine atom), an alkoxy group (preferably having a carbon number of 1 to 1).
4, for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), acyl group (preferably having 2 to 5 carbon atoms, for example, formyl group, acetyl group, etc.), acyloxy group (preferably having 2 to 5 carbon atoms, for example, An acetoxy group), an aryl group (preferably having a carbon number of 6 to 14, for example, a phenyl group), and the like.

Specific examples of the repeating unit represented by the general formula (VIII) include the following [I'-1] to [I'-7], but the present invention is limited to these specific examples. Not a thing.

[0122]

[Chemical 47]

[0123]

[Chemical 48]

The acid-decomposable resin includes, in addition to the repeating structural units described above, dry etching resistance, suitability for a standard developing solution, substrate adhesion, resist profile, and resolution, heat resistance, and sensitivity which are generally required properties of a resist. Various repeating structural units can be contained for the purpose of controlling the like.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers. Thereby, the performance required for the acid-decomposable resin, in particular, (1) solubility in a coating solvent, (2) film-forming property (glass transition point),
Fine adjustments such as (3) alkali developability, (4) film slippage (hydrophilicity / hydrophobicity, selection of alkali-soluble groups), (5) adhesion of the unexposed area to the substrate, and (6) dry etching resistance are possible. . Examples of such monomers include acrylic acid esters, methacrylic acid esters, acrylamides,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.

In addition, any addition-polymerizable unsaturated compound copolymerizable with the monomers corresponding to the above various repeating structural units may be copolymerized.

In the acid-decomposable resin, the content molar ratio of each repeating structural unit depends on the dry etching resistance of the resist, suitability for a standard developing solution, substrate adhesion, resist profile, and resolution and heat resistance which are general required performances of the resist. It is appropriately set in order to adjust the sex, sensitivity and the like.

Preferred examples of the acid-decomposable resin of the present invention include the following. (1) Those containing a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the above general formulas (pI) to (pVI) (side chain type) (2) General formula (II-AB) Containing a repeating unit represented (main chain type) However, in (2), for example,
Further examples include the following. (3) Those having a repeating unit represented by the general formula (II-AB), a maleic anhydride derivative and a (meth) acrylate structure (hybrid type)

In the acid-decomposable resin, the compounds represented by the general formulas (pI) to (pV)
The content of the repeating unit having a partial structure containing an alicyclic hydrocarbon represented by I) is 30 to 30 in all repeating structural units.
70 mol% is preferable, 35-65 mol% is more preferable, and 40-60 mol% is still more preferable. The content of the repeating unit represented by the general formula (II-AB) in the acid-decomposable resin is preferably 10 to 60 mol% in all the repeating structural units, more preferably 15 to 55 mol%, and further preferably 20. ˜50 mol%.

Further, the content of the repeating structural unit in the resin based on the monomer of the additional copolymerization component may be appropriately set depending on the desired performance of the resist, but in general, the above general content is used. Based on the total total number of moles of the repeating structural units having a partial structure containing an alicyclic hydrocarbon represented by formulas (pI) to (pVI) and the repeating units represented by the general formula (II-AB). It is preferably 99 mol% or less, more preferably 90 mol% or less, still more preferably 80 mol% or less. When the composition of the present invention is for ArF exposure,
From the viewpoint of transparency to ArF light, the resin preferably does not have an aromatic group.

The acid-decomposable resin used in the present invention can be synthesized by a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer species is charged in a batch or in the middle of the reaction into a reaction vessel, and if necessary, a reaction solvent, for example, tetrahydrofuran, 1,4-dioxane, ethers such as diisopropyl ether or methyl ethyl ketone, Ketones such as methyl isobutyl ketone, ester solvents such as ethyl acetate, and further homogenized by dissolving in a solvent dissolving the composition of the present invention such as propylene glycol monomethyl ether acetate described later, nitrogen, argon, etc. If necessary, heating is performed in an inert gas atmosphere, and polymerization is initiated using a commercially available radical initiator (azo initiator, peroxide, etc.).
If desired, an initiator is added or added in portions, and after completion of the reaction, the reaction mixture is put into a solvent to recover the desired polymer by a method such as powder or solid recovery. Reaction concentration is 20% by weight
It is at least 30% by weight, preferably at least 40% by weight. Reaction temperature is 10 ° C to 150
C., preferably 30 to 120.degree. C., more preferably 50 to 100.degree.

The weight average molecular weight of the resin according to the present invention is G
The polystyrene conversion value by the PC method is preferably 1,000 to 200,000. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, which is not preferable, and when it exceeds 200,000, developability is deteriorated and film forming property is deteriorated due to extremely high viscosity. It produces less favorable results.

In the positive resist composition for deep UV exposure of the present invention, the compounding amount of all the resins according to the present invention in the entire composition is preferably 40 to 99.99% by weight in the total resist solid content, It is preferably 50 to 99.97% by weight.

