JP2002341543A - Positive resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive resist composition suitable for the use of an exposure light source at <=160 nm wavelength, in particular, for F2 excimer laser light (at 157 nm wavelength), and specifically, to provide a positive resist composition showing sufficient transmittance and preferable contrast by dissolution when the light source at 157 nm wavelength is used. SOLUTION: The positive resist composition contains (A) a resin which has at least one structural unit of a specified structure and which is decomposed by the effect of an acid to increase the solubility with an alkali developer, (B) a compound which produces an acid by irradiation of active rays or radiation and (C) a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive resist composition suitable for use in microlithography processes such as the production of VLSI and high-capacity microchips, and other photofabrication processes. More specifically, the present invention relates to a positive resist composition capable of forming a high-definition pattern using vacuum ultraviolet light of 160 nm or less.

[0002]

2. Description of the Related Art The degree of integration of integrated circuits has been increasing, and in the manufacture of semiconductor substrates such as ultra LSIs, it has become necessary to process ultrafine patterns having a line width of less than quarter micron. Was. As one of means for miniaturizing a pattern, it is known to shorten the wavelength of an exposure light source used in forming a resist pattern. This means Rayleigh's equation representing the resolution (line width) R of the optical system, R = k · λ / NA (where λ is the wavelength of the exposure light source, NA is the numerical aperture of the lens,
k is a process constant). From this equation, it can be seen that in order to achieve high resolution, that is, to reduce the value of R, the wavelength λ of the exposure light source may be reduced.

For example, to manufacture a semiconductor device having a degree of integration of up to 64 Mbits, an i-line (365 n
m) has been used as a light source. As a positive resist corresponding to this light source, a number of compositions containing a novolak resin and a naphthoquinonediazide compound as a photosensitive material have been developed in large numbers, and have achieved satisfactory results in processing a line width up to about 0.3 μm. . In the manufacture of a semiconductor device having an integration degree of 256 Mbits or more, KrF excimer laser light (248 nm) has been employed as an exposure light source instead of i-line. Furthermore, for the purpose of manufacturing a semiconductor having a degree of integration of 1 Gbit or more, use of an ArF excimer laser beam (193 nm), which is a light source of a shorter wavelength, has been recently used.
The use of F ₂ excimer laser light (157 nm) to form a pattern of m or less has been studied.

[0004] With the shortening of the wavelength of these light sources, the constituent components of the resist material and the compound structure thereof have also changed greatly. That is, a conventional resist containing a novolak resin and a naphthoquinonediazide compound has a large absorption in the far ultraviolet region of 248 nm, so that it is difficult for light to sufficiently reach the bottom of the resist, and only a tapered pattern with low sensitivity can be obtained. To solve such problems, 24
Composition composed of poly (hydroxystyrene) having low absorption in the 8 nm region as a basic skeleton and a resin protected with an acid-decomposable group as a main component, combined with a compound (photoacid generator) that generates an acid upon irradiation with far ultraviolet light. Products, so-called chemically amplified resists, have been developed. A chemically amplified resist changes the solubility in a developing solution by a catalytic decomposition reaction of an acid generated in an exposed portion, so that a high-sensitivity, high-resolution pattern can be formed.

Effective acid-decomposable resins and photoacid generators are described in Polym. Eng. Sci., 23, 1012 (1983) and ACS. Sym., 242, 11 (198).
4), Macromolecules, 21, 1475 (198)
8), Journal of the Society of Synthetic Organic Chemistry, 49, 437 (199)
1), "Microfabrication and resist" (Kyoritsu Shuppan, 1987)
And many other papers and patents. A
When rF excimer laser light (193 nm) was used, the compound having an aromatic group essentially had a large absorption in the 193 nm wavelength region, and thus the above-described chemically amplified resist could not provide sufficient performance.

To solve this problem, an acid-decomposable resin having poly (hydroxystyrene) as a basic skeleton has been replaced with an acid-decomposable resin having an alicyclic structure having no absorption at 193 nm introduced into the main chain or side chain of the polymer. Instead, improvement of a chemically amplified resist has been attempted. These alicyclic acid-decomposable resins are described in, for example, JP-A-4-39665 and JP-A-7-23451.
No. 1, No. 9-73173, No. 7-199467, No. 8-259626, No. 9-221519, No. 10-
No. 10739, No. 9-230595, No. 10-111
No. 569, No. 10-218947, No. 10-1538
No. 64 and WO-97 / 33198.

Further, F ₂ excimer laser light (157n)
m), the alicyclic resin also has a thickness of 157 nm.
It was found that the absorption in the region was large and was insufficient to obtain the desired pattern of 0.1 μm or less. On the other hand, it is confirmed that the resin having a fluorine atom (perfluoro structure) introduced therein has sufficient transparency at 157 nm.
ol. 3678. Reported on page 13 (1999), and the effective fluororesin structure was found in Proc. SPIE. Vol. 3999. 330 (2000), 35
7 pages (2000), 365 pages (2000), WO-00 / 1771
No. 2 has been proposed. However, the resists containing these fluororesins did not always have sufficient dissolution contrast between exposed and unexposed portions.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a laser beam having a wavelength of 160 nm or less, especially an F ₂ excimer laser
A positive resist composition suitable for use with an exposure light source of 57 nm). Specifically, a positive resist composition exhibiting sufficient transparency when using a light source of 157 nm and having good dissolution contrast is provided. To provide.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies while paying attention to the above-mentioned characteristics, and as a result, have found that the object of the present invention is excellently achieved by using the following specific compositions. Reached the present invention. That is, the present invention has the following configuration.

(1) (A) The following general formulas (I) and (I)
A resin having at least one repeating unit represented by I), which is decomposed by the action of an acid to increase the solubility in an alkali developer, (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (C) A) positive resist composition containing a solvent.

[0011]

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In the formulas (I) and (II), R ₁ and R ₅ may be the same or different and represent a hydrogen atom, a fluorine atom or an alkyl group which may have a substituent. R ₂ , R ₃ , R ₆ and R ₇ may be the same or different and may have a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, or an optionally substituted alkoxy group,
Represents an acyl group, an alkyl group, an alkenyl group, an aralkyl group or an aryl group. R ₄ represents an alkyl group, an acyl group or an alkoxycarbonyl group which may have a substituent. R ₃₀ represents an alkyl group. Further, R ₄ and R ₃₀ may be bonded to each other to form a ring.

