JP2003140349A - Positive resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive resist composition causing little problem relating to developing defects. SOLUTION: The positive resist composition is characterized in containing (A) a fluorine group-containing resin which has a structure substituted with a fluorine atom in the main chain and/or side chain of the polymer skeleton and which is decomposed by the effect of an acid to increase the solubility with an alkali developing liquid, (B) a compound which generates an acid by irradiation with active rays or radiation, and (D) a nitrogen-containing compound having at least one fluorine atom.

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 manufacturing of ultra-LSIs and high-capacity microchips, and other photofabrication processes. More specifically, it relates to a positive resist composition capable of forming a highly detailed pattern by using deep ultraviolet light of 180 nm or less.

[0002]

2. Description of the Related Art The degree of integration of integrated circuits is increasing more and more, and in the manufacture of semiconductor substrates such as VLSI, it has become necessary to process ultrafine patterns having a line width of less than quarter micron. It was As one of means for achieving a finer pattern, it is known to shorten the wavelength of an exposure light source used when forming a resist pattern.

For example, to manufacture a semiconductor device with an integration degree of up to 64 Mbits, up to now, the i-line (365n) of a high pressure mercury lamp has been used.
m) has been used as a light source. As a positive resist compatible with this light source, many compositions containing a novolac resin and a naphthoquinonediazide compound as a photosensitive material have been developed, and have achieved sufficient results in processing line widths up to about 0.3 μm. . Further, KrF excimer laser light (248 nm) has been adopted as an exposure light source instead of the i-line in the manufacture of a semiconductor device having an integration degree of 256 Mbits or more. Furthermore, for the purpose of manufacturing semiconductors with a degree of integration of 1 Gbit or more, the use of ArF excimer laser light (193 nm), which is a light source with a shorter wavelength in recent years, has a
The use of F2 excimer laser light (157 nm) for forming a pattern of m or less has been studied.

With the shortening of the wavelength of these light sources, the constituent components of the resist material and the compound structure thereof have changed greatly. That is, in the conventional resist containing a novolac resin and a naphthoquinonediazide compound, since absorption in the far ultraviolet region of 248 nm is large, it is difficult for light to reach the bottom of the resist, and only a tapered pattern with low sensitivity can be obtained. To solve such problems, 24
Composition in which a compound (photo-acid generator) that generates an acid by irradiation with far-ultraviolet light is used by using as a main component a resin that has a basic skeleton of poly (hydroxystyrene) having a small absorption in the 8 nm region and is protected by an acid-decomposing group. The thing, what is called a chemically amplified resist, came to be developed. Since the chemically amplified resist changes its solubility in a developing solution due to the catalytic decomposition reaction of the acid generated in the exposed portion, a highly sensitive and high resolution pattern can be formed.

However, when ArF excimer laser light (193 nm) is used, since the compound having an aromatic group essentially has a large absorption in the wavelength region of 193 nm, sufficient performance cannot be obtained even with the above chemically amplified resist. It was

To solve this problem, an acid-decomposable resin having a basic skeleton of poly (hydroxystyrene) is used as an acid-decomposable resin in which an alicyclic structure having no absorption at 193 nm is introduced into the polymer main chain or side chain. Instead, the chemically amplified resist is being improved.

However, with respect to the F2 excimer laser light (157 nm), the alicyclic resin also has a large absorption in the 157 nm region, which is 0.1 μm.
It was found to be insufficient to obtain the following pattern. On the other hand, a resin having a fluorine atom (perfluoro structure) introduced may have sufficient transparency at 157 nm.
Proc. SPIE. Vol. 3678. Reported on page 13 (1999), effective structure of fluororesin is Proc. SPIE. Vol. 3
999. 330 pages (2000), 357 pages (200)
0), p. 365 (2000), WO-00 / 1771.
No. 2, etc., it has been proposed, but even the resists containing these fluororesins were insufficient with respect to the problem of development defects.

[0008]

As described above, the known techniques of conventional photoresist compositions do not provide a stable pattern, and the problem of development defects is observed. Therefore, further improvement is desired. It was Therefore, the object of the present invention is
0 nm or less, especially F2 excimer laser light (157n
m) to provide a positive resist composition suitable for use with an exposure light source, and specifically to provide a positive resist composition in which the problem of development defects caused when using a 157 nm light source is improved. is there.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies with the above characteristics in mind. As a result, the above object was achieved by combining a specific acid-decomposable resin and a nitrogen-containing compound containing a fluorine atom. It was found that the present invention has led to the present invention. That is, the above object is achieved by the following configurations.

(1) (A) Main chain of polymer skeleton and /
Alternatively, a fluorine group-containing resin having a structure in which a fluorine atom is substituted in the side chain and having a group that decomposes by the action of an acid to increase the solubility in an alkali developing solution, (B) actinic ray or radiation, A positive resist composition containing a compound which generates a hydrogen atom, and (D) a nitrogen-containing compound containing at least one fluorine atom.

(2) The resin (A) has at least one site selected from a perfluoroalkylene group and a perfluoroarylene group in the main chain of the polymer skeleton, or a perfluoroalkyl group or a perfluoroaryl group. , A hexafluoro-2-propanol group, and a fluorine group-containing resin having at least one site selected from the group protecting the OH group of the hexafluoro-2-propanol group in the side chain of the polymer skeleton. The positive resist composition as described in (1) above, wherein

(3) The composition for exposure by far-ultraviolet light having a wavelength of 180 nm or less, (1)
Alternatively, the positive resist composition as described in (2).

The preferred embodiments will be described below. (4) The positive resist composition as described in any of (1) to (3) above, which further contains (E) a compound having a basic nitrogen atom as an acid diffusion inhibitor.

(5) The compound of the component (B) is a perfluoroalkylsulfonic acid having 2 or more carbon atoms, a perfluoroarylsulfonic acid, or an arylsulfone having a perfluoroalkyl group substituted by irradiation with actinic rays or radiation. The positive resist composition as described in any of (1) to (4) above, wherein the positive resist composition is selected from compounds of sulfonium salts or iodonium salts that generate an acid.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention are described in detail below. [(A) Component Fluorine Group-Containing Resin] The fluorine group-containing resin in the present invention (A) has a structure in which a fluorine atom is substituted in the main chain and / or side chain of the polymer, and decomposes by the action of an acid, A resin characterized by having a group that increases solubility in an alkaline developer, preferably having at least one site selected from a perfluoroalkylene group and a perfluoroarylene group in the main chain of the polymer skeleton, A site selected from a perfluoroalkyl group, a perfluoroaryl group, a hexafluoro-2-propanol group, and a group in which the OH group of the hexafluoro-2-propanol group is protected is attached to the side chain of the polymer skeleton. It is a resin containing at least one fluorine group.

Specifically, it is a resin having at least one repeating unit represented by the following general formulas (I) to (X).

