JP2002139839A - Positive type resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type photosensitive composition having diminished stationary waves, superior sensitivity and resolving power and an excellent shape of a pattern profile. SOLUTION: The positive type photosensitive composition contains a compound which generates an acid when irradiated with active light or radiation, a resin having an alicyclic hydrocarbon structure and having solubility in an alkali developing solution increased by decomposition by the action of the acid and a fluorine-containing compound of formula (I) (where R is a fluorine- containing hydrocarbon group and X is a fluorine-free divalent linking group).

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 used in the process of manufacturing semiconductors such as ICs, the manufacture of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes.

[0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive resist composition used in the process of manufacturing semiconductors such as ICs, the manufacture of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes. More specifically, the present invention relates to a positive resist composition suitable for use as a light source for exposure to far ultraviolet rays of 250 nm or less.

[0003]

2. Description of the Related Art When a conventional resist composed of a novolak and a naphthoquinonediazide compound is used for pattern formation in lithography using deep ultraviolet light or excimer laser light, the absorption of novolak and naphthoquinonediazide in the deep ultraviolet region is strong. Light hardly reaches the bottom of the resist, and only a low-sensitivity, tapered pattern can be obtained.

One of the means for solving such a problem is as follows.
U.S. Pat. No. 4,491,628, EP 249,1
No. 39 or the like. The chemically amplified positive resist composition generates an acid in the exposed portion by irradiation with radiation such as far ultraviolet light, and the reaction using the acid as a catalyst dissolves the active radiation-irradiated portion and the non-irradiated portion in the developing solution. It is a pattern forming material that changes the properties and forms a pattern on a substrate.

[0005] Examples of such a combination include a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (JP-A-48-89003), a combination of an orthoester or an amide acetal compound. (JP-A-51-120714), combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429), combination with an enol ether compound (JP-A-55-12995) ), N-acyliminocarbonate compounds (JP-A-55-126)
236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), and a combination with a tertiary alkyl ester compound (JP-A-60-1985).
No. 3625), combinations with silyl ester compounds (JP-A-60-10247), combinations with silyl ether compounds (JP-A-60-37549 and JP-A-60-12146). Can be mentioned. These have high photosensitivity because the quantum yield exceeds 1 in principle.

[0006] Similarly, a system which is decomposed by heating in the presence of an acid and solubilized in an alkali is disclosed in, for example,
9-45439, JP-A-60-3625, JP-A-6-6
2-229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250542,
JP-A-5-181279, Polym. En
g. Sce. 23, 1012 (1983); AC
S. Sym. 242, 11 (1984); Semi
conductor World, 1987, November, p. 91; Macromolecules, 21,
1475 (1988); SPIE, vol. 920, p. 42 (1988), etc., and a compound capable of generating an acid upon exposure to a tertiary or secondary carbon (for example, t-butyl,
2-cyclohexenyl) in combination with an ester or carbonate compound, JP-A-4-219775,
Nos. 2,496,682 and 6,65,332, and the like, in combination with an acetal compound described in
And combinations with t-butyl ether compounds described in JP-A-212258 and JP-A-6-65333.

Since these systems mainly use a resin having a poly (hydroxystyrene) basic skeleton having a small absorption in the 248 nm region as a main component, a high sensitivity is obtained when a KrF excimer laser is used as an exposure light source. A high-resolution and good pattern can be formed, and it can be a good system as compared with the conventional naphthoquinonediazide / novolak resin system.

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

On the other hand, the polymer having an alicyclic hydrocarbon group has the same dry etching resistance as an aromatic group and has a small absorption in the 193 nm region.
c. of SPIE, 1672, 66 (1992), and the use of the polymer has been energetically studied in recent years. Specifically, JP-A-4-39665 and JP-A-5-8
0515, 5-265212, 5-29759
No. 1, 5-346668, 6-289615,
6-324494, 7-49568, 7-1
No. 85046, No. 7-191463, No. 7-1994
Polymers described in JP-A Nos. 67, 7-234511, 7-252324 and the like can be mentioned. Since these polymers have an alicyclic hydrocarbon having a very high hydrophobicity, they have problems in developability (generation of development residues, generation of development defects, etc.).

[0010] In particular, when it is difficult to improve the performance only by combining the acid-decomposable resin and the photoacid generator, the improvement of the performance by adding a low-molecular acid-decomposable compound is disclosed. . JP-A-10-20501 discloses an improvement in performance by using a compound selected from alkylcarboxylic acids having 4 to 20 carbon atoms and fluorocarboxylic acids. However, these techniques did not show any effect on the improvement.