(2) The positive resist composition according to (1), wherein R _{4 in the} general formula (I) is an alkyl group partially or wholly substituted by a fluorine atom. (3) The positive resist composition according to (1) or (2), wherein the resin (A) further has at least one repeating unit represented by the following general formula (III).

[0014]

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In the general formula (III), R₈And R₉Is the same
But may be different, such as a hydrogen atom, a halogen atom,
An ano group or an alkyl group which may have a substituent
You. R _TenHas a hydrogen atom, a halogen atom and a substituent
An optionally substituted alkyl group or -A ₁Represents a —CN group. A
₁Is a single bond, an optionally substituted divalent alkylene
Group, alkenylene group or arylene group, or -O
-CO-R₁₁-, -CO-OR₁₂-, -CO-N (R
₁₃) -R₁₄Represents-. R₁₁, R₁₂And R₁₄Is the same
May be different, a single bond, or an ether group,
Contains a ter group, amide group, urethane group or ureide group
Or a divalent alkylene group, alkenylene group or
Represents an arylene group. R₁₃Has a hydrogen atom and a substituent
An alkyl group, an aralkyl group or an aryl group
Represents

(4) The resin of (A) further has a general formula (I)
V) The positive resist composition according to any one of (1) to (3), which has at least one repeating unit represented by (XI).

[0017]

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In the general formulas (IV) to (XI), R ₁₅ and R
₁₆ may be the same or different and represents a hydrogen atom, a fluorine atom, or an alkyl or aryl group which may have a substituent. R _{17 to} R ₁₉ may be the same or different and represent an alkyl group or an aryl group which may have a substituent. R ₁₅ and R ₁₆ , R ₁₅ and R ₁₇ , and R ₁₈ and R ₁₉ may be bonded to each other to form a ring. R
₂₀ represents a hydrogen atom, an alkyl group, an acyl group or an alkoxycarbonyl group which may have a substituent.
R ₂₁ , R ₂₂ and R ₂₃ may be the same or different;
A hydrogen atom, a halogen atom, which may have a substituent,
Represents an alkyl group or an alkoxy group. R ₂₄ represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group. R ₂₅ represents an alkyl group, an aralkyl group or an aryl group which may have a substituent. B ₁ and B ₂ may be the same or different and may have a single bond, a substituent, a divalent alkylene group, an alkenylene group or an arylene group, or —O—CO—R ₂₆
—, —CO—O—R ₂₇ — or —CO—N (R ₂₈ ) —
R ₂₉ - represents a. R ₂₆ , R ₂₇ and R ₂₉ may be the same or different and may have a single bond or an ether group, an ester group, an amide group, a urethane group or a ureido group, a divalent alkylene group or an alkenylene group Or an arylene group. R ₂₈ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group which may have a substituent.
n represents 0 or 1.

(5) The resin of (A) further has the general formula (X)
The positive resist composition according to any one of (1) to (4), which has at least one repeating unit represented by II).

[0020]

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In the general formula (XII), R ₃₁ and R ₃₂ may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent.
_R33 is -C ( _R34 ) ( _R35 ) ( _R36 ), -C ( _R34 )
(R ₃₅ ) (OR ₃₇ ) or a group represented by the formula (XIII). R _{34 to} R ₃₇ may be the same or different and represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group or an aryl group which may have a substituent. Two of R ₃₄ , R ₃₅ , R ₃₆ , or R ₃₄ , R ₃₅ ,
Two _{members out} of R ₃₇ may combine to form a ring. A
₂ is a single bond, an optionally substituted divalent alkylene group, alkenylene group or arylene group, or -O
_{-CO-R 43 -, - CO} -O-R 44 -, - CO-N (R
₄₅₎ -R ₄₆ - represents a. R ₄₃ , R ₄₄ and R ₄₆ may be the same or different and may have a single bond or an ether group, an ester group, an amide group, a urethane group or a ureido group, a divalent alkylene group, an alkenylene Represents an arylene group or an arylene group. R ₄₅ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group which may have a substituent. In the formula (XIII), R ₃₈ represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group which may have a substituent. Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with a carbon atom.

[0022]

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(6) The resin of (A) further has a general formula (X)
The positive resist composition according to any one of (1) to (5), which has at least one repeating unit represented by (IV).

[0024]

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In the general formula (XIV), R ₃₉ , R ₄₀ and R ₄₁
Represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group or an alkoxy group, which may be the same or different and may have a hydrogen atom, a halogen atom, a cyano group or a substituent. R ₄₂ represents an optionally substituted alkyl group, alkenyl group, aralkyl group or aryl group. n represents 0 or 1.

[0026] (7) R ₄ of general formula (I), characterized by being represented by the following general formula (XV) (1) ~ ( 6)
The positive resist composition according to any one of the above.

[0027]

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In the general formula (XV), X represents a hydrogen atom or a fluorine atom. n represents an integer of 0 to 3. m is 0
Represents an integer of 10 to 10.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. [1] Resin of the present invention (A) The resin in the present invention (A) is represented by the general formula (I)
A resin having at least one repeating unit represented by I), which is decomposed by the action of an acid and increases the solubility in an alkali developing solution. The resin in the present invention (A) is preferably further one of the general formulas (III) to (XII)
And at least one repeating unit represented by (XIV).

In the formulas (I) and (II), R ₁ and R ₅ may be the same or different and represent a hydrogen atom, a fluorine atom or an alkyl group which may have a substituent. R ₂ , R ₃ , R ₆ and R ₇ may be the same or different and may have a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, or an optionally substituted alkoxy group,
Represents an acyl group, an alkyl group, an alkenyl group, an aralkyl group or an aryl group. R ₄ represents an alkyl group, an acyl group or an alkoxycarbonyl group which may have a substituent. R ₃₀ represents an alkyl group. Further, R ₄ and R ₃₀ may be bonded to each other to form a ring.