[0017]

[Chemical 1]

In the general formula, R ₀ and R ₁ represent a hydrogen atom, a fluorine atom, or an optionally substituted alkyl group, perfluoroalkyl group, cycloalkyl group or aryl group. R _{2 to} R ₄ represent an alkyl group, a perfluoroalkyl group, a cycloalkyl group or an aryl group which may have a substituent. Also, R ₀ and R ₁ , R ₀ and R ₂ , R ₃
And R ₄ may combine to form a ring. R ₅ represents a hydrogen atom, an alkyl group which may have a substituent, a perfluoroalkyl group, a monocyclic or polycyclic cycloalkyl group, an acyl group or an alkoxycarbonyl group. R ₆ , R ₇ and R ₈ may be the same or different and each represent a hydrogen atom, a halogen atom or an alkyl group, a perfluoroalkyl group or an alkoxy group, which may have a substituent.

R ₉ and R _{10, which} may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group or a haloalkyl group which may have a substituent.
R ₁₁ and R ₁₂ may be the same or different and each is a hydrogen atom,
It represents a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group or an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. R ₁₃ and R ₁₄ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or a haloalkyl group which may have a substituent.

R ₁₅ is an alkyl group having a fluorine atom,
It represents a monocyclic or polycyclic cycloalkyl group, alkenyl group, aralkyl group or aryl group. R ₁₆ , R ₁₇ , R ₁₈
May be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group, or a substituent, an alkyl group, a perfluoroalkyl group, an alkoxy group, -CO-
Represents OR ₁₅ . R ₁₉ , R ₂₀ , and R ₂₁ may be the same or different and each is a hydrogen atom, a fluorine atom, an alkyl group having a fluorine atom, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, or Represents an alkoxy group. However, at least one of R ₁₉ , R ₂₀ , and R ₂₁ is a group other than a hydrogen atom.

A ₁ and A ₂ are a single bond, a divalent alkylene group which may have a substituent, an alkenylene group, a cycloalkylene group or an arylene group, or --O--CO--R _22.
-, - CO-O-R 23 -, - CO-N (R 24) -R 25 -
Represents R ₂₂ , R ₂₃ and R _{25, which} may be the same or different, are a single bond, or an ether group, an ester group, an amide group,
It represents a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group which may have a urethane group or an ureido group. R ₂₄ represents a hydrogen atom, or an optionally substituted alkyl group, cycloalkyl group, aralkyl group or aryl group. n represents 0 or 1,
x, y, z represent the integer of 0-4.

In the present invention, the resin (A) is preferably a fluorine group-containing resin having an acid-decomposable group having at least one repeating unit represented by the following general formulas (XI) to (XIII).

[0023]

[Chemical 2]

In the formula, R ₂₆ , R ₂₇ and R ₃₂ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group or a haloalkyl group which may have a substituent. R ₂₈ and R ₃₃ are -C (R ₃₆ ) (R ₃₇ )
(R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), or a group represented by general formula (XIV) shown below.

[0025]

[Chemical 3]

In the formula, R ₂₉ , R ₃₀ , and R ₃₁ may be the same or different, and are a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, a perfluoroalkyl group, It represents an alkoxy group, -CO-OR ₂₈ .

R₃₄, R₃₅Can be the same or different
Hydrogen atom, hydroxyl group, halogen atom, cyano
Having a group, an alkoxy group, an acyl group, or a substituent
Good, alkyl group, cycloalkyl group, alkenyl
Represents a group, an aralkyl group or an aryl group. R₃₆, R
₃₇, R₃₈, R₃₉May be the same or different, and the substituents
Which may have an alkyl group, a cycloalkyl group,
Alkenyl group, alkynyl group, aralkyl group or
Represents a reel group. R₃₆, R₃₇, R₃₈2 out of, or R
₃₆, R ₃₇, R₃₉Two of them may combine to form a ring
Yes. In addition, the ring formed contains an oxo group
Good. R₄₀Is an optionally substituted alkyl
Group, cycloalkyl group, alkenyl group, alkynyl group,
Represents an aralkyl group or an aryl group.

A _{3 to} A ₄ are a single bond, a divalent alkylene group which may have a substituent, an alkenylene group, a cycloalkylene group or an arylene group, or --O--CO--R _22.
-, - CO-O-R 23 -, - CO-N (R 24) -R 25 -
Represents R _{22 to} R ₂₅ have the same meaning as above. Z represents an atomic group forming a monocyclic or polycyclic alicyclic group together with a carbon atom. n represents 0 or 1.

Further, in the present invention, in order to control the physical properties such as hydrophilicity / hydrophobicity of the fluorine group-containing resin, glass transition point, and transmittance to exposure light, or to control the polymerizability at the time of polymer synthesis, It may have at least one repeating unit derived from a maleic anhydride represented by (XV) to (XVII), a vinyl ether or a vinyl compound containing a cyano group.

[0030]

[Chemical 4]

In the formula, R ₄₁ may have a substituent,
It represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. R ₄₂ represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group or haloalkyl group. A ₅ represents may have a single bond, a substituent, a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group, or -O-CO-R
_{22 -, - CO-O-} R 23 -, - CO-N (R 24) -R 25
Represents-. R _{22 to} R ₂₅ have the same meaning as above.

Further, as the more preferred fluorine group-containing resin (A) in the present invention, the following general formulas (IA) and (I
A resin having at least one repeating unit represented by formula (IA), and the following general formulas (IIA) and (VIA)
Examples of the resin include at least one repeating unit represented by: The following general formula (IA)
And a resin having at least one repeating unit represented by (IIA), and at least one repeating unit represented by the following general formulas (IIA) and (VIA).
The resin (A) having one of the general formulas (I) to (V)
You may have the repeating unit shown by.

[0033]

[Chemical 5]

[0034]

[Chemical 6]

In formulas (IA) and (IIA), R _1a and R _{5a, which} may be the same or different, each represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. Represent R _2a , R _3a , R _6a and R _7a may be the same or different and may have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group or a substituent,
It represents an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, an alkenyl group, an aryl group or an aralkyl group. R _50a to R _55a may be the same or different, represent a hydrogen atom, an alkyl group which may have a fluorine atom or a substituent. However, at least one of R _{50a to} R _55a represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. R _56a represents a hydrogen atom or an alkyl group, a cycloalkyl group, an acyl group or an alkoxycarbonyl group which may have a substituent, and is preferably a hydrogen atom. R _4a is the following general formula (IVA) or (VA)
Represents the group of.

[0036]

[Chemical 7]

In the general formula (IVA), R _11a , R _12a and R
_13a may be the same or different and represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, which may have a substituent. General formula (V
In A), R _14a and R _{15a, which} may be the same or different, each represents a hydrogen atom or an alkyl group which may have a substituent. R _16a represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a substituent. Two of R _{14a to} R _16a may combine with each other to form a ring.