<< (B) Compound that Generates Acid by Irradiation with Actinic Rays or Radiation >> The positive resist composition of the present invention contains a compound (photoacid generator) that generates an acid by irradiation with actinic rays or radiation. To do. Such photo-acid generators include photo-initiators for photo-cationic polymerization, photo-initiators for photo-radical polymerization, photo-decoloring agents for dyes, photo-color-changing agents, or actinic rays used for micro resists or the like. Known compounds that generate an acid upon irradiation with radiation and mixtures thereof can be appropriately selected and used.

For example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium salts,
Organic halogen compounds, organic metal / organic halides, o
Examples thereof include a photoacid generator having a nitrobenzyl-type protecting group, a compound represented by iminosulfonate and the like, which photolyzes to generate a sulfonic acid, and a disulfone compound.

Further, a group in which an acid-generating group or a compound is introduced into the main chain or side chain of a polymer by irradiation with these actinic rays or radiation, for example, US Pat. No. 3,849,137, German Patent No. 3,914,407, JP-A-63-26653, JP-A-55-164824.
No. 62-69263, 63-1460.
38, JP-A-63-163452, JP-A-62-
The compounds described in JP-A-153853 and JP-A-63-146029 can be used.

Further, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712 and the like can also be used.

Among the compounds which decompose when exposed to actinic rays or radiation to generate an acid, those which are particularly effectively used are described below.

(1) An iodonium salt represented by the following general formula (PAG1) or a sulfonium salt represented by the following general formula (PAG2).

[0140]

[Chemical 49]

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

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Of these, an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and a substituted derivative thereof are preferable. Preferred substituents are 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 hydroxy group and a halogen atom for an aryl group,
The alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group or an alkoxycarbonyl group.

Z ⁻ represents a counter anion, for example, BF ₄ ⁻ ,
_{^{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
Perfluoroalkane sulfonate anions such as CF ₃ SO ₃ ⁻ , pentafluorobenzene sulfonate anions, condensed polynuclear aromatic sulfonate anions such as naphthalene-1-sulfonate anions, anthraquinone sulfonate anions, sulfonate group-containing dyes, etc. Examples thereof include, but are not limited to:

Two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded to each other via a single bond or a substituent.

Specific examples thereof include, but are not limited to, the compounds shown below.

[0146]

[Chemical 50]

[0147]

[Chemical 51]

[0148]

[Chemical 52]

[0149]

[Chemical 53]

[0150]

[Chemical 54]

[0151]

[Chemical 55]

[0152]

[Chemical 56]

[0153]

[Chemical 57]

[0154]

[Chemical 58]

[0155]

[Chemical 59]

[0156]

[Chemical 60]

The onium salts represented by the general formulas (PAG1) and (PAG2) are known, for example, US Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331. It can be synthesized by the method described in each publication.

(2) A disulfone derivative represented by the following general formula (PAG3) or an iminosulfonate derivative represented by the general formula (PAG4).

[0159]

[Chemical formula 61]

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, or arylene group. Specific examples thereof include the compounds shown below, but the invention is not limited thereto.

[0161]

[Chemical formula 62]

[0162]

[Chemical formula 63]

[0163]

[Chemical 64]

[0164]

[Chemical 65]

[0165]

[Chemical formula 66]

(3) A diazodisulfone derivative represented by the following general formula (PAG5).

[0167]

[Chemical formula 67]

Here, R represents a linear, branched or cyclic alkyl group or an aryl group which may be substituted. Specific examples include the compounds shown below,
It is not limited to these.

[0169]

[Chemical 68]

In addition to the above compounds, compounds represented by the following general formula (I) are also effectively used as the photoacid generator of the present invention.

[0171]

[Chemical 69]

In the formula (I), R _{1 to} R ₅ represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a halogen atom, an alkyloxycarbonyl group or an aryl group, and R ₁ to R ₅
At least two or more of R ₅ may combine 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 alkyl group, an aryl group, an aralkyl group or an aromatic group containing a hetero atom, and Y ₁ and Y ₂ may be bonded to each other to form a ring. Y ₃ represents a single bond or a divalent linking group. X ^- is
Represents a non-nucleophilic anion. Provided that at least one of R ₁ to R ₅ and at least one of Y ₁ or Y ₂ are combined to form a ring, or at least one of R ₁ to R ₅ and R
_At least one of ₆ or R ₇ is bonded to form a ring.
In addition, it may have two or more structures of formula (I), which are bonded via a linking group at any of R ₁ to R ₇ or at any of Y ₁ or Y ₂ .

The alkyl group represented by R _{1 to} R ₇ is a substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 5 carbon atoms. Examples of the unsubstituted alkyl group include methyl group and ethyl group. Group, propyl group, n-butyl group,
Examples thereof include sec-butyl group and t-butyl group. The alkoxy group of R _{1 to} R _{5 and} the alkoxy group in the alkyloxycarbonyl group are substituted or unsubstituted alkoxy groups, preferably alkoxy groups having 1 to 5 carbon atoms, and examples of the unsubstituted alkoxy group include , A methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. The aryl group represented by R _{1 to} R ₇ , Y ₁ and Y ₂ is a substituted or unsubstituted aryl group, preferably an aryl group having 6 to 14 carbon atoms, and examples of the unsubstituted aryl group include phenyl. Group, tolyl group,
Examples thereof include a naphthyl group. Examples of the halogen atom of R _{1 to} R ₅ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group of Y ₁ and Y ₂ is a substituted or unsubstituted alkyl group, preferably having 1 to 30 carbon atoms.
Is an alkyl group. As the unsubstituted alkyl group, for example, a linear or branched alkyl group such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, and cyclopropyl group, Examples thereof include cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group and boronyl group.