Therefore, even when the above-described techniques are used, a photoresist composition for exposure to far ultraviolet rays can
There are many points that are inadequate for preventing the generation of standing waves and resist pattern profiles, and improvements have been required. In particular, as the resist pattern size becomes smaller than a quarter micron, the demand for improvement has been further increased, but no guideline for the improvement has been disclosed so far.

[0012]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to improve the inherent performance of the above-described microphotofabrication using far ultraviolet light, particularly ArF excimer laser light, and to improve sensitivity, resolution, and resist pattern profile. Another object of the present invention is to provide a positive resist composition which is excellent in the above-mentioned properties and has a reduced standing wave.

[0013]

SUMMARY OF THE INVENTION The present invention is a positive resist composition having the following constitution, thereby achieving the above object of the present invention.

(1) (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (B) a compound having a monocyclic or polycyclic alicyclic hydrocarbon structure in a main chain or a side chain thereof, and A resin that decomposes to increase solubility in an alkali developer,
(C) A positive resist composition comprising a compound having a structure represented by the following general formula (I).

[0015]

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In the general formula (I), R represents a hydrocarbon group containing a fluorine atom. X is a fluorine-free 2
Represents a valent linking group. (2) It has a group decomposable by an acid, and its dissolution rate in an alkaline developer is increased by the action of an acid.
The positive resist composition according to the above (1), further comprising a low molecular weight dissolution inhibiting compound of 0 or less. (3) (A) a compound that generates an acid upon irradiation with actinic rays or radiation, (C) a compound having a structure represented by the following general formula (I), (D) an acid-decomposable group, A low-molecular-weight dissolution inhibiting compound having a molecular weight of 3000 or less, in which the dissolution rate in a developer is increased by the action of an acid;
(E) A positive resist composition comprising a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure in a main chain or a side chain, which is insoluble in water and soluble in an alkali developing solution.

[0017]

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In the general formula (I), R represents a hydrocarbon group containing a fluorine atom. X is a fluorine-free 2
Represents a valent linking group.

(4) The positive resist composition according to any one of the above (1) to (3), further comprising (F) a nitrogen-containing basic compound. (5) The above (1) to (G), further comprising (G) a fluorine-based and / or silicon-based surfactant.
The positive resist composition according to any of (4). (6) The positive resist composition according to any one of claims 1 to 5, wherein the irradiation light is far ultraviolet light having a wavelength of 220 nm or less.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION {(A) Photoacid Generator}
(A) A compound (photoacid generator) that generates an acid upon irradiation with actinic rays or radiation will be described. The photoacid generator used in the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation. Examples of the compound used in the present invention, which decomposes upon irradiation with actinic rays or radiation to generate an acid, include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, and a photodiscoloration agent. Or a known light (400 to 2) used for a micro resist or the like.
00 nm ultraviolet light, far ultraviolet light, particularly preferably g-line,
h-rays, i-rays, KrF excimer laser light), ArF excimer laser light, electron beams, X-rays, compounds generating an acid by a molecular beam or an ion beam, and mixtures 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, S.I. I. Schlesinger, Ph
otogr. Sci. Eng. , 18, 387 (197
4). S. Bal etal, Polymer, 2
1,423 (1980); U.S. Pat. Nos. 4,069,055 and 4,069,056;
No. Re 27,992, JP-A-3-140,1
No. 40, etc .; C. Necke
et al, Macromolecules, 17,
2468 (1984), C.I. S. Wen et al, T
eh, Proc. Conf. Rad. Curing A
SIA, p478 Tokyo, Oct (1988),
U.S. Pat. Nos. 4,069,055 and 4,069,0
No. 56, etc .; V. Clive
Ilo et al, Macromorecules, 1
0 (6), 1307 (1977), Chem. & En
g. News, Nov .; 28, p31 (1988), European Patent Nos. 104,143 and 339,049,
No. 410,201, JP-A-2-150,848,
Iodonium salts described in JP-A-2-296,514 and the like;