In the general formula (III), R₈And R₉Is the same
But may be different, such as a hydrogen atom, a halogen atom,
An ano group or an alkyl group which may have a substituent
You. R _TenHas a hydrogen atom, a halogen atom and a substituent
An optionally substituted alkyl group or -A ₁Represents a —CN group. A
₁Is a single bond, an optionally substituted divalent alkylene
Group, alkenylene group or arylene group, or -O
-CO-R₁₁-, -CO-OR₁₂-, -CO-N (R
₁₃) -R₁₄Represents-. R₁₁, R₁₂And R₁₄Is the same
May be different, a single bond, or an ether group,
Contains a ter group, amide group, urethane group or ureide group
Or a divalent alkylene group, alkenylene group or
Represents an arylene group. R₁₃Has a hydrogen atom and a substituent
An alkyl group, an aralkyl group or an aryl group
Represents

In the general formulas (IV) to (XI), R ₁₅ and R
₁₆ may be the same or different and represents a hydrogen atom, a fluorine atom, or an alkyl or aryl group which may have a substituent. R _{17 to} R ₁₉ may be the same or different and represent an alkyl group or an aryl group which may have a substituent. R ₁₅ and R ₁₆ , R ₁₅ and R ₁₇ , and R ₁₈ and R ₁₉ may be bonded to each other to form a ring. R
₂₀ represents a hydrogen atom, an alkyl group, an acyl group or an alkoxycarbonyl group which may have a substituent.
R ₂₁ , R ₂₂ and R ₂₃ may be the same or different;
A hydrogen atom, a halogen atom, which may have a substituent,
Represents an alkyl group or an alkoxy group. R ₂₄ represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group. R ₂₅ represents an alkyl group, an aralkyl group or an aryl group which may have a substituent. B ₁ and B ₂ may be the same or different and may have a single bond, a substituent, a divalent alkylene group, an alkenylene group or an arylene group, or —O—CO—R ₂₆
—, —CO—O—R ₂₇ — or —CO—N (R ₂₈ ) —
R ₂₉ - represents a. R ₂₆ , R ₂₇ and R ₂₉ may be the same or different and may have a single bond or an ether group, an ester group, an amide group, a urethane group or a ureido group, a divalent alkylene group or an alkenylene group Or an arylene group. R ₂₈ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group which may have a substituent.
n represents 0 or 1.

In the general formula (XII), R ₃₁ and R ₃₂ may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent.
_R33 is -C ( _R34 ) ( _R35 ) ( _R36 ), -C ( _R34 )
(R ₃₅ ) (OR ₃₇ ) or a group represented by the formula (XIII). R _{34 to} R ₃₇ may be the same or different and represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group or an aryl group which may have a substituent. Two of R ₃₄ , R ₃₅ , R ₃₆ , or R ₃₄ , R ₃₅ ,
Two _{members out} of R ₃₇ may combine to form a ring. A
₂ is a single bond, an optionally substituted divalent alkylene group, alkenylene group or arylene group, or -O
_{-CO-R 43 -, - CO} -O-R 44 -, - CO-N (R
₄₅₎ -R ₄₆ - represents a. R ₄₃ , R ₄₄ and R ₄₆ may be the same or different and may have a single bond or an ether group, an ester group, an amide group, a urethane group or a ureido group, a divalent alkylene group, an alkenylene Represents an arylene group or an arylene group. R ₄₅ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group which may have a substituent. In the formula (XIII), R ₃₈ represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group which may have a substituent. Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with a carbon atom.

In the general formula (XIV), R ₃₉ , R ₄₀ and R ₄₁
Represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group or an alkoxy group, which may be the same or different and may have a hydrogen atom, a halogen atom, a cyano group or a substituent. R ₄₂ represents an optionally substituted alkyl group, alkenyl group, aralkyl group or aryl group. n represents 0 or 1.

Examples of the alkyl group include linear, branched and cyclic alkyl groups. The straight-chain and branched alkyl groups are, for example, alkyl groups having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group,
Preferred examples include a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, and an octyl group. The cyclic alkyl group may be monocyclic or polycyclic. The monocyclic type has 3 to 8 carbon atoms, and preferably includes, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic type include those having 6 to 20 carbon atoms, such as an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an a-pinel group, a tricyclodecanyl group, a tetracyclododecyl group, Preferable examples include an androstanyl group.

The aryl group includes, for example, those having 6 to 1 carbon atoms.
5 aryl groups, specifically, a phenyl group,
Tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, anthryl group, 9,10-
A dimethoxyanthryl group and the like can be preferably mentioned. The aralkyl group is, for example, an aralkyl group having 7 to 12 carbon atoms, and specific examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

The alkenyl group includes, for example, those having 2 to 2 carbon atoms.
8 alkenyl groups, specifically, a vinyl group,
An allyl group, a butenyl group, and a cyclohexenyl group can be preferably exemplified. The alkoxy group is, for example, an alkoxy group having 1 to 8 carbon atoms, specifically, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a butoxy group, a pentoxy group, an allyloxy group, an octoxy group. And the like.

Examples of the acyl group include those having 1 to 10 carbon atoms.
Specific examples thereof include a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, an octanoyl group, and a benzoyl group. As the alkoxycarbonyl group, t-
Butoxycarbonyl group, t-amyloxycarbonyl group,
A tertiary alkoxycarbonyl group such as a 1-methyl-1-cyclohexyloxycarbonyl group is exemplified. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkylene group include linear, branched and cyclic alkylene groups which may have a substituent. Examples of the linear or branched alkylene group include those having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. Examples of the cyclic alkylene group include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group. Examples of the alkenylene group preferably include those having 2 to 6 carbon atoms such as an ethenylene group, a propenylene group, and a butenylene group which may have a substituent. The arylene group preferably has 6 to 15 carbon atoms such as a phenylene group, a tolylene group and a naphthylene group which may have a substituent.

R ₄ and R ₃₀ , R ₁₅ and R ₁₆ , R ₁₅ and R ₁₇ , R
₁₈ and R ₁₉ or two of R _{34 to} R ₃₆ or R ₃₄ , R
_The ring formed by combining two of ₃₅ and R ₃₇ with each other is, for example, a 3- to 8-membered ring, specifically, a cyclopropane ring, a cyclopentane ring, a cyclohexane ring, a tetramethylene oxide ring, a pentamethylene ring. Examples include an oxide ring, a hexamethylene oxide ring, a furan ring, a pyran ring, a dioxonol ring, and a 1,3-dioxolane ring. Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group, and the formed alicyclic group is a monocyclic type having 3 to 8 carbon atoms, for example, a cyclopropyl group , Cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups. The polycyclic type has 6 to 20 carbon atoms, such as an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an a-pinel group, a tricyclodecanyl group, a tetracyclododecyl group, An androstanyl group and the like can be preferably mentioned.