The aralkyl group of Y ₁ and Y ₂ is a substituted or unsubstituted aralkyl group, preferably having 7 to 7 carbon atoms.
Examples of the aralkyl group of 12 and the unsubstituted aralkyl group include a benzyl group, a phenethyl group, and a cumyl group.

The aromatic group containing a hetero atom means a group having a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom in an aromatic group such as an aryl group having 6 to 14 carbon atoms. The aromatic group containing a hetero atom of Y ₁ and Y ₂ is an aromatic group containing a substituted or unsubstituted hetero atom, and examples of the unsubstituted group include furan, thiophene, pyrrole, pyridine and indole. And a heterocyclic aromatic hydrocarbon group.

Y ₁ and Y ₂ are combined to form S ⁺ in the formula (I).
Together, they may form a ring. In this case, the group formed by combining Y ₁ and Y ₂ has, for example, 4 to 1 carbon atoms.
And an alkylene group of 0, preferably a butylene group, a pentylene group and a hexylene group, particularly preferably a butylene group and a pentylene group. Further, a hetero atom may be contained in the ring formed together with S ⁺ in the formula (I) by combining with Y ₁ and Y ₂ .

Each of the above alkyl group, alkoxy group, alkoxycarbonyl group, aryl group and aralkyl group is, for example, a nitro group, a halogen atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group or an alkoxy group (preferably having a carbon number. 1-5) etc. may be substituted. Further, the aryl group and aralkyl group may be substituted with an alkyl group (preferably having 1 to 5 carbon atoms). Moreover, a halogen atom is preferable as a substituent of the alkyl group.

Y ₃ represents a single bond or a divalent linking group, and as the divalent linking group, an optionally substituted alkylene group, alkenylene group, —O—, —S—, —CO—,
-CONR- (R is hydrogen, an alkyl group, an acyl group.), And a linking group which may include two or more of these are preferable.

Examples of the non-nucleophilic anion of X ⁻ include sulfonate anion and carboxylate anion. The non-nucleophilic anion is an anion having an extremely low ability to cause a nucleophilic reaction, and is an anion capable of suppressing decomposition over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist. Examples of the sulfonate anion include an alkyl sulfonate anion, an aryl sulfonate anion, and a camphor sulfonate anion. Examples of the carboxylic acid anion include an alkylcarboxylic acid anion, an arylcarboxylic acid anion, and an aralkylcarboxylic acid anion.

The alkyl group in the alkylsulfonate anion is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. , Pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group Group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group and the like. The aryl group in the aryl sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, for example, a phenyl group, a tolyl group, a naphthyl group and the like.

The alkyl group and aryl group in the alkyl sulfonate anion and aryl sulfonate anion may have a substituent. As a substituent,
For example, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group and the like can be mentioned.

Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. As the alkyl group, for example, an alkyl group preferably having 1 to 15 carbon atoms, for example, a methyl group, an ethyl group,
Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Examples thereof include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group. As the alkoxy group, for example, preferably an alkoxy group having 1 to 5 carbon atoms,
For example, methoxy group, ethoxy group, propoxy group, butoxy group and the like can be mentioned. The alkylthio group is, for example, preferably an alkylthio group having 1 to 15 carbon atoms, for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, pentylthio group,
Neopentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, undecylthio group, dodecylthio group, tridecylthio group,
Tetradecylthio group, pentadecylthio group, hexadecylthio group, heptadecylthio group, octadecylthio group,
Examples thereof include nonadecylthio group and eicosylthio group. The alkyl group, alkoxy group and alkylthio group may be further substituted with a halogen atom (preferably a fluorine atom).

Examples of the alkyl group in the alkylcarboxylic acid anion include those similar to the alkyl group in the alkylsulfonic acid anion. Examples of the aryl group in the arylcarboxylic acid anion include the same as the aryl group in the arylsulfonic acid anion. The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, for example, benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylmethyl group and the like.

The alkyl group, aryl group and aralkyl group in the above alkylcarboxylic acid anion, arylcarboxylic acid anion and aralkylcarboxylic acid anion may have a substituent, and examples of the substituent include:
The same halogen atom, alkyl group, alkoxy group, alkylthio group and the like as in the aryl sulfonate anion can be mentioned.

Examples of other non-nucleophilic anions include fluorinated phosphorus, fluorinated boron and fluorinated antimony.

In the formula (I) of the present invention, at least one of R ₁ to R ₅ and at least one of Y ₁ or Y ₂ are bonded to each other to form a ring, or R ₁ to R ₅ At least one and at least one of R _{6 and} R ₇ are combined to form a ring. By forming a ring, the compound represented by the formula (I) has a fixed three-dimensional structure and improves optical resolution. Any _one of R ₁ to R ₇ or Y ₁
Or at any position of Y ₂ is bonded via a linking group,
It may have two or more structures of formula (I).