[0038]

[Chemical 8]

In the general formula (VIA), R _17a1 and R _17a1
17a2 may be the same or different and represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. R _18a is -C (R _18a1 ) (R _18a2 )
(R _18a3 ) or -C (R _18a1 ) (R _{18a 2} ) (OR _18a4 )
Represents R _{18a1 to} R _18a4 may be the same or different and each represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, which may have a hydrogen atom or a substituent. _Two of R _18a1 , R _18a2 and R _18a3 or two of R _18a1 , R _18a2 and R _18a4 may combine to form a ring. A ₀ represents a single bond or a divalent linking group which may have a substituent, and it is preferably a single bond.

In these fluorine group-containing resins (A), R _18a in the general formula (VIA) is preferably a group represented by the following general formula (VIA-A) or general formula (VIA-B). . Further, in these fluorine group-containing resins (A), at least one of R _1a in the general formula (IA), R _5a in the general formula (IIA) and R _{17a2 in} the general formula (VIA) is trifluoromethyl. It is preferably a group.

[0041]

[Chemical 9]

[0042]

[Chemical 10]

In the general formula (VIA-A), R _18a5 and R _18a5
18a6 may be the same or different and represents an alkyl group which may have a substituent. R _18a7 represents a cycloalkyl group which may have a substituent.

In formula (VIA-B), R _18a8 represents an _optionally substituted alkyl group, alkenyl group, alkynyl group, aralkyl group or aryl group.

Further, the above general formulas (IA) and (IIA)
The resin having at least one repeating unit represented by and the resin (A) having at least one repeating unit represented by the general formulas (IIA) and (VIA) each have the following general formula (IIIA) or ( VII
It may have at least one repeating unit represented by A).

[0046]

[Chemical 11]

In formula (IIIA), R _8a represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. R _9a and R _10a may be the same or different and each may have a hydrogen atom, a halogen atom, a cyano group or a substituent, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, It represents an alkenyl group, an aryl group or an aralkyl group.
In formula (VIIA), R _19a and R _{20a, which} may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. R
_21a represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group or -A ₁ -CN group. A ₁ represents a single bond or a divalent linking group.

The above alkyl group has, for example, 1 carbon atom.
~ 8 alkyl groups, specifically, a methyl group,
Preferable examples include ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group and octyl group. The cycloalkyl group may be monocyclic or polycyclic. The monocyclic type has 3 to 8 carbon atoms, and preferred examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The polycyclic type has 6 to 20 carbon atoms,
Preferred examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camfanyl group, a dicyclopentyl group, an a-pinel group, a tricyclodecanyl group, a tetracyclododecyl group and an androstanyl group. However, the carbon atom in the above monocyclic or polycyclic cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The perfluoroalkyl group is, for example, one having 4 to 12 carbon atoms, specifically, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perfluorooctylethyl group, perfluoro. Dodecyl group and the like can be preferably mentioned. The haloalkyl group is, for example, a haloalkyl group having 1 to 4 carbon atoms, and specific examples thereof include a chloromethyl group, a chloroethyl group, a chloropropyl group, a chlorobutyl group, a bromomethyl group and a bromoethyl group.

The aryl group has, for example, 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-
Preferred examples thereof include a dimethoxyanthryl group. The aralkyl group is, for example, an aralkyl group having a carbon number of 7 to 12, and specific examples thereof include a benzyl group, a phenethyl group and a naphthylmethyl group. The alkenyl group is, for example, an alkenyl group having a carbon number of 2 to 8, and specific examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

The alkoxy group has, for example, 1 to 1 carbon atoms.
Of the eight alkoxy groups, specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a butoxy group, a pentoxy group, an allyloxy group and an octoxy group. As the acyl group, for example, an acyl group having 1 to 10 carbon atoms, specifically, formyl group, acetyl group, propanoyl group, butanoyl group, pivaloyl group, octanoyl group,
A benzoyl group and the like can be preferably mentioned. As the acyloxy group, an acyloxy group having 2 to 12 carbon atoms is preferable, for example, an acetoxy group, a propionyloxy group,
A benzoyloxy group etc. can be mentioned. The alkynyl group is preferably an alkynyl group having 2 to 5 carbon atoms, and examples thereof include an ethynyl group, a propynyl group and a butynyl group. Examples of the alkoxycarbonyl group include i-propoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, 1-methyl-1.
-Cyclohexyloxycarbonyl group and the like, preferably 2
And more preferably a tertiary alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom,
Examples thereof include chlorine atom, bromine atom and iodine atom.

As the alkylene group, those having 1 to 8 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group which may have a substituent are preferable. As the alkenylene group, those having 2 to 6 carbon atoms such as an ethenylene group, a propenylene group and a butenylene group which may have a substituent are preferable. As the cycloalkylene group, those having 5 to 8 carbon atoms such as a cyclopentylene group which may have a substituent and a cyclohexylene group are preferable. The arylene group is preferably an arylene group having a carbon number of 6 to 15, such as a phenylene group which may have a substituent, a tolylene group and a naphthylene group.

The divalent linking group means a divalent alkylene group, cycloalkylene group, alkenylene group or arylene group which may have a substituent, or -O-CO-R.
_22a -,-CO-OR- _23a -or-CO-N (R
_24a) -R _25a - represents a. R _22a , R _23a and R _{25a, which} may be the same or different, 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, It represents an alkenylene group, a cycloalkylene group or an arylene group. R _24a represents a hydrogen atom or an optionally substituted alkyl group, cycloalkyl group, aralkyl group or aryl group.

The ring formed by combining R ₀ and R ₁ , R ₀ and R ₂ , and R ₃ and R ₄ is, for example, a 5- to 7-membered ring, specifically, a pentane ring substituted with fluorine, Examples thereof include a hexane ring, a furan ring, a dioxonol ring, and a 1,3-dioxolane ring. Two of R _{36 to} R ₃₈ , or R _{36 to} R ₃₇ and R
A ring formed by combining two of ₃₉ is, for example, 3
To 8 membered rings, and specific examples thereof include a cyclopropane ring, a cyclopentane ring, a cyclohexane ring, a furan ring and a pyran ring.

R_14a~ R_16aTwo of the, R_18a1~ R_18a3
2 of or R_18a1, R_18a2, R _18a4Two of the
The ring formed by combining is preferably a 3- to 8-membered ring, examples
For example, cyclopropane ring, cyclopentane ring, cyclohexene
Sun ring, tetramethylene oxide ring, pentamethylene
Xide ring, hexamethylene oxide ring, furan ring, pyra
Ring, dioxonol ring, 1,3-dioxolane ring, etc.
Can be mentioned.

Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group, and the alicyclic group formed is a monocyclic group having 3 to 8 carbon atoms, for example, A cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group can be preferably mentioned. The polycyclic type has 6 to 20 carbon atoms, and includes, for example, 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.