Examples of the substituent to be substituted on these groups include those having active hydrogen such as an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group and a carboxyl group, and halogen atoms (a fluorine atom, a chlorine atom). , A bromine atom, an iodine atom), an alkoxy group (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), a thioether group,
Acyl group (acetyl group, propanoyl group, benzoyl group, etc.), acyloxy group (acetoxy group, propanoyloxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc.), alkyl Groups (butyl group, cyclohexyl group), cyano group, nitro group and the like.

R _{4 in the} general formula (I) is preferably an alkyl group partially or wholly substituted by a fluorine atom. More preferably, R ₄ in the general formula (I) is represented by the general formula (XV).

Action of acid contained in the resin of the present invention (A)
As a group that is decomposed by and shows alkali solubility, for example,
-OC (R₃₄) (R₃₅) (R₃₆), -OC (R₃₄)
(R ₃₅) (OR₃₇), -O-COO-C (R₃₄)
(R₃₅) (R₃₆), -OC (R₀₁) (R₀₂) COO-
C (R₃₄) (R₃₅) (R₃₆), -COO-C (R₃₄)
(R₃₅) (R₃₆), -COO-C (R₃₄) (R₃₅) (O
R₃₇) And the like. R₃₄~ R₃₇Is synonymous with the above
R₀₁, R₀₂Is a hydrogen atom, having the substituents indicated above.
Alkyl group, cycloalkyl group, alkenyl
Represents an aryl group, an aralkyl group, or an aryl group.

Preferred specific examples include a t-butyl group,
t-amyl group, 1-alkyl-1-cyclohexyl group,
2-alkyl-2-adamantyl group, 2-adamantyl-2-propyl group, 2- (4-methylcyclohexyl)
Tert-alkyl group such as -2-propyl group, ether group or ester group, 1-alkoxy-1-ethoxy group, acetal group or acetal ester group such as tetrahydropyranyl group, t-alkyl carbonate group, t-alkylcarbonyl A methoxy group and the like are preferred. More preferably, it is an acetal group such as a 1-alkoxy-1-ethoxy group and a tetrahydropyranyl group. In the case of an acetal group, the acid-decomposability is large, the range of choice of the acid-generating compound to be used in combination is widened, the sensitivity is improved, and the performance varies over time from exposure to heating. Particularly preferred is an acetal group containing an alkoxy group derived from the perfluoroalkyl group as the 1-alkoxy component of the acetal group. In this case, the transmittance with short-wave exposure light (for example, 157 nm of F ₂ excimer laser light) can be further improved.

The content of the repeating unit represented by the general formula (I) is in the range of 5 to 80 mol%, preferably 7 to 70 mol%, more preferably 10 to 50 mol% in the whole polymer composition. . The content of the repeating unit represented by the general formula (II) is 1 to 90 in the whole polymer composition.
Mol%, preferably 3 to 80 mol%, more preferably 5 mol%.
It is used in the range of ~ 70 mol%. The content of the repeating unit represented by the general formula (III) is used in the range of 5 to 80 mol%, preferably 7 to 70 mol%, more preferably 10 to 50 mol% in the whole polymer composition. The content of the repeating units represented by the general formulas (IV) to (IX) is 5 to 80 mol%, preferably 7 to 70 mol%, more preferably 10 to 50 mol% in the whole polymer composition.
Used in the range. The content of the repeating unit represented by the general formula (X) is 1 to 30 mol%, preferably 3 to 25 mol%, more preferably 5 to 2 mol% in the whole polymer composition.
It is used in the range of 0 mol%. The content of the repeating unit represented by the general formula (XI) is 5 in the total polymer composition.
It is used in the range of from 80 to 80 mol%, preferably from 7 to 70 mol%, more preferably from 10 to 50 mol%. The general formula (X
The content of the repeating unit represented by II) is used in the range of 1 to 30 mol%, preferably 3 to 25 mol%, more preferably 5 to 20 mol% in the whole polymer composition. The content of the repeating unit represented by the general formula (XIV) is 5 to 80 mol%, preferably 7 to 70 mol%, more preferably 10 to 50 mol% in the whole polymer composition.
Used in the range.

The resin of the present invention (A) may be copolymerized with other polymerizable monomers for the purpose of further improving the performance of the positive resist of the present invention, in addition to the repeating structural units described above. .

The copolymerizable monomers that can be used include the following. For example, acrylates other than the above, acrylamides, methacrylates, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, addition polymerizable unsaturated bonds selected from crotonates and the like. It is a compound having one.

Specifically, for example, acrylic esters such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (eg, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate 2, etc.)
2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) aryl acrylate (for example, phenyl acrylate);

Methacrylic esters, for example, alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, 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, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.), aryl methacrylate (for example, phenyl methacrylate) , Cresyl methacrylate, naphthyl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide, (where the alkyl group has 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl) Group, octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-arylacrylamide (aryl group includes, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group,
Examples include a cyanophenyl group, a hydroxyphenyl group, and a carboxyphenyl group. ), N, N-dialkylacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a butyl group, an isobutyl group, an ethylhexyl group, a cyclohexyl group, etc.), N-diarylacrylamide (an aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like ;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl Group, cyclohexyl group, etc.), N
-Aryl methacrylamide (an aryl group includes a phenyl group and the like), N, N-dialkyl methacrylamide (an alkyl group includes an ethyl group, a propyl group and a butyl group), N, N-diaryl Methacrylamide (an aryl group includes a phenyl group and the like), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide and the like;
Allyl compounds, for example, allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxyethanol Such;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether,
Ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, Tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ethers (for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-
2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.);

Vinyl esters, for example, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate , Vinylphenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-
Phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like;

Styrenes such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl Styrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc., alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene) , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluors Ren, trifluoromethyl styrene, 2
-Bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), carboxystyrene, vinylnaphthalene;

Crotonic esters, for example, alkyl crotonates (eg, butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.); dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.) ); Dialkyl esters of maleic acid or fumaric acid (eg,
Dimethyl maleate, dibutyl fumarate, etc.). In addition, generally, any addition-polymerizable unsaturated compound that can be copolymerized may be used.