Further, the compound of formula (I) is preferably of the following general formula (IA) or (IB).

[0189]

[Chemical 70]

In formula (IA), R _{1 to} R ₄ , R ₇ , Y ₁ and Y ₂
And X ⁻ are the same as those in the above formula (I), and Y
Represents a single bond or a divalent linking group. In formula (IB), R
_{1 to} R ₄ , R ₆ , R ₇ , Y ₁ and X ⁻ are the same as those in the above formula (I), and Y represents a single bond or a divalent linking group.

Y represents a single bond or a divalent linking group, and 2
As the valent linking group, an optionally substituted alkylene group, alkenylene group, -O-, -S-, -CO-, -C
ONR- (R is hydrogen, an alkyl group, or an acyl group), and a linking group which may include two or more of these are preferable. In formula (IA), Y is preferably an alkylene group, an alkylene group containing an oxygen atom, or an alkylene group containing a sulfur atom, and specifically, a methylene group, an ethylene group, a propylene group, —CH ₂ —O—, —CH. ₂ -S- are preferred, and most preferably an ethylene group, -CH ₂ -O-,
A connecting group forming a 6-membered ring such as —CH ₂ —S—. By forming a 6-membered ring, the carbonyl plane and C-
The S + sigma bond becomes closer to vertical, and the photolysis efficiency is improved by the orbital interaction.

The compound of formula (IA) has the corresponding α-
A method of reacting a halo cyclic ketone with a sulfide compound,
Alternatively, it can be obtained by converting the corresponding cyclic ketone into a silyl enol ether and then reacting it with a sulfoxide. The compound represented by the formula (IB) can be obtained by reacting an arylalkyl sulfide with an α- or β-halogenated halide.

Specific examples of the compound represented by the above formula (I) are shown below, but the invention is not limited thereto.

[0194]

[Chemical 71]

[0195]

[Chemical 72]

[0196]

[Chemical formula 73]

[0197]

[Chemical 74]

[0198]

[Chemical 75]

[0199]

[Chemical 76]

[0200]

[Chemical 77]

[0201]

[Chemical 78]

[0202]

[Chemical 79]

In the specific examples of the photoacid generator represented by the general formula (I), (IA-1) to (IA-30) and (IB-1) to (IB-12) are more preferable.

The compounds of general formula (I) can be used alone or in combination of two or more.

In the present invention, a photoacid generator capable of generating perfluoroalkanesulfonic acid upon irradiation with actinic rays or radiation is more preferable.

The content of the photo-acid generator in the positive resist composition is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, and further preferably, based on the solid content of the composition. Is 1 to 7% by weight.

Among the compounds capable of generating an acid upon irradiation with actinic rays or radiation used in the present invention, particularly preferable examples are shown below.

[0208]

[Chemical 80]

[0209]

[Chemical 81]

[0210]

[Chemical formula 82]

[0211]

[Chemical 83]

<< (C) Basic Compound >> The positive resist composition of the present invention preferably contains (C) a basic compound in order to reduce the change in performance over time from exposure to heating. As a preferred structure, the following formula (A)
The structure shown by (E) can be mentioned. Formula (B)
~ (E) may be a part of the ring structure.

[0213]

[Chemical 84]

R ²⁵⁰ , R ^251, and R ²⁵² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵⁰ and R ²⁵¹ may combine with each other to form a ring. Moreover, these may contain an oxygen atom, a sulfur atom, and a nitrogen atom in the alkyl chain.

[0215]

[Chemical 85]

(In the formula, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R
²⁵⁶ independently represents an alkyl group having 1 to 6 carbon atoms). Preferred specific examples 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 amino Examples thereof include morpholine, substituted or unsubstituted aminoalkylmorpholine and the like, and mono, di, trialkylamines, substituted or unsubstituted aniline, substituted or unsubstituted piperidine, mono or diethanolamine and the like can be mentioned. Preferred substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group. Is.

Preferred compounds include guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylamino Pyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 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, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 2,4.
5-triphenylimidazole, tri (n-butyl) amine, tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine,
2,6-diisopropylaniline, N-cyclohexyl-N'-morpholinoethylthiourea and the like,
It is not limited to this.

Further preferred compounds are substituted or unsubstituted guanidine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted amino. Examples thereof include morpholine, substituted or unsubstituted aminoalkylmorpholine, substituted or unsubstituted piperidine, and further a compound having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, or an aniline structure.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole and benzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] noner5-ene, 1,8-diazabicyclo [5,4,0]. Undecker 7-en and the like are included. Examples of the compound having an onium hydroxide structure are triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium. Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. The compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion portion is a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. As an aniline compound,
2,6-diisopropylaniline, N, N-dimethylaniline and the like can be mentioned. None of them are limited to the illustrated specific examples.

These (C) basic compounds may be used alone or in combination of two or more. The amount of the basic compound (C) used is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content of the positive photosensitive composition.
% By weight. If it is less than 0.001% by weight, the effect of adding the basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed area tends to deteriorate.