Substituents substituted by these groups have active hydrogen such as alkyl group, cycloalkyl group, aryl group, amino group, amide group, ureido group, urethane group, hydroxyl group and carboxyl group. Or halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.) ), An acyloxy group (acetoxy group, propanoyloxy group, benzoyloxy group, etc.), an alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc.), a cyano group, a nitro group and the like. Here, examples of the alkyl group, cycloalkyl group, and aryl group include those described above, and the alkyl group is
Further, it may be substituted with a fluorine atom or a cycloalkyl group.

The group contained in the fluorine group-containing resin of the present invention, which is decomposed by the action of an acid to be alkali-soluble, is
For example _{-O-C (R 36) (} R 37) (R 38), - O-C
_{(R 36) (R 37)} (OR 39), - O-COO-C
( _R36 ) ( _R37 ) ( _R38 ), -OC ( _R01 ) ( _R02 )
COO-C ( _R36 ) ( _R37 ) ( _R38 ), -COO-C
(R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -COO-C (R ₃₆ ) (R
₃₇ ) (OR ₃₉ ) and the like. R _{36 to} R ₃₉ have the same meanings as described above, and R ₀₁ and R ₀₂ are each a hydrogen atom, an alkyl group which may have a substituent shown above, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group. Represents

A preferred specific example is 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)
Ether group or ester group of tertiary alkyl group such as 2-propyl group, acetal group or acetal ester group such as 1-alkoxy-1-ethoxy group, tetrahydropyranyl group, t-alkyl carbonate group, t-alkylcarbonyl A methoxy group and the like are preferable.

The total content of the repeating units represented by the general formulas (I) to (X) is generally 10 to 80 mol%, preferably 30 to 70 mol%, in the total polymer composition.
More preferably, it is used in the range of 35 to 65 mol%.
The content of the repeating units represented by the general formulas (XI) to (XIII) is generally 0 to 70 mol%, preferably 10 to 60 mol%, more preferably 20 in the total polymer composition.
It is used in the range of 50 mol%. General formula (XV) ~ (XV
The content of the repeating unit represented by II) is generally 0 to 70 mol%, preferably 10 in the total polymer composition.
-60 mol%, more preferably 20-50 mol% is used.

The resin (A) of the present invention has at least one repeating unit represented by the general formulas (I) to (III) and at least one repeating unit represented by the general formulas (IV) to (VI). It is more preferable to have one. Also,
Examples of the resin (A) of the present invention include those represented by general formulas (IV) to (VI)
It is more preferable to have at least one repeating unit represented by and at least one repeating unit represented by the general formulas (VIII) to (X), as in the above.

Further, the resin (A) of the present invention comprises at least one repeating unit represented by the general formulas (IV) to (VII) and repeating units represented by the general formulas (XV) to (XVII). It is more preferable to have at least one similarly to the above. As a result, it is possible to sufficiently enhance the transmittance of the resin at 157 nm and suppress the deterioration of the dry etching resistance.

The resin (A) of the present invention has the general formula (I) to
At least one repeating unit represented by (III),
When it has at least one repeating unit represented by general formulas (IV) to (VI), the total content of repeating units represented by general formulas (I) to (III) is 0 to 70 mol%, preferably 10 to 6
It is used in an amount of 0 mol%, more preferably 20 to 50 mol%. The total content of the repeating units represented by formulas (IV) to (VI) is generally 10 to 80 mol%, preferably 30 to 70 mol%, more preferably 35 to 65 mol% in the total polymer composition. Used in the mol% range.

The resin (A) of the present invention has the general formula (IV)
In the case of having at least one repeating unit represented by (VI) and at least one repeating unit represented by general formulas (VIII) to (X), the repeating units represented by general formulas (IV) to (VI) The total content is generally 10 to 80 mol%, preferably 30 to 7 in the total polymer composition.
It is used in an amount of 0 mol%, more preferably 35 to 65 mol%. The total content of the repeating units represented by formulas (VIII) to (X) is generally 0 to 70 mol%, preferably 10 to 60 mol%, more preferably 20 to 50 in the total polymer composition. Used in the mol% range.

The resin (A) of the present invention has the general formula (IV)
At least one repeating unit represented by (VII),
When it has at least one repeating unit represented by general formulas (XV) to (XVII), the total content of repeating units represented by general formulas (IV) to (VII) is 10 to 80 mol%, preferably 30
˜70 mol%, more preferably 35 to 65 mol%. The total content of the repeating units represented by the general formulas (XV) to (XVII) is, in the total polymer composition,
Generally, it is used in the range of 0 to 70 mol%, preferably 10 to 60 mol%, and more preferably 20 to 50 mol%.

In the fluorine group-containing resin (A) having at least one repeating unit represented by the general formulas (IA) and (IIA), the content of the repeating unit represented by the general formula (IA) is generally 5 to 80 mol%, preferably 10 to 75 mol%, and more preferably 20 to 70 mol%. In the fluorine group-containing resin (A) having at least one repeating unit represented by the general formulas (IA) and (IIA), the content of the repeating unit represented by the general formula (IIA) is generally 5 to 5. 80 mol%, preferably 1
It is 0 to 70 mol%, more preferably 20 to 65 mol%. In the fluorine group-containing resin (A) having at least one repeating unit represented by the general formulas (IIA) and (VIA), the content of the repeating unit represented by the general formula (IIA) is generally 5 to 80 mol%, preferably 1
It is 0 to 70 mol%, more preferably 20 to 65 mol%. In the fluorine group-containing resin (A) having at least one repeating unit represented by the general formulas (IIA) and (VIA), the content of the repeating unit represented by the general formula (VIA) is generally 5 to 80 mol%, preferably 1
It is 0 to 70 mol%, more preferably 20 to 65 mol%. In the fluorine group-containing resin (A), the content of the repeating unit represented by the general formula (IIIA) is generally 1 to 40 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%. Mol%. In these fluorine group-containing resins (A), the content of the repeating unit represented by the general formula (VIIA) is generally 1 to 40 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%. Mol%.

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

Copolymerizable monomers that can be used include those shown below. For example, addition-polymerizable unsaturated bonds selected from acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters, etc. other than the above It is a compound having one.

Specifically, for example, acrylates such as alkyl (wherein the alkyl group has 1 to 1 carbon atoms).
0 acrylate) (eg, methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate) , Chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2
-Dimethyl hydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) Aryl acrylate (eg phenyl acrylate etc.);

Methacrylic acid esters, for example, alkyl (alkyl groups preferably having 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate,
Amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
Chlorbenzyl 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 (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.);

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

Methacrylamides such as methacrylamide and N-alkylmethacrylamide (wherein the alkyl group has 1 to 10 carbon atoms, for example, methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group). Group, cyclohexyl group, etc.), N
-Aryl methacrylamide (an aryl group includes a phenyl group, etc.), N, N-dialkyl methacrylamide (an alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N, N-diaryl. Methacrylamide (such as a phenyl group as an aryl group), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide, etc .;
Allyl compounds, such as allyl esters (eg, 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 ether (eg vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-
2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate. , Vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl-β-
Phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc .;

Styrenes such as styrene, alkylstyrenes (eg methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethyl). Styrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene). , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromstyrene, dibromostyrene, iodostyrene, fluoros Ren, trifluoromethyl styrene, 2
-Bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), carboxystyrene, vinylnaphthalene;

Crotonic acid esters, for example, alkyl crotonic acid (eg, butyl crotonic acid, hexyl crotonic acid, glycerin monocrotonate, etc.); Dialkyl itaconic acids (eg, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc.) ); Dialkyl esters of maleic acid or fumaric acid (eg,
Dimethyl maleate, dibutyl fumarate, etc.), maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleironitrile and the like. In addition, any addition-polymerizable unsaturated compound that is generally copolymerizable may be used.