Hereinafter, specific examples of the repeating structural unit represented by the general formula (I) will be shown, but the present invention is not limited thereto.

[0057]

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[0058]

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Hereinafter, specific examples of the repeating structural unit represented by the general formula (II) will be shown, but the present invention is not limited thereto.

[0060]

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Hereinafter, specific examples of the repeating structural unit represented by the general formula (III) will be shown, but the present invention is not limited thereto.

[0062]

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The specific examples of the repeating structural units represented by formulas (IV) to (IX) are shown below, but the present invention is not limited thereto.

[0064]

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[0065]

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[0066]

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[0067]

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The following formulas (XII) and (XIV)
Specific examples of the repeating structural unit represented by are shown below, but the present invention is not limited thereto.

[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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Each of the repeating structural units represented by the above specific examples may be used alone or in combination. The preferred molecular weight of the resin (A) of the present invention having the above repeating structural unit is from 1,000 to 2 in weight average.
00,000, more preferably 3,000 to 2,
Used in the range of 0000. Molecular weight distribution is 1-10
And preferably those in the range of 1 to 3, more preferably 1 to 2. The smaller the molecular weight distribution,
The resolution, the resist shape, and the side walls of the resist pattern are smooth and excellent in roughness. The addition amount of the resin (A) of the present invention is 50% based on the total solid content of the composition.
-99.5% by weight, preferably 60-98% by weight, more preferably 65-95% by weight.

[2] The compound of the present invention (B) which generates an acid upon irradiation with actinic rays or radiation The compound used in the present invention which decomposes upon irradiation with actinic rays or radiation to generate an acid includes: Known light (4) used in photoinitiators for cationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, micro resists, etc.
Ultraviolet rays of from 200 to 200 nm, far ultraviolet rays, particularly preferably g-line, h-line, i-line, KrF excimer laser light),
A compound capable of generating an acid by an ArF excimer laser beam, an electron beam, an X-ray, a molecular beam or an ion beam, and a mixture thereof can be appropriately selected and used.

Other compounds that generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, SI Schlesinger, Photogr. Sci. En.
g., 18,387 (1974), TS Bal et al, Polymer, 21, 4
23 (1980) and the like diazonium salts, U.S. Pat.
No. 055, 4,069,056, Re 27,992, JP-A-3-401
Ammonium salt described in No. 40, etc., DC Necker et al,
Macromolecules, 17, 2468 (1984), CS Wen et al, T
eh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1
988), U.S. Pat.Nos. 4,069,055 and 4,069,056, phosphonium salts described in JV Crivello et al, Macromorec
ules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 2
8, p31 (1988), European Patent Nos. 104,143, 339,049, 410,201, JP-A-2-150848, Iodonium salts described in JP-A-2-295514, etc., JVCrivello et al, Polym
er J. 17, 73 (1985), JV Crivello et al., J. Org.
Chem., 43, 3055 (1978), WR Watt et al, J. Polyme
r Sci., Polymer Chem. Ed., 22, 1789 (1984), JV Cr
ivello et al, Polymer Bull., 14, 279 (1985), JV
Crivello et al, Macromorecules, 14 (5), 1141 (198
1), JV Crivello et al, J. Polymer Sci., Polymer
Chem. Ed., 17, 2877 (1979), European Patent No. 370,693,
No. 161,811, No. 410,201, No. 339,049, No. 233,567
Nos. 297,443 and 297,442; U.S. Pat.No.4,933,377
Nos. 3,902,114, 4,760,013, 4,734,444,
No. 2,833,827, Dokoku Patent No. 2,904,626, No. 3,604,580
No. 3,604,581, etc., JV C
rivello et al, Macromorecules, 10 (6), 1307 (1977),
JV Crivello et al, J. Polymer Sci., Polymer Che
m. Ed., 17, 1047 (1979) and the like.
S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p
Onium salts such as arsonium salts described in 478 Tokyo, Oct (1988), U.S. Pat.No. 3,905,815, JP-B-46-4605,
JP-A-48-36281, JP-A-55-32070, JP-A-60-23973
No. 6, JP-A-61-169835, JP-A-61-169837, JP-A-61-69837
2-58241, JP-A-62-212401, JP-A-63-70243, Organic halogen compounds described in JP-A-63-298339, K. Me
ier et al, J. Rad. Curing, 13 (4), 26 (1986), TPG
ill et al, Inorg. Chem., 19, 3007 (1980), D. Astru
c, Acc.Chem.Res., 19 (12), 377 (1896), JP-A-2-161
Organometallic / organic halide described in No. 445, etc., S. Haya
se et al, J. Polymer Sci., 25, 753 (1987), E. Reich
manis et al, J. Pholymer Sci., Polymer Chem. Ed.,
23, 1 (1985), QQ Zhuetal, J. Photochem., 36, 85,
39, 317 (1987), B. Amit et al, Tetrahedron Lett., (2
4) 2205 (1973), DHR Barton et al, J. Chem Soc.,
3571 (1965), PM Collins et al, J. Chem. Soc., P
erkin I, 1695 (1975), M. Rudinstein et al, Tetrahed
ron Lett., (17), 1445 (1975), JW Walker et al,
J. Am. Chem. Soc., 110, 7170 (1988), SC Busman e
t al, J. Imaging Technol., 11 (4), 191 (1985), HM
Houlihan et al, Macromolecules, 21, 2001 (1988),
PMCollins et al, J. Chem. Soc., Chem. Commun., 5
32 (1972), S. Hayase et al, Macromolecules, 18, 179
9 (1985), E. Reichmanis et al, J. Electrochem. Soc.,
Solid State Sci. Technol., 130 (6), FM Houlihan
et al, Macromolcules, 21, 2001 (1988), European Patent No. 02
90,750, 046,083, 156,535, 271,851,
No. 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531
JP-A-60-198538, JP-A-53-133022 and the like, a photoacid generator having a 0-nitrobenzyl-type protecting group, M.TU
NOOKA et al, Polymer Preprints Japan, 35 (8), G. Be
rner et al, J. Rad. Curing, 13 (4), WJ Mijs et
al, Coating Technol., 55 (697), 45 (1983), Akzo, H.A.
dachi et al, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 044,115, 618,56
No. 4, 0101,122, U.S. Pat.Nos. 4,371,605, 4,431,
No. 774, JP-A-64-18143, JP-A-2-245756, JP-A
Compounds which generate sulfonic acid upon photolysis, such as iminosulfonates described in JP-A-3-140109, etc.
-166544 and the like.