<< (D) Fluorine-based and / or Silicon-based Surfactant >> The positive resist composition of the present invention comprises a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon-based surfactant). , A surfactant containing both a fluorine atom and a silicon atom), or two or more kinds thereof. Since the positive resist composition of the present invention contains the above-mentioned (D) surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, good sensitivity and resolution are obtained, and adhesion and development defects are few. It becomes possible to provide a resist pattern. Examples of these (D) surfactants include those disclosed in JP-A-62-62.
-36663, JP-A-61-226746, JP-A-61-226745,
JP 62-170950 A, JP 63-34540 A, JP 7-23016 A
5, JP 8-62834A, JP 9-54432A, JP 9-598A
8, U.S. Pat.Nos. 5,405,720, 5,360,692, 5,528,981,
5296330, 5436098, 5576143, 5294511
No. 5824451, and the following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC
430, 431 (Sumitomo 3M Limited), MegaFac F171,
F173, F176, F189, R08 (manufactured by Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.) )) And / or fluorine-based and / or silicon-based surfactants. Also polysiloxane polymer
KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the silicon-based surfactant.

The amount of the surfactant used is preferably 0.0 based on the total amount of the positive resist composition (excluding the solvent).
001 to 2% by weight, more preferably 0.001 to 1% by weight.

<< (E) Organic Solvent >> The positive resist composition of the present invention is used by dissolving the above components in a predetermined organic solvent. Examples of the organic solvent that can be used include ethylene dichloride, cyclohexanone, cyclopentanone,
2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether,
Propylene glycol monomethyl ether acetate,
Toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc. Can be mentioned.

In the present invention, as the organic solvent, chain ketone such as methyl ethyl ketone, alkyl lactate such as methyl lactate and ethyl lactate, propylene glycol monoalkyl ether carboxylate such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and the like. Of at least one organic solvent having a boiling point of 140 to 180 ° C. selected from propylene glycol monoalkyl ether, an acetic acid alkyl ester such as methyl acetate, and an alkyl alkoxypropionate such as methyl methoxypropionate and ethyl ethoxypropionate. preferable.

<< (F) Acid-decomposable dissolution inhibiting compound >> The positive resist composition of the present invention has a group (F) which is decomposed by the action of an acid to increase the solubility in an alkali developing solution, It is preferable to contain a dissolution inhibiting low molecular weight compound having a molecular weight of 3000 or less (hereinafter, also referred to as “(F) acid-decomposable dissolution inhibiting compound”). Proceeding of SPIE, 2724, 355 (19
Aliphatic or aliphatic compounds containing an acid-decomposable group, such as the cholic acid derivative containing an acid-decomposable group described in (96), are preferable as the (F) acid-decomposable dissolution inhibiting compound. Examples of the acid-decomposable group and the alicyclic structure include the same ones as described above for the acid-decomposable resin. The molecular weight of the acid-decomposable dissolution inhibiting compound of the present invention is 3000 or less, preferably 300 to 3000, more preferably 50.
It is 0 to 2500.

The amount of the (F) acid-decomposable dissolution inhibiting compound added is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, based on the solid content of the positive resist composition.
Is.

Specific examples of the acid-decomposable dissolution inhibiting compound (F) are shown below, but the invention is not limited thereto.

[0228]

[Chemical 86]

<< (G) Alkali-Soluble Resin >> The positive resist composition of the present invention does not contain an acid-decomposable group,
(D) A resin that is insoluble in water and soluble in an alkali developing solution can be contained, which improves the sensitivity. In the present invention, novolak resins having a molecular weight of about 1,000 to 20,000 and polyhydroxystyrene derivatives having a molecular weight of about 3,000 to 50,000 can be used as such resins, but they have large absorption for light of 250 nm or less. It is preferable to use it by partially hydrogenating it, or to use it in an amount of 30% by weight or less based on the total amount of the resin. A resin containing a carboxyl group as an alkali-soluble group can also be used. The resin containing a carboxyl group preferably has a monocyclic or polycyclic alicyclic hydrocarbon group for improving dry etching resistance.
Specifically, a copolymer of methacrylic acid ester having an alicyclic hydrocarbon structure which does not exhibit acid decomposability and (meth) acrylic acid, or a (meth) acrylic acid ester of an alicyclic hydrocarbon group having a carboxyl group at the terminal. And the like.

<< Other Additives >> In the positive resist composition of the present invention, a dye, a plasticizer, a surfactant other than the above-mentioned component (D), a photosensitizer, and a developing solution may be added, if necessary. A compound or the like that promotes solubility can be contained. The compound capable of accelerating dissolution in a developer usable in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable for the same reason as above. The preferred addition amount of these dissolution accelerating compounds is 2 to 50% by weight, more preferably 5 to 50% by weight, with respect to the resin that is decomposed by the action of the acid (B) and the solubility in the alkali developing solution is increased.
It is 30% by weight. If the addition amount exceeds 50% by weight, the development residue is deteriorated and a new defect that the pattern is deformed during development is not preferable.