Specific examples of the repeating structural units represented by formulas (I) to (X) are shown below, but the invention is not limited thereto.

[0078]

[Chemical 12]

[0079]

[Chemical 13]

[0080]

[Chemical 14]

[0081]

[Chemical 15]

[0082]

[Chemical 16]

[0083]

[Chemical 17]

[0084]

[Chemical 18]

Specific examples of the repeating structural units represented by formulas (XI) to (XIII) are shown below, but the invention is not limited thereto.

[0086]

[Chemical 19]

[0087]

[Chemical 20]

[0088]

[Chemical 21]

[0089]

[Chemical formula 22]

Specific examples of the repeating structural units represented by formulas (XVI) to (XVII) are shown below, but the invention is not limited thereto.

[0091]

[Chemical formula 23]

Specific examples of the repeating structural unit represented by formula (IA) are shown below, but the invention is not limited thereto.

[0093]

[Chemical formula 24]

[0094]

[Chemical 25]

[0095]

[Chemical formula 26]

[0096]

[Chemical 27]

[0097]

[Chemical 28]

[0098]

[Chemical 29]

[0099]

[Chemical 30]

[0100]

[Chemical 31]

[0101]

[Chemical 32]

Specific examples of the repeating structural unit represented by formula (IIA) are shown below, but the invention is not limited thereto.

[0103]

[Chemical 33]

[0104]

[Chemical 34]

[0105]

[Chemical 35]

[0106]

[Chemical 36]

Further, as specific examples of the repeating unit represented by the general formula (IIA), (F-40) to (F-40) mentioned above are exemplified.
(F-45) can be mentioned.

Specific examples of the repeating structural unit represented by formula (VIA) are shown below, but the invention is not limited thereto.

[0109]

[Chemical 37]

[0110]

[Chemical 38]

[0111]

[Chemical Formula 39]

[0112]

[Chemical 40]

[0113]

[Chemical 41]

Further, as specific examples of the repeating unit represented by the general formula (VIA), (F-29) to (F) mentioned above are exemplified.
-38) and (F-47) to (F-54).

Specific examples of the repeating structural unit represented by formula (IIIA) are shown below, but the invention is not limited thereto.

[0116]

[Chemical 42]

[0117]

[Chemical 43]

Specific examples of the repeating structural unit represented by formula (VIIA) are shown below, but the invention is not limited thereto.

[0119]

[Chemical 44]

The repeating structural units represented by the above specific examples may be used alone or in combination of two or more. The preferred molecular weight of the resin (A) of the present invention having the repeating structural unit is 1,000 to 2 on a weight average basis.
0,000, and more preferably 3,000 to 2
Used in the range of 10,000. Molecular weight distribution is 1-10
And preferably 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 wall of the resist pattern are smooth, and the roughness is excellent.

The addition amount of the resin (A) of the present invention is generally 50 to 100% by weight, preferably 60 to 98% by weight, more preferably 65 to 95% by weight based on the total solid content of the composition.
Used in the weight% range.

[Component (B) Compound that Generates Acid upon Irradiation with Actinic Rays or Radiation (hereinafter sometimes referred to as photoacid generator)] In the composition of the present invention, actinic ray or It contains a compound (photoacid generator) that generates an acid upon irradiation with radiation. 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.

Also, a group in which an acid-generating group upon irradiation with actinic rays or radiation or a compound is introduced into the main chain or side chain of a polymer, 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 and European Patent 126,712 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).

[0128]

[Chemical formula 45]

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 include the compounds shown below, but the invention is not limited thereto.

[0134]

[Chemical formula 46]

[0135]

[Chemical 47]

[0136]

[Chemical 48]

[0137]

[Chemical 49]

[0138]

[Chemical 50]

[0139]

[Chemical 51]

[0140]

[Chemical 52]

[0141]

[Chemical 53]

[0142]

[Chemical 54]

[0143]

[Chemical 55]

[0144]

[Chemical 56]

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. Can be synthesized by the method described in No.

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

[0147]

[Chemical 57]

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.

[0149]

[Chemical 58]

[0150]

[Chemical 59]

[0151]

[Chemical 60]

[0152]

[Chemical formula 61]

[0153]

[Chemical formula 62]

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

[0155]

[Chemical formula 63]

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.

[0157]

[Chemical 64]

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

[0159]

[Chemical 65] In 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 at least two or more of R _{1 to} R ₅ are It may combine with each other 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 ⁻ 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 at least one of R ₆ or R ₇ are combined. To form a ring. In addition, R ₁
To R ₇ or any of Y ₁ or Y ₂ via a linking group to form a structure of formula (I)
You may have one or more.

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 for 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-mentioned 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 alkyl sulfonate 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, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a 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.

Other non-nucleophilic anions include, for example, 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 combined to form a ring, or a ring of 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).

[0176]

[Chemical formula 66]

In the 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.

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

[0181]

[Chemical formula 67]

[0182]

[Chemical 68]

[0183]

[Chemical 69]

[0184]

[Chemical 70]

[0185]

[Chemical 71]

[0186]

[Chemical 72]

[0187]

[Chemical formula 73]

[0188]

[Chemical 74]

[0189]

[Chemical 75]

Specific examples of the acid generator represented by the above general formula (I) include (IA-1) to (IA-30) and (I).
B-1) to (IB-12) are more preferable.

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

The content of the compound of the component (B) in the positive resist composition of the present invention is based on the solid content of the composition.
0.1 to 20% by weight is preferable, and 0.5 is more preferable.
10 to 10% by weight, more preferably 1 to 7% by weight.

Among the compounds (B) which generate an acid upon irradiation with actinic rays or radiation used in the present invention, particularly preferable examples are shown below.

[0194]

[Chemical 76]

[0195]

[Chemical 77]

[0196]

[Chemical 78]

[0197]

[Chemical 79]

[Component (D) Nitrogen-containing compound containing at least one fluorine atom] (hereinafter sometimes simply referred to as nitrogen-containing compound) The positive resist composition of the present invention comprises (D) at least one compound, It preferably contains a nitrogen-containing compound containing 1 to 30 fluorine atoms.