Further, a compound in which a group or a compound capable of generating an acid upon irradiation with an actinic ray or radiation is introduced into a main chain or a side chain of a polymer, for example, ME Woodho
useet al, J. Am. Chem. Soc., 104, 5586 (1982), S.
P. Pappas et al, J. Imaging Sci., 30 (5), 218 (198
6), S. Kondo et al, Makromol. Chem., Rapid Commu
n., 9, 625 (1988), Y. Yamada et al, Makromol. Che
m., 152, 153, 163 (1972); JV Crivello et al, J.
Polymer Sci., Polymer Chem. Ed., 17, 3845 (1979),
U.S. Patent No. 3,849,137, Dokoku Patent No. 3914407, JP-A-63
-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-15385
No. 3, JP-A-63-146029 and the like can be used.

Further, VNR Pillai, Synthesis, (1),
1 (1980), A. Abad et al, Tetrahedron Lett., (47) 45
55 (1971), DHR Barton et al, J. Chem. Soc.,
(C), 329 (1970), U.S. Patent 3,779,778, European Patent 1
Compounds that generate an acid by light described in No. 26,712 and the like can also be used.

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those which are used particularly effectively are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PAG)
An S-triazine derivative represented by 2).

[0080]

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In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Is shown. Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0082]

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[0083]

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[0084]

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(2) An iodonium salt represented by the following formula (PAG3) or a sulfonium salt represented by the following formula (PAG4).

[0086]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred 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. Preferably, an aryl group having 6 to 14 carbon atoms, 1 to 8 carbon atoms
And substituted derivatives thereof. Preferred substituents are, for the aryl group, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, a nitro group, a carboxyl group, a mercapto group, a hydroxy group and a halogen atom. And an alkyl group includes an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group.

Z ⁻ represents an anion. Specifically, alkyl sulfonic acid, cycloalkyl sulfonic acid, perfluoroalkyl sulfonic acid, and aryl sulfonic acid which may have a substituent (for example, And anions such as benzenesulfonic acid, naphthalenesulfonic acid, and anthracenesulfonic acid.

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

Specific examples include the following compounds, but are not limited thereto.

[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JW Knapcz
yk et al, J. Am. Chem. Soc., 91, 145 (1969), AL
Maycok et al, J. Org.Chem., 35, 2532, (1970), E.
Goethas et al, Bull.Soc.Chem.Belg., 73, 546, (196
4), HM Leicester, J. Ame. Chem. Soc., 51, 3587.
(1929), JV Crivello et al, J. Polym. Chem. Ed.,
18, 2677 (1980), U.S. Pat.Nos. 2,807,648 and 4,247,
No. 473, JP-A-53-101331, and the like.

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0104]

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In the formula, Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
It represents an unsubstituted alkyl group or aryl group. A is a substitution
Or unsubstituted alkylene, alkenylene, arylene
Shows a substituent group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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(4) A diazodisulfone derivative represented by the following general formula (PAG7).

[0113]

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Here, R represents a linear, branched or cyclic alkyl group or an optionally substituted aryl group. Specific examples include the following compounds, but are not limited thereto.

[0115]

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(5) An oxime sulfonate derivative represented by the following general formula (PAG8).

[0117]

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In the formula, R ₂₀₇ represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group or aralkyl group. R ₂₀₈ and R _{209 each} represent a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, aralkyl group, cyano group, or acyl group. R ₂₀₈ and R ₂₀₉ may combine to form a carbocyclic ring or a heterocyclic ring having an oxygen atom, a nitrogen atom, or a sulfur atom. Specific examples include the following compounds, but are not limited thereto.

[0119]

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The amount of the compound that generates an acid upon irradiation with actinic rays or radiation of the present invention (B) is 0.1 to 20% by weight, based on the total solid content of the composition of the present invention. Preferably it is 0.5 to 10% by weight, more preferably 1 to 7% by weight. These compounds may be used alone or in combination of two or more.

[3] Solvent of the present invention (C) The composition of the present invention is dissolved in a solvent capable of dissolving each of the above-mentioned components, and coated on a support. As the solvent used here,
1-methoxy-2-propanol acetate, 1-methoxy-2-propanol, 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 monoethyl 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, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like. -Methoxy-
2-propanol acetate and 1-methoxy-2-propanol are particularly preferred. These solvents are used alone or as a mixture.

[4] Acid Diffusion Inhibitor that can be Used in the Present Invention The composition of the present invention has a performance variation (T-to-pattern of the pattern) over time from irradiation of actinic rays or radiation to heat treatment.
The purpose is to prevent p-shape formation, sensitivity fluctuation, pattern line width fluctuation, etc.), performance fluctuation with time after coating, and excessive diffusion of acid (deterioration of resolution) during heat treatment after irradiation with actinic rays or radiation. It is preferable to add an acid diffusion inhibitor. As an acid diffusion inhibitor, an organic basic compound,
For example, an organic base compound containing a basic nitrogen, and a compound having a pKa value of 4 or more of a conjugate acid is preferably used. Specifically, there can be mentioned the structures of the following formulas (A) to (E).

[0123]

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and include a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, and 1 Represents 6 to 6 hydroxyalkyl groups or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R
²⁵¹ and R ²⁵² may combine with each other to form a ring. 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. Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred are both substituted or unsubstituted amino groups and ring structures containing nitrogen atoms. Or a compound having an alkylamino group.

Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, imidazole, 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, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, a cyano group It is.

Particularly preferred compounds are guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, , 4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine,
-(Aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, -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, and the like, but are not limited thereto. These nitrogen-containing basic compounds are used alone or in combination of two or more.

The ratio of the acid generator and the organic basic compound used in the composition is preferably (acid generator) / (organic basic compound) (molar ratio) = 2.5 to 300. When the molar ratio is less than 2.5, the sensitivity becomes low and the resolving power may decrease. On the other hand, when the molar ratio exceeds 300, the thickness of the resist pattern increases over time until the heat treatment after exposure, and the resolving power may decrease. . (Acid generator) / (organic basic compound) (molar ratio) is preferably from 5.0 to 200, more preferably from 7.0 to 150.