J. V. Crivello etal, P
polymer J .; 17, 73 (1985);
V. Crivello et al. J. Org. Che
m. 43, 3055 (1978); R. Watt
et al. PolymerSci. , Polym
er Chem. Ed. , 22, 1789 (198
4). V. Crivello etal, Poly
mer Bull. , 14, 279 (1985);
V. Crivello etal, Macromore
cules, 14 (5), 1141 (1981);
V. Crivelloetal, J. et al. PolymerS
ci. , Polymer Chem. Ed. , 17,2
877 (1979), EP 370,693,
No. 161, 811; No. 410, 201; No. 339,
No. 049, No. 233,567, No. 297,443,
No. 297,442, U.S. Pat. No. 3,902,114
Nos. 4,933,377 and 4,760,013
Nos. 4,734,444, 2,833,827
, German Patent Nos. 2,904,626 and 3,604,
Nos. 580 and 3,604,581, and JP-A-7-282.
No. 37, the sulfonium salts described in 8-27102 and the like,

J. V. Crivello etal, M
acromorecules, 10 (6), 1307
(1977); V. Crivello etal,
J. PolymerSci. , Polymer Che
m. Ed. , 17, 1047 (1979) and the like; S. Wen et al, Teh,
Proc. Conf. Rad. Curing ASI
A, p478 Onkyo salts, such as arsonium salts described in Tokyo, Oct (1988), US Pat.
05,815, JP-B-46-4605, JP-A-48-48
JP-A-36-281, JP-A-55-32070, JP-A-55-32070
0-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241
JP-A-62-212401, JP-A-63-702
No. 43, JP-A-63-298339, etc .; Meier et al, J. Mol. Ra
d. Curing, 13 (4), 26 (1986),
T. P. Gill et al, Inorg. Che
m. , 19, 3007 (1980); Astru
c, Acc. Chem. Res. , 19 (12), 37
7 (1896), organic metal / organic halides described in JP-A-2-161445 and the like;

S. Hayase et al. Pol
ymer Sci. , 25, 753 (1987);
Reichmanis et al. Polyme
r Sci. , Polymer Chem. Ed. , 2
3, 1 (1985); Q. Zhu et al.
Photochem. , 36, 85, 39, 317 (1
987); Amit etal, Tetrahe
drone Lett. , (24) 2205 (197
3), D. H. R. Barton et al. Ch
em Soc. , 3571 (1965); M. Co
llins et al, J. Mol. Chem. SoC. ,
Perkin I, 1695 (1975); Rud
instein etal, Tetrahedron
Lett. , (17), 1445 (1975);
W. Walker et al. Am. Chem. So
c. , 110, 7170 (1988); C. Bus
man et al, J.M. Imaging Techno
l. , 11 (4), 191 (1985); M. Ho
ulihan etal, Macormolecule
s, 21, 2001 (1988); M. Coll
ins et al. Chem. Soc. , Che
m. Commun. , 532 (1972); Hay
ase etal, Macromolecules, 1
8, 1799 (1985); Reichmanis
et al. Electrochem. Soc. ,
Solid State Sci. Technol. ,
130 (6), F.R. M. Houlihan etal,
Macromolcules, 21, 2001 (198
8), EP 0290,750, EP 046,0
No. 83, No. 156,535, No. 271,851, No. 0,388,343, U.S. Pat. No. 3,901,71
Nos. 0 and 4,181,531, JP-A-60-1985
No. 38, a photoacid generator having an O-nitrobenzyl-type protecting group described in JP-A-53-133022 and the like,

M. TUNOOKA etal, Poly
mer Preprints Japan, 35
(8), G. Berner et al. Rad. C
uring, 13 (4); J. Mijs eta
1, Coating Technology. , 55 (69
7), 45 (1983), Akzo, H .; Adachi
et al, Polymer Preprints, J
apan, 37 (3), EP 0199,672.
Nos. 84515, 044, 115 and 61
No. 8,564, No. 0101,122, U.S. Pat.
Nos. 371,605, 4,431,774, JP-A-64-18143, JP-A-2-245756, and JP-A-3-140109. Compounds generating sulfonic acid, JP-A-61-166544, JP-A-2-712
No. 70, etc .;
No. 854, No. 3-103856, No. 4-210960
And diazoketosulfone and diazodisulfone compounds.