The nitrogen-containing compound is not limited as long as it contains at least one fluorine atom at any position in the molecule, and the position of the fluorine atom is directly bonded to the main skeleton. Or may be attached to a side chain.

Examples of the nitrogen-containing compound of the component (D) of the present invention include the compounds shown below, but the present invention is not limited thereto.

[0201]

[Chemical 80]

These nitrogen-containing compounds may be used alone or in combination with 2.
A combination of two or more species can be used. The amount of the nitrogen-containing compound (D) used is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content of the positive resist composition. If it is too small, the effect of adding the nitrogen-containing compound is not sufficient, while if it is too large, the sensitivity tends to decrease and the developability of the unexposed area tends to deteriorate.

[Component (C) Fluorine-based and / or Silicon-based Surfactant] The positive resist composition of the present invention comprises:
(C) Fluorine-based and / or silicon-based surfactant may be contained. That is, the positive resist composition of the present invention contains at least one of a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom, or two or more thereof. You can Addition of these fluorine-based and / or silicon-based surfactants is effective in suppressing development defects and improving coating properties.

Examples of these surfactants include JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-62-170950.
JP-A-63-34540, JP-A-7-23016
No. 5, JP-A-8-62834, and JP-A-9-54432.
U.S. Pat. No. 5,405,720.
No. 5,360,692, No. 55298881, No. 52
No. 96330, No. 5436098, No. 5576143.
Nos. 5,294,511 and 5,824,451 can be mentioned, and the following commercially available surfactants can be used as they are. Examples of commercially available surfactants that can be used include Ftop EF301 and EF30.
3, (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 43
1 (Sumitomo 3M Limited), Megafac F171, F
173, F176, F189, R08 (manufactured by Dainippon Ink and Chemicals, Inc.), Surflon S-382, SC101, 10
2, 103, 104, 105, 106 (Asahi Glass Co., Ltd.
Manufactured by Troy Sol S-366 (Troy Chemical Co., Ltd.)
Fluorine-based surfactants or silicon-based surfactants. Also polysiloxane polymer K
P-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the silicon-based surfactant.

When a surfactant is contained, its content is usually 0.00 based on the solid content in the composition of the present invention.
It is 1% to 2% by weight, preferably 0.01% to 1% by weight. These surfactants may be added alone or in some combinations.

[Component (E) Acid Diffusion Inhibitor] In the composition of the present invention, the performance variation (T-top shape formation of the pattern, sensitivity variation, pattern of the pattern) with time after irradiation with actinic rays or radiation until heat treatment is performed. Addition of an acid diffusion inhibitor for the purpose of preventing fluctuations in line width, etc.) and performance fluctuations with time after coating, and excessive acid diffusion (deterioration in resolution) during heat treatment after irradiation with actinic rays or radiation. Preferably. The acid diffusion inhibitor is an organic basic compound, for example, an organic basic compound containing basic nitrogen, and p of the conjugate acid is used.
A compound having a Ka value of 4 or more is preferably used. Specifically, the structures of the following formulas (A) to (E) can be mentioned.

[0207]

[Chemical 81]

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aminoalkyl group having 1 to 10 carbon atoms, or 1 carbon atom. 10 hydroxyalkyl groups or 6 to 6 carbon atoms
It represents 20 substituted or unsubstituted aryl groups, wherein R ²⁵¹ and R ²⁵² may combine with each other to form a ring. R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ^{256, which} may be the same or different, each represents an alkyl group having 1 to 10 carbon atoms.
More preferable compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, or aliphatic tertiary amines.

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 Alternatively, unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine 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.

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, 2 , 4,5-Triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2
-(Aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4 -Aminoethylpyridine,

3-aminopyrrolidine, piperazine, N-
(2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-
Iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole,
5-amino-3-methyl-1-p-tolylpyrazole,
Pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6
-Dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine and the like, but not limited thereto. These nitrogen-containing basic compounds may be 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. If the molar ratio is less than 2.5, the sensitivity may be low and the resolution may be lowered. If the molar ratio is more than 300, the resist pattern may become thicker with the lapse of time after the post-exposure heat treatment, and the resolution may be lowered. . The (acid generator) / (organic basic compound) (molar ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.

[Other Components Used in the Composition of the Present Invention] (1) Solvents The composition of the present invention is dissolved in a solvent that dissolves each of the above components and applied onto a support. As the solvent used here,
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, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc. Are preferred, and these solvents are used alone or as a mixture.

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

The developer for the positive resist composition of the present invention includes sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, ethylamine, n-propylamine. Primary amines such as diethylamine, di-
Secondary amines such as n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and primary amines such as choline. An aqueous solution of alkali such as quaternary ammonium salt, cyclic amines such as pyrrole and piperidine, and the like can be used. Furthermore, alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants may be added to the aqueous solution of the above alkalis in appropriate amounts. Of these developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and choline are more preferable.

The resist composition of the present invention may be a composition for any exposure source, but especially 180
A composition for exposure by far ultraviolet light having a wavelength of nm or less is preferable.

[0217]

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

[Synthesis Example 1] 9.4 g (0.10 mol) of norbornene and norbornene-2 in a 1 L autoclave.
-Carboxylic acid t-butyl ester 19.4 g (0.10
Mol) of 1,1,2-trichloro-trifluoroethylene in 150 ml, and the pressure was increased to 200 psi under a nitrogen atmosphere. Furthermore, 20 g of tetrafluoroethylene (0.2
0 mol) was added and heated to 50 ° C. with stirring. A solution of 1.2 g of di (4-t-butylcyclohexyl) peroxydicarbonate in 15 ml of 1,1,2-trichloro-trifluoroethylene was added to this reaction solution over 20 minutes, and stirring was continued for another 20 hours. After completion of the reaction, the reaction solution was poured into 2 L of methanol with vigorous stirring to precipitate a white resin. The precipitated resin was separated by filtration and dried under vacuum to obtain 23.5 g of Resin (1) of the present invention. According to GPC measurement, the molecular weight of the resin (1) is 6, in terms of weight average (Mw).
It was 200. Moreover, when the composition of the resin (1) was examined by C ¹³ -NMR measurement, a structural example (F-
1) / norbornene / (B-16) = 45/30/25
Met.

[Synthesis Example 2] Monomer (a) 14.3 shown below
g (0.04 mol), maleic anhydride 3.9 g (0.0
4 mol), t-butyl acrylate 2.6 g (0.02
Mol) in 100 ml of MEK, and under a nitrogen stream, 70
Heated to ° C. 0.2 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a polymerization initiator, and the mixture was stirred for 3 hours. Further, 0.2 g of V-601 was added, and stirring was continued for 4 hours.
Then, the reaction solution was poured into 1 L of t-butyl methyl ether with vigorous stirring to precipitate a white resin. The precipitated resin is separated by filtration and dried under vacuum, and then the resin (2) of the present invention
12.1 g was obtained. The weight average molecular weight (Mw) of the resin (2) was 8,900 by GPC measurement. Also C
^When the composition of the resin (2) was examined by ^13- NMR measurement, a structural example (F-21) / maleic anhydride / molar ratio was obtained.
(B-4) = 39/38/23.