[5] Fluorine and / or silicon surfactant usable in the present invention The positive resist composition of the present invention may contain a fluorine and / or silicon surfactant. . That is, the positive resist composition of the present invention contains one or more of a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom. Can be. The addition of these fluorine-based and / or silicon-based surfactants is effective in suppressing development defects and improving coatability.

As these surfactants, for example, those described in
No. 62-36663, JP-A-61-226746, JP-A-61-226745,
JP-A-62-170950, JP-A-63-34540, JP-A-7-23016
No. 5, JP-A-8-62834, JP-A-9-54432, JP-A-9-598
8, U.S. Patent 5,405,720, U.S. Patent 5,306,692, U.S. Patent 5,529,881, U.S. Patent 5,296,330, U.S. Patent 5436098
No., US Patent No. 5,576,143, US Patent No. 5,296,143, US Patent
Surfactants described in 5294511 and US Pat. No. 5,824,451 can be mentioned, and the following commercially available surfactants can be used as they are. As such commercially available surfactants, for example, F-top EF301, EF303, EF352 (Shin-Akita Kasei
Co., Ltd.), Florado FC430, 431 (Sumitomo 3M Limited)
), Megafac F171, F173, F176, F189, R08 (Dai Nippon Ink Co., Ltd.), Asahi Guard AG710, Surflon S
-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), and other fluorine-based surfactants or silicon-based surfactants. . In addition, polysiloxane polymer KP
-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

The amount of the surfactant is usually 0.001 to 2% by weight, preferably 0.01 to 1% by weight, based on the solid content in the composition of the present invention. These surfactants may be added alone or in some combination.

In the production of precision integrated circuit elements, the pattern formation step on the resist film is performed by forming the positive electrode of the present invention on a substrate (eg, a silicon / silicon dioxide cover, a glass substrate, a transparent substrate such as an ITO substrate, etc.). A good resist pattern can be formed by applying a mold resist composition, then irradiating with an actinic ray or radiation drawing apparatus, heating, developing, rinsing and drying.

Examples of the developer for the positive resist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, ethylamine, and n-propylamine. Primary amines such as diethylamine, di-
Secondary amines such as n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, and tertiary amines such as tetramethylammonium hydroxide, Aqueous solutions of alkalis such as quaternary ammonium salts, cyclic amines such as pyrrole, and piperidine can be used. Further, an appropriate amount of an alcohol such as isopropyl alcohol or a surfactant such as a nonionic surfactant may be added to an aqueous solution of the above alkalis. Of these developers, quaternary ammonium salts are preferred, and tetramethylammonium hydroxide and choline are more preferred.

[0134]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the contents of the present invention are not limited thereto.

[0135] 1. Synthesis Example 1 (Synthesis of Resin (3)) 4- (1-ethoxyethoxy) styrene (Tosoh Corporation)
19.2 g) and 4- (2-hydroxyhexafluoroisopropyl) styrene (Central Glass Co., Ltd.)
After adding 27.0 g to 92.4 g of tetrahydrofuran, the mixture was heated to 65 ° C. under a nitrogen stream. There, 1.48 azo polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.).
8 g was added and reacted for 6 hours while stirring under a nitrogen stream. Hexane was added to the obtained reaction solution, and the resulting polymer (resin (3)) was precipitated from the solution to separate and purify unreacted monomers. GPC (TH
Analysis by F solvent in terms of standard polystyrene) revealed that the weight average molecular weight was 8200, the dispersity was 2.20, and the ratio of the molecular weight of 1000 or less contained in the polymer was 15% by weight.
Met. Hereinafter, the resins of the present invention shown in Table 1 were synthesized in the same manner.

[0136]

[Table 1]

[0137] 2. Example (Measurement of Transmittance) 1.36 g of the resin shown in Table 1 and 0.04 g of a naphthalate salt of triphenylsulfonium were combined with 6.0 g of 1-methoxy-2-propanol acetate and 1-methoxy-2-.
It was dissolved in a mixed solvent of 2.5 g of propanol to prepare a polymer solution. After each polymer solution was filtered through a 0.1 μm Teflon (registered trademark) filter, the solution was applied on a calcium fluoride disk by a spin coater, and then applied to a 120 μm filter.
The resultant was dried by heating at 90 ° C. for 90 minutes to obtain a 0.1 μm resist film. The absorption of the coating film was measured with an Acton CAMS-507 spectrometer, and the transmittance at 157 nm was calculated. Table 2 shows the results. As Comparative Example 1, the polymer A used in the KrF resist: p
-Hydroxystyrene / p- (1-ethoxyethoxystyrene) (70/30) was prepared in the same manner, and the transmittance was measured.

[0138]

[Table 2]

From the results in Table 2, it can be seen that the resist film using the composition of the present invention has a sufficient transmittance at 157 nm.

3. Example (Measurement of Dissolution Contrast) Using the resin of the present invention, a resist solution was prepared in the same manner as in Example 1. After each resist solution was filtered through a 0.1 μm Teflon filter, it was coated on a silicon wafer that had been subjected to hexamethyldisilazane treatment by a spin coater, and was heated and dried on a vacuum hot plate at 120 ° C. for 90 seconds. A resist film having a thickness of 0.1 μm was obtained. With respect to the obtained resist film, a laser exposure / dissolution behavior analyzer VUVES-4500 (manufactured by Lithotec Japan) of 157 nm was used to measure the dissolution contrast of the exposed / unexposed portion at 157 nm. However, for Comparative Example 1, KrF exposure was performed using a KrF polymer. Table 3 shows the results.

[0141]

[Table 3]

From the results shown in Table 3, it can be seen that the composition of the present invention has a dissolution contrast equivalent to or higher than that of the resist practically used for the KrF excimer of the comparative example, that is, the image forming ability.