Such phenol compounds having a molecular weight of 1000 or less can be prepared by those skilled in the art with reference to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294 and the like. It can be easily synthesized. Specific examples of the alicyclic or aliphatic compound having a carboxyl group include cholic acid, deoxycholic acid, carboxylic acid derivative having a steroid structure such as lithocholic acid, adamantanecarboxylic acid derivative, adamantanedicarboxylic acid, cyclohexanecarboxylic acid, and cyclohexane. Examples thereof include, but are not limited to, dicarboxylic acids.

In the present invention, a surfactant other than the (D) fluorine-based and / or silicon-based surfactant may be added. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, etc. Polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate,
Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,
Examples thereof include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate. These surfactants may be added alone or in some combinations.

<< Production Method >> The production method of the positive resist composition according to the present invention includes a filtration step (FA) of filtering the acid-decomposable resin with an ion exchange filter, and preferably further comprises an acid-decomposable resin. And a filtration step (FB) for filtering the water with an insoluble colloid removal filter.

Examples of the method of filtering the acid-decomposable resin with an ion exchange filter include a method of dissolving the acid-decomposable resin in the organic solvent and filtering the solution as an organic solvent solution. Examples of the method for filtering the acid-decomposable resin with the insoluble colloid removal filter include, for example, a method for filtering an organic solvent solution of the acid-decomposable resin, a photo-acid generator and an optional base in the organic solvent solution of the acid-decomposable resin. Examples thereof include a method of adding a reactive compound or the like and filtering the mixture as a mixed solution, and the method of filtering the mixed solution is preferable. The filter used is preferably pretreated with the organic solvent, alcohol having 1 to 20 carbon atoms or the like before use.

The order of the filtration step (FA) and the filtration step (FB) does not matter. However, in the resist,
Some include ionic compounds (mainly photoacid generators).
If you filter such a thing with an ion exchange filter,
Part of the ionic compound may be removed, and desired performance may not be obtained.

Accordingly, as a preferred method for producing the positive resist composition according to the present invention, for example, a filtration step (FA) of filtering an organic solvent solution of an acid-decomposable resin with an ion exchange filter, and then an organic solvent solution is used. A method for producing a positive resist composition, comprising a step of preparing a mixed solution by adding a photo-acid generator and a basic compound and the like as necessary, and a filtration step (FB) of filtering the mixed solution with an insoluble colloid removal filter. Can be mentioned.

As the ion exchange filter that can be used in the present invention, a cation exchange type filter having ion exchange groups fixed to a polyethylene membrane is preferable.
AEON CLEAN (manufactured by Nippon Pole Co., Ltd.), AEON CLEAN A
Q (manufactured by Nippon Pall Ltd.) and the like can be mentioned, but the present invention is not limited thereto. Filtration process (FA)
This makes it possible to remove insoluble ionic compounds.

As the insoluble colloid removing filter that can be used in the present invention, a synthetic resin filter is preferable, for example, Microlith Optimizer DEV-1.
6/40 (Polylith filter manufactured by Microlith), Microguard Minichem (Polyethylene filter manufactured by Microlith), Enflon (Polytetrafluoroethylene filter manufactured by Nippon Pall), Ultipore N
Examples include 66 (Nylon 66 filter manufactured by Nippon Pole Co., Ltd.), Zeta Plus (cellulosic filter manufactured by Cuno Co., Ltd.), and Electropore II (nylon 66 filter manufactured by Cuno Co., Ltd.), but the present invention is not limited thereto. Absent. When the filtration step (FB) is carried out after adding an ionic compound such as a photoacid generator, the insoluble colloid removal filter preferably has no ion exchange capacity. Insoluble colloid can be removed by the filtration step (FB).

The pore diameters of the ion exchange type filter and the insoluble colloid removal filter are both 0.01 to 0.5 μm.
The thickness is preferably m, and more preferably 0.01 to 0.1 μm.

<< Method of Use >> The positive resist composition of the present invention is used by coating it on a predetermined support as follows. That is, the positive resist composition is applied onto a substrate (eg, silicon / silicon dioxide coating) used for manufacturing precision integrated circuit devices by a suitable coating method such as a spinner or coater. After coating, it is exposed through a predetermined mask, baked and developed. By doing so, a good resist pattern can be obtained. Here, the exposure light is preferably 250 nm or less, more preferably 2 nm.
It is deep ultraviolet light having a wavelength of 20 nm or less. Specifically, K
rF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (15
7 nm), X-rays, electron beams, etc., but ArF
Excimer lasers are most preferred.

In the developing step, the developing solution is used as follows. Examples of the developer for the positive resist composition include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine,
Alkaline amines such as triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and alkaline aqueous solutions such as cyclic amines such as pyrrole and pyrelidine can be used. Furthermore, alcohols and surfactants may be added in appropriate amounts to the alkaline aqueous solution before use.

[0242]

EXAMPLES The present invention will be specifically described below based on examples, but the scope of the present invention is not limited to the examples.