[0220]

[Chemical formula 82]

[Synthesis Example 3] 6.7 g of the following monomer (b)
(0.015 mol), 2-methyl-2-adamantanemethacrylate 1.4 g (0.006 mol), mevalonic lactone methacrylate 1.8 g (0.009 mol)
Is dissolved in 30 ml of 1-methoxy-2-propanol,
Polymerization initiator 2,2'- at 70 ° C under nitrogen stream and stirring
Azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd .; trade name V-65) 0.1 g and monomer (b) 15.6 g (0.035 mol), 2-methyl-2
-Adamantane methacrylate 3.3 g (0.014 mol), mevalonic lactone methacrylate 4.2 g
A solution of (0.021 mol) in 1-methoxy-2-propanol (70 ml) was added dropwise over 2 hours. After 2 hours, 0.1 g of an initiator was added, and the reaction was further performed for 2 hours. Then 9
The temperature was raised to 0 ° C. and stirring was continued for 1 hour. After allowing the reaction solution to cool, it was poured into 1 L of ion-exchanged water / methanol (1/1) with vigorous stirring to precipitate a white resin. After drying the obtained resin under reduced pressure, the resin (3) 1 of the present invention
5.8 g was obtained. When the molecular weight was measured by GPC,
The weight average (Mw) was 10,200. Also C ¹³ −
When the composition of the resin (3) was examined by NMR measurement,
Structural example (F-30) / (B-7) / (B-1 in molar ratio
1) = 48/21/31.

[0222]

[Chemical 83]

[Synthesis Examples 4 to 12] [Table 1]
The resin of the present invention (A) shown in was synthesized.

[0224]

[Table 1]

[Synthesis Example 13] 150 ml of 1,1,2-trichloro-trifluoroethylene containing 9.4 g (0.10 mol) of norbornene and 35.8 g (0.10 mol) of the following monomer (a) in a 1 L autoclave. Add the solution,
Pressurized to 200 psi under a nitrogen atmosphere. Further, 20 g (0.20 mol) of tetrafluoroethylene was injected, and the mixture was heated to 50 ° C with stirring. 1.2 g of di (4-t-butylcyclohexyl) peroxydicarbonate was added to the reaction solution.
1,1,2-trichloro-trifluoroethylene 15
The ml solution was injected over 20 minutes and stirring was continued for another 20 hours. After completion of the reaction, the reaction solution was poured into 2 L of methanol with vigorous stirring to precipitate a white resin. The precipitated resin is separated by filtration and dried under vacuum, and then the resin (13) 3 of the present invention
7.4 g was obtained. According to GPC measurement, the molecular weight of the resin (13) was 8,800 in weight average (Mw). Also C
^When the composition of the resin (13) was examined by ^13- NMR measurement, it was Structural Example (F-1) / (F-21) / norbornene = 48/30/22 in molar ratio.

[0226]

[Chemical 84]

[Synthesis Example 14] 32.2 g of the following monomer (c) was used instead of the monomer (a) of Synthesis Example 13.
(0.04 mol) was used in the same manner as in Synthesis Example 13 to synthesize 34.1 g of the resin (14) of the present invention. GP
According to C measurement, the molecular weight of the resin (14) is a weight average (M
It was 7,400 in w). Moreover, when the composition of the resin (14) was examined by C ¹³ -NMR measurement, a structural example (F-1) / (F-15) / norbornene = 49/2 was obtained in a molar ratio.
It was 5/26.

[0228]

[Chemical 85]

[Synthesis Examples 15 to 22] The resins of the present invention (A) shown in Table 2 were synthesized in the same manner.

[0230]

[Table 2]

Synthesis Example 23 Monomer (a) 14.
3 g (0.04 mol), maleic anhydride 3.9 g (0.
04 mol) and 11.7 g (0.02 mol) of perfluorooctylethyl norbornene-2-carboxylate in MEK
It was dissolved in 100 ml and heated to 70 ° C. under a nitrogen stream.
As a polymerization initiator, V-601 (Wako Pure Chemical Industries, Ltd.)
0.2 g) was added and the mixture was stirred for 3 hours. Further V-601
0.2 g was added and stirring was continued for 4 hours. Then, the reaction solution was poured into 1 L of t-butyl methyl ether with vigorous stirring to precipitate a white resin. The precipitated resin was separated by filtration and dried under vacuum, and then 16.2 g of the resin (23) of the present invention
Got The weight average molecular weight (Mw) of the resin (23) was 8,700 as measured by GPC. Also C ¹³ -NM
When the composition of the resin (23) was examined by R measurement, it was Structural Example (F-21) / (F-55) / maleic anhydride = 42/18/40 in molar ratio.

[0232]

[Chemical 86]

[Synthesis Example 24] The following monomer (b) 6.7 was used.
g (0.015 mol), perfluorooctylethyl methacrylate 2.7 g (0.005 mol), 2-methyl-2-adamantanemethacrylate 1.2 g (0.00
5 mol), mevalonic lactone methacrylate 1.0
g (0.005 mol) was dissolved in 30 ml of 1-methoxy-2-propanol, and a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (sum was added at 70 ° C. under nitrogen stream and stirring). Kojunyaku Kogyo Co., Ltd .; trade name V-6
5) 0.1 g and monomer (b) 15.6 g (0.035
Mol), 6.4 g (0.012 mol) of perfluorooctylethyl methacrylate, 2.8 g (0.012 mol) of 2-methyl-2-adamantane methacrylate, 2.4 g (0.01 of mevalonic lactone methacrylate).
A 70 ml solution of 1-methoxy-2-propanol (2 mol) was added dropwise over 2 hours. After 2 hours, 0.1 g of an initiator was added, and the reaction was further performed for 2 hours. Then, the temperature was raised to 90 ° C. and stirring was continued for 1 hour. After allowing the reaction solution to cool, it was poured into 1 L of ion-exchanged water / methanol (1/1) with vigorous stirring to precipitate a white resin. The obtained resin was dried under reduced pressure to obtain 21.5 g of Resin (24) of the present invention. When the molecular weight was measured by GPC, the weight average (Mw) was 10,500. Moreover, when the composition of the resin (24) was examined by C ¹³ -NMR measurement, a structural example (F-30) / (F-48) / (B-7) /
(B-11) = 48/15/18/19.

[0234]

[Chemical 87]

[Synthesis Examples 25 to 32] The resins (A) of the present invention shown in Table 3 were synthesized in the same manner.