[0143]

According to the present invention, it is possible to provide a positive resist composition having a sufficient transmittance even at a short wavelength of 157 nm and having a good dissolution contrast.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AA04 AB16 AC04 AC08 AD03 BE00 BG00 CC03 4J100 AB07P AB07Q AB07R AC22S AC26S AE38S AE39S AL08R AL08S AM02R AR11S BA02P BA02Q BA02S BA03H BA18B BABBABBABBABBABBAQ BC04P BC04Q BC04S BC08S BC09S BC27S BC53P BC53S HA08 HA61 HE22 HE26 JA38

Claims (7)

[Claims] (A) a resin having at least one repeating unit represented by the following general formulas (I) and (II), which is decomposed by the action of an acid and increases the solubility in an alkali developing solution: A positive resist composition comprising a compound capable of generating an acid upon irradiation with actinic rays or radiation and a solvent (C). Embedded image In the formulas (I) and (II), R ₁ and R ₅ may be the same or different and represent a hydrogen atom, a fluorine atom or an alkyl group which may have a substituent. R ₂ , R ₃ , R
₆ and R ₇ may be the same or different and include a hydrogen atom,
It represents a hydroxyl group, a halogen atom, a cyano group, or an optionally substituted alkoxy group, acyl group, alkyl group, alkenyl group, aralkyl group or aryl group. R ₄ represents an alkyl group, an acyl group or an alkoxycarbonyl group which may have a substituent. R ₃₀
Represents an alkyl group. Further, R ₄ and R ₃₀ may be bonded to each other to form a ring. 2. The positive resist composition according to claim 1, wherein R _{4 in the} general formula (I) is an alkyl group partially or wholly substituted by a fluorine atom. 3. The resin of (A) further comprises the following general formula (II)
Having at least one repeating unit represented by I)
The positive resist according to claim 1, wherein:
Composition. Embedded imageIn the general formula (III), R₈And R₉Are the same but different
Hydrogen atom, halogen atom, cyano group or
Represents an alkyl group which may have a substituent. R _TenIs the water
Elemental atom, halogen atom, and optionally substituted
Kill group or -A ₁Represents a —CN group. A₁Is a single bond, substituted
Divalent alkylene group which may have a group, alkenylene
Or an arylene group, or -O-CO-R₁₁−, −
CO-OR₁₂-, -CO-N (R₁₃) -R₁₄-
You. R₁₁, R₁₂And R₁₄Are the same or different
Well, single bond, or ether group, ester group, amide
Group, a urethane group or a ureido group,
Divalent alkylene group, alkenylene group or arylene group
Represent. R₁₃Represents a hydrogen atom, which may have a substituent,
Represents an alkyl group, an aralkyl group or an aryl group. 4. The resin of (A) further comprises a compound represented by the general formula (IV):
The positive resist composition according to any one of claims 1 to 3, wherein the composition has at least one repeating unit represented by (XI). Embedded image In the general formulas (IV) to (XI), R ₁₅ and R ₁₆ may be the same or different and represent a hydrogen atom, a fluorine atom, or an alkyl group or an aryl group which may have a substituent. R _{17 to} R ₁₉ may be the same or different and represent an alkyl group or an aryl group which may have a substituent. R ₁₅ and R ₁₆ , R ₁₅ and R ₁₇ , R ₁₈ and R ₁₉ are
It may combine with each other to form a ring. R ₂₀ represents a hydrogen atom, an alkyl group, an acyl group or an alkoxycarbonyl group which may have a substituent. R _21, R _22, and R
₂₃ represents the same or different, and represents a hydrogen atom, a halogen atom, or an alkyl group or an alkoxy group which may have a substituent. R ₂₄ represents a hydrogen atom, a halogen atom,
Represents a cyano group or an alkyl group which may have a substituent. R ₂₅ is an alkyl group which may have a substituent,
Represents an aralkyl group or an aryl group. B ₁ and B ₂ may be the same or different and may have a single bond, a substituent, a divalent alkylene group, an alkenylene group or an arylene group, or —O—CO—R ₂₆ —, —CO -OR ₂₇
— Or —CO—N (R ₂₈ ) —R ₂₉ —. R ₂₆ ,
R ₂₇ and R ₂₉ may be the same or different and may have a single bond or an ether group, an ester group, an amide group, a urethane group or a ureide group, and may have a divalent alkylene group, alkenylene group or arylene group. Represents R ₂₈ is
Represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group which may have a substituent. n represents 0 or 1. 5. The resin of (A) further comprises a compound of the general formula (XII)
The positive resist composition according to any one of claims 1 to 4, wherein the positive resist composition has at least one repeating unit represented by the formula: Embedded image In the general formula (XII), R ₃₁ and R ₃₂ may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R ₃₃ is -C
( _R34 ) ( _R35 ) ( _R36 ), -C ( _R34 ) ( _R35 ) (O
R ₃₇ ) or a group represented by the formula (XIII).
R _{34 to} R ₃₇ may be the same or different, and represent a hydrogen atom,
It represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group which may have a substituent. R ₃₄ , R
Two of R ₃₅ and R ₃₆ or two of R ₃₄ , R ₃₅ and R ₃₇ may combine to form a ring. A ₂ represents a single bond, a divalent alkylene group, an alkenylene group or an arylene group which may have a substituent, or —O—CO—R ₄₃ —,
_{CO-O-R 44 -,} - CO-N (R 45) -R 46 - represents a. R ₄₃ , R ₄₄ and R ₄₆ may be the same or different and may have a single bond or an ether group, an ester group, an amide group, a urethane group or a ureido group;
Represents a valent alkylene group, alkenylene group or arylene group. R ₄₅ may have a hydrogen atom or a substituent,
Represents an alkyl group, an aralkyl group or an aryl group. In the formula (XIII), R ₃₈ may have a substituent,
Represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group. Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with a carbon atom. Embedded image 6. The resin of (A) further comprises a compound of the general formula (XIV)
The positive resist composition according to any one of claims 1 to 5, wherein the positive resist composition has at least one repeating unit represented by the formula: Embedded image In the general formula (XIV), R ₃₉ , R ₄₀ and R ₄₁ may be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group, alkenyl group, Represents an aralkyl group, an aryl group or an alkoxy group. R ₄₂ represents an optionally substituted alkyl group, alkenyl group, aralkyl group or aryl group. n represents 0 or 1. 7. A compound represented by the following general formula (X) wherein R _{4 in the} general formula (I) is
The positive resist composition according to any one of claims 1 to 6, which is represented by V). Embedded image In the general formula (XV), X represents a hydrogen atom or a fluorine atom. n represents an integer of 0 to 3. m represents an integer of 0 to 10.