<Synthesis Example of Resin> Synthesis Example (1) Synthesis of Resin (1) (Side Chain Type) 2-Ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were charged at a ratio of 55/45 methyl ethyl ketone / tetrahydrofuran = 5 / It was dissolved in 5 to prepare 100 mL of a solution having a solid content concentration of 20%. 2 mol% of V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added to this solution, and this was added dropwise to 10 mL of methyl ethyl ketone heated to 60 ° C. over 4 hours under a nitrogen atmosphere. After completion of the dropping, the reaction solution was heated for 4 hours, V-65 was added again at 1 mol% and the mixture was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature and distilled water / ISO propyl alcohol = 1/1 mixed solvent 3 L
The resin (1), which is a white powder that was crystallized and precipitated in the above, was recovered. Polymer composition ratio determined from C ¹³ NMR is 46/54
Met. Further, the weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 10700.

Resins (2) to (17) and (38) to (39) were synthesized by the same operation as in Synthesis Example (1) above.
The composition ratios and molecular weights of the above resins (2) to (17) are shown below. (Repeating units 1, 2, 3, and 4 are in order from the left of the structural formula.)

[0245]

[Table 1]

[0246]

[Table 2]

The structures of the above resins (1) to (17) are shown below.

[0248]

[Chemical 87]

[0249]

[Chemical 88]

[0250]

[Chemical 89]

[0251]

[Chemical 90]

[0252]

[Chemical Formula 91]

[0253]

[Chemical Formula 92]

[0254]

[Chemical formula 93]

[0255]

[Chemical 94]

Synthesis Example (2) Synthesis of Resin (18) (Main Chain Type) Norbornenecarboxylic acid t-butyl ester, norbornenecarboxylic acid butyrolactone ester, maleic anhydride (molar ratio 40/10/50) and THF (reaction temperature 6
0 wt%) was charged into a separable flask and heated at 60 ° C. under a nitrogen stream. When the reaction temperature became stable, 2 mol% of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. Heated for 12 hours. The resulting reaction mixture was diluted twice with tetrahydrofuran and then diluted with hexane /
It was put into a mixed solution of isopropyl alcohol = 1/1 to precipitate a white powder. The precipitated powder is filtered out,
After drying, the target Resin (18) was obtained. When the molecular weight analysis of the obtained resin (18) by GPC was tried, it was 8300 (weight average) in terms of polystyrene. Further, from the NMR spectrum, it was confirmed that the molar ratio of norbornenecarboxylic acid t-butyl ester / norbornenecarboxylic acid butyrolactone ester / maleic anhydride repeating unit of the resin (1) was 42/8/50.

Resins (19) to (29) were synthesized in the same manner as in Synthesis example (2). The following resin (1
The composition ratios and molecular weights of 9) to (29) are shown. (Alicyclic olefin units 1, 2, and 3 are in order from the left in the structural formula.)

[0258]

[Table 3]

Further, the following resins (18) to (29)
Shows the structure of.

[0260]

[Chemical 95]

[0261]

[Chemical 96]

Synthesis Example (3) Synthesis of Resin (30) (Hybrid Type) Norbornene, maleic anhydride, t-butyl acrylate and 2-methylcyclohexyl-2-propyl acrylate were reacted at a molar ratio of 35/35/20/10. It was charged in a container and dissolved in tetrahydrofuran to prepare a solution having a solid content of 60%. This was heated at 65 ° C. under a nitrogen stream. When the reaction temperature became stable, 1 mol% of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 8 hours, the reaction mixture was diluted twice with tetrahydrofuran and then poured into hexane in an amount 5 times the volume of the reaction mixture to precipitate a white powder. The precipitated powder was taken out by filtration, dissolved in methyl ethyl ketone, reprecipitated in 5 times volume of hexane / t-butyl methyl ether = 1/1 mixed solvent, and the precipitated white powder was taken out by filtration, dried, and purposed. A resin (30) which is a product was obtained. When the molecular weight analysis of the obtained resin (30) by GPC was tried, it was 1 in terms of polystyrene.
It was 2100 (weight average). Further, from the NMR spectrum, the composition of the resin (1) was as follows: norbornene / maleic anhydride / t-butyl acrylate / 2-methylcyclohexyl-2-propyl acrylate of the present invention in a molar ratio of 32 /
It was 39/19/10. Resins (31) to (37) were synthesized in the same manner as in Synthesis Example (3).

The composition ratios and molecular weights of the resins (31) to (37) and the resins (38) to (39) are shown below.

[0264]

[Table 4]

[0265]

[Table 5]

In addition, the following resins (30) to (37)
And the structures of the resins (38) to (39).

[0267]

[Chemical 97]

[0268]

[Chemical 98]

[0269]

[Chemical 99]

[Examples 1 to 39 and Comparative Example 1] <Resist preparation> The resins shown in Table 6 below were dissolved in a solvent to prepare a solution having a solid content concentration of 10% by weight. Filter by the indicated filter (process FA),
A photoacid generator, a basic compound and a surfactant shown in Table 6 were added to the filtered solution to prepare a mixed solution, and the obtained mixed solution was filtered through a filter shown in Table 6 (Step F
By performing B), a positive resist composition was prepared. Comparative Example 1 was the same as Example 1 except that the step FA was omitted.