[0236]

[Table 3]

[Synthesis Example 33] 13.5 g of 4- [bis (trifluoromethyl) -hydroxymethyl] styrene
(0.05 mol), methacrylonitrile 3.4 g (0.
(05 mol) to 100 ml of N, N-dimethylacetamide
And was heated to 70 ° C. under a nitrogen stream. 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd .; trade name V-65)
0.1 g was added and stirred for 3 hours. Furthermore, V-65 is set to 0.
An additional 1 g was added and stirring was continued for 4 hours. Then, the reaction solution was poured into 1 L of methanol / t-butyl methyl ether with vigorous stirring to precipitate a white resin. The precipitated resin was separated by filtration, dried under vacuum, dissolved in 100 ml of THF, 2.9 g (0.04 mol) of ethyl vinyl ether was added, a catalytic amount of p-toluenesulfonic acid was added, and the mixture was stirred at room temperature for 8 hours. . P- was added to the reaction solution
The reaction was stopped by adding twice the amount of the toluenesulfonic acid catalyst, and the mixture was put into 3 L of ultrapure water with vigorous stirring. The precipitated resin is separated by filtration and dried to obtain the resin (33) of the present invention 14.
1 g was obtained. According to GPC measurement, the molecular weight of the resin (33) was 10,900 in weight average (Mw). Also C ¹³
When the composition of the resin (33) was examined by -NMR and IR measurements, a structural example (F-39) / (F-42) was obtained in a molar ratio.
/ (C-10) = 16/36/48.

[Synthesis Examples 34 to 40] In the same manner, the resin (A) of the present invention shown in Table 4 was synthesized.

[0239]

[Table 4]

[Synthesis Examples 41 to 68] Synthesis of Resin (42) 4- (2-hydroxyhexafluoroisopropyl) styrene (manufactured by Central Glass Co., Ltd.) was placed in a 100 ml three-necked flask equipped with a reflux tube and a nitrogen inlet tube. ), 4- (1-
Methoxyethoxy) styrene (manufactured by Tosoh Corporation) was charged at a molar ratio of 50/50, and then tetrahydrofuran was added to prepare a total of 30 g of a reaction liquid having a monomer concentration of 30% by weight. It was stirred and heated to 65 ° C. under a stream of nitrogen. 5.0 mol% of azo polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) based on the total number of moles of the two monomers.
The mixture was added and reacted for 8 hours with stirring under a nitrogen stream. 200 ml of hexane was added to the obtained reaction solution to precipitate the produced polymer from the solution, and unreacted monomers were separated and purified. The polymer composition determined from C ¹³ -NMR is 49
It was / 51. When the obtained polymer was analyzed by GPC (in a THF solvent, converted to standard polystyrene), the weight average molecular weight was 10,200, the dispersity was 2.20, and the proportion of the polymer having a molecular weight of 1,000 or less was 15% by weight. It was Hereinafter, the resin (A) of the present invention shown in Table 5 was synthesized in the same manner.

[0241]

[Table 5]

Examples 1 to 22 and Comparative Examples 1 to 3 1.36 g of the resins shown in Tables 1 to 5 and 0.04 g of triphenylsulfonium nonaphlate salt were dissolved in 8.5 g of propylene glycol monomethyl ether acetate. In addition, 0.01 g of a fluorine-based and / or silicon-based surfactant described in Table 6 below and 0.005 g of a nitrogen-containing compound containing at least one fluorine atom in Examples 1 to 18 and Examples 19 to 22. 0.025 g, and (E) component is 0.0025 g in Examples 19 to 22,
In Comparative Examples 1 to 3, 0.005 g was added to prepare the resist composition of the present invention.

Each sample solution was filtered through a 0.1 μm Teflon (registered trademark) filter, and then applied on a hexamethyldisilazane-treated silicon wafer with a spin coater, and vacuum contact type hot at 110 ° C. for 90 seconds. It was heated and dried on the plate to obtain a resist film having a film thickness of 0.3 μm. For the obtained resist film, Kr
Image exposure was performed using an F excimer stepper (FPA-3000EX5), post-heating was performed at 110 ° C. for 90 seconds, and then development was performed with a 0.262N TMAH aqueous solution to form a 0.5 μL / S pattern. It was

[0244]

[Table 6]

In the table, the surfactants W1 to W4 represent the following. W1: Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine-based) W2: Megafacque R08 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine and silicon-based) W3: Polysiloxane polymer KP-341 (Manufactured by Shin-Etsu Chemical Co., Ltd.) W4: polyoxyethylene nonylphenyl ether

The abbreviations of the component (E) represent the following. TBA: tributylamine DBN: diazabicyclononene DPA: 2,6-diisopropylaniline

(Evaluation test) [Development defect]: KL manufactured by KLA-Tencor Co., Ltd. was used for the resist pattern obtained as described above.
A-2112 machine was used to measure the number of development defects, and the number was 1
The next data value was defined as the number of development defects. From the results of Tables 6 and 7, it is understood that the measured transmittance values of the coating film using the composition of the present invention exceed about 50% and have sufficient transmittance at 157 nm. The performance evaluation results are shown in Table 7.

[0248]

[Table 7]

From the results shown in Table 7, it can be seen that the composition of the present invention to which the nitrogen-containing compound containing at least one fluorine atom is added has very few development defects as compared with the comparative example without the same component.

[0250]

INDUSTRIAL APPLICABILITY The present invention can provide a positive resist composition in which the problem of development defects is improved.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 16/38 C08F 16/38 20/22 20/22 20/28 20/28 20/44 20/44 32 / 04 32/04 G03F 7/004 501 G03F 7/004 501 H01L 21/027 H01L 21/30 502R F Term (reference) 2H025 AA04 AB16 AC04 AC08 AD03 BE00 BG00 CC20 FA03 FA12 FA17 4J100 AB07P AB07Q AC26P AC27P AE38R AL08Q AL32Q AL32Q AL08Q AL08R AL08S AM02P AR11P AR11Q AR11R BA02P BA02Q BA03Q BA11Q BA15R BA20R BB10P BB18Q BB18R BB18S BC08P BC09Q BC09R BC53P BC53Q CA04 CA05 CA06 DA39 FA03 JA38

Claims (3)

[Claims] 1. A fluorine group having (A) a structure having a fluorine atom substituted in the main chain and / or side chain of a polymer skeleton, and having a group that decomposes by the action of an acid to increase the solubility in an alkali developing solution. A positive resist composition comprising a contained resin, (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and (D) a nitrogen-containing compound containing at least one fluorine atom. 2. The resin (A) has at least one site selected from a perfluoroalkylene group and a perfluoroarylene group in the main chain of the polymer skeleton, or a perfluoroalkyl group, a perfluoroaryl group, It is a fluorine group-containing resin having at least one site selected from a hexafluoro-2-propanol group and a group protecting the OH group of the hexafluoro-2-propanol group in the side chain of the polymer skeleton. The positive resist composition according to claim 1, wherein 3. The positive resist composition according to claim 1, which is a composition for exposure by far ultraviolet light having a wavelength of 180 nm or less.