[0271]

[Table 6]

The abbreviations in Table 6 are as follows. DBN; 1,5-diazabicyclo [4.3.0] nona
5-ene TPI; 2,4,5-triphenylimidazole TPSA; triphenylsulfonium acetate HEP; N-hydroxyethylpiperidine DIA; 2,6-diisopropylaniline DCMA; dicyclohexylmethylamine TPA; tripentylamine TOA; tri-n -Octylamine HAP; hydroxyantipyrine TBAH; tetrabutylammonium hydroxide TMEA; tris (methoxyethoxyethyl) amine PDEA; N-phenyldiethanolamine

W-1; Megafac F176 (manufactured by Dainippon Ink Co., Ltd.) (fluorine) W-2; Megafac R08 (manufactured by Dainippon Ink Co., Ltd.)
(Fluorine and silicon type) W-3; Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (Silicone type) W-4; Troisol S-366 (Troy Chemical Co., Ltd.)
Made)

S1; propylene glycol methyl ether acetate S2; 2-heptanone S3; ethyl ethoxypropionate S4; γ-butyrolactone S5; cyclohexanone S6; propylene glycol methyl ether S7; ethyl lactate

F1; Aeon Clean (manufactured by Nippon Pall Co.,
Pore diameter 0.1 μm) F2; ION CLEAN AQ (manufactured by Nippon Pall Ltd., pore diameter 0.
1 μm) F3; Microlith Optimizer DEV-16 / 4
0 (polyethylene filter manufactured by Microlith, pore size 0.05 μm) F4; Microguard Minichem (polyethylene filter manufactured by Microlith, pore size 0.05 μm) F5; Enflon (polytetrafluoroethylene filter manufactured by Nippon Pall, pore size 0. 1 μm) F6; Ultipore N66 (Nylon 66 manufactured by Nippon Pall Ltd.)
Filter, pore size 0.05 μm) F7; Zeta Plus (Cuno Cellulosic filter, pore size 0.05 μm) F8; Electropore II (Cuno Nylon 66 filter, pore size 0.1 μm)

<Evaluation of Sensitivity Variation with Time> 78 ARC29a manufactured by Brewer Science Co., Ltd. was placed on a silicon wafer treated with hexamethyldisilazane by a spin coater.
The coating was evenly applied at 0 angstrom, dried on a hot plate at 100 ° C. for 90 seconds, and then dried by heating at 205 ° C. for 60 seconds to form an antireflection film. Then, each positive resist composition immediately after preparation was applied by a spin coater and dried at 120 ° C. for 90 seconds to form a resist film of 0.30 μm. ArF excimer laser stepper (ISI N
A = 0.6), and immediately after the exposure, heating was performed at 120 ° C. for 90 seconds on a hot plate. 2.38% by weight
23 ℃ with tetramethylammonium hydroxide aqueous solution
Developed for 60 seconds, rinsed with pure water for 30 seconds, and then dried to obtain a resist line pattern. The sensitivity was expressed by the exposure dose for reproducing a 0.15 μm line-and-space (1/1) pattern. Then, after adjustment, at room temperature 90
The sensitivity of each positive resist composition after storage for a day was measured in the same manner, and the change in sensitivity with time was evaluated, and the results are shown in Table 7.
It was shown to.

<Evaluation of developer developing property> A silicon wafer having an antireflection film and a resist film formed thereon was held on a horizontal electronic balance in the same manner as above, while slowly dropping an alkaline developing solution from the center of the wafer. The weight of the alkaline developer was measured just before the alkaline developer spilled from the wafer. Table 7 shows the weights of the alkaline developers of the respective examples when the weight of the alkaline developer of Comparative Example 1 was 100%. The smaller the value is, the more the alkaline developer can be spread on the entire surface of the wafer with a small amount, and the better the spreadability of the developer is.

[0278]

[Table 7]

From Table 7, it can be seen that the method for producing a positive resist composition according to the present invention shows a small change in sensitivity with time,
It is clear that a positive resist composition having excellent developing property can be produced.

[0280]

EFFECT OF THE INVENTION According to the present invention, it is possible to produce a positive resist composition having a small sensitivity variation with the passage of time and having an excellent developing property.

Claims (3)

[Claims] 1. A process for producing a positive resist composition containing a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, the solubility of which in an alkali developing solution is increased by the action of an acid. Alternatively, a method for producing a positive resist composition, comprising a filtration step of filtering a resin having a polycyclic alicyclic hydrocarbon structure and having an increased solubility in an alkali developing solution by the action of an acid with an ion exchange filter. . 2. A method for producing a positive resist composition containing a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, the solubility of which in an alkali developing solution is increased by the action of an acid. A resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, the solubility of which in an alkali developing solution is increased by the action of an acid, is filtered by an insoluble colloid removal filter, and a filtration step is included. A method for producing the positive resist composition as described above. 3. A method for producing a positive resist composition containing a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, the solubility of which in an alkali developing solution is increased by the action of an acid. Or a filtration step of filtering an organic solvent solution of a resin having a polycyclic alicyclic hydrocarbon structure and having increased solubility in an alkali developing solution by the action of an acid with an ion exchange filter, and then applying actinic rays or radiation to the organic solvent solution. The method for producing a positive resist composition, comprising: a step of preparing a mixed solution by mixing a compound that generates an acid upon irradiation with the above step; and a filtration step of filtering the mixed solution with an insoluble colloid removal filter.