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, E. FIG. Woodhouse et
al, J .; Am. Chem. Soc. , 104,558
6 (1982); P. Pappas et al,
J. Imaging Sci. , 30 (5), 218
(1986); Kondo etal, Makro
mol. Chem. , Rapid Commun. ,
9, 625 (1988); Yamada eta
1, Makromol. Chem. , 152, 153,
163 (1972); V. Crivello et
al, J .; PolymerSci. , Polymer
Chem. Ed. , 17, 3845 (1979), U.S. Patent No. 3,849,137, German Patent No. 39144.
07, JP-A-63-26653, JP-A-55-164
No. 824, JP-A-62-269263, JP-A-63-1
46038, JP-A-63-163452, JP-A-62-153853, and JP-A-63-14629 can be 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, and photoacid generators having o-nitrobenzyl-type protecting groups , A compound that generates sulfonic acid upon photolysis, such as an agent, iminosulfonate, etc., a disulfone compound, a diazoketosulfone, and a diazodisulfone compound. Further, a group in which an acid is generated by such light or a compound in which a compound is introduced into a main chain or a side chain of a polymer can be used.

V. N. R. Pilai, Syn
thesis, (1), 1 (1980); Abad
et al, Tetrahedron Lett. ,
(47) 4555 (1971); H. R. Bart
on et al, J.A. Chem. Soc. , (C),
329 (1970); U.S. Pat. No. 3,779,778.
And compounds capable of generating an acid by light described in EP 126,712 and the like can also be used.

Among the compounds which decompose upon irradiation with actinic rays or radiation to generate an acid, those which are particularly effectively used will be 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).

[0029]

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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.

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

[0032]

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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, the carbon number is 6 to
They are a 14 aryl group, an alkyl group having 1 to 8 carbon atoms, and substituted derivatives thereof. 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 the aryl group, and a substituent for the alkyl group. It is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, or an alkoxycarbonyl group.

[0034] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
Alkanesulfonic acid which may be substituted, perfluoroalkanesulfonic acid, benzenesulfonic acid which may be substituted, naphthalenesulfonic acid, anthracenesulfonic acid,
Examples include but are not limited to camphorsulfonic acid anion, saccharin anion, and the like. Preferred are anions of alkanesulfonic acid, perfluoroalkanesulfonic acid, alkyl-substituted benzenesulfonic acid, pentafluorobenzenesulfonic acid, and saccharin anion.

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.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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The onium salts represented by the general formulas (PAG3) and (PAG4) are known, and are described, for example, in J. Am. W. Kn
apczyk et al. Am. Chem. So
c. , 91, 145 (1969); L. Mayco
k et al. Org. Chem. , 35,25
32, (1970); Goethas etal,
Bull. Soc. Chem. Belg. , 73,54
6, (1964); M. Leicester,
J. Ame. Chem. Soc. , 51, 3587 (1
929); V. Crivello et al.
Polym. Chem. Ed. , 18, 2677 (19
80); U.S. Patent Nos. 2,807,648 and 4,2;
No. 47,473, JP-A-53-101,331 and the like.

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

[0050]

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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 include the following compounds, but are not limited thereto.

[0052]

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[0053]

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[0054]

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[0055]

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

[0057]

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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,
It is not limited to these.

[0059]

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In the present invention, the compound represented by the above general formula (PAG-
The compound represented by 3), (PAG-4) or (PAG-7) is most preferable in terms of sensitivity and resolution. The amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.001 to 40% by weight based on the total composition (excluding the solvent) of the positive photosensitive composition of the present invention. %, Preferably 0.01 to 20% by weight, more preferably 0.01 to 5% by weight. If the amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid is less than 0.01% by weight, the sensitivity becomes low, and if it is more than 40% by weight, the light absorption of the resist becomes high. This is not preferable because the profile is deteriorated and the process (especially baking) margin is narrowed.

<< (B) a resin whose solubility in an alkali developing solution is increased by the action of an acid >>
A resin whose solubility in an alkaline developer is increased by the action of an acid (hereinafter also referred to as “acid-decomposable resin”) has a group that is decomposed by the action of an acid. A group that decomposes under the action of an acid (hereinafter also referred to as an “acid-decomposable group”) is, for example, a group that hydrolyzes under the action of an acid to form an acid, and further, a carbon cation is desorbed under the action of an acid to form an acid. Group. Preferred are groups represented by the following general formulas (x) and (y), acid-decomposable groups having a lactone structure, and acid-decomposable groups having an alicyclic structure. Thereby, the stability over time becomes excellent.

[0062]

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Here, Ra, Rb and Rc each independently represent a hydrogen atom or an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent.
However, at least one of Ra, Rb and Rc in the formula (x) is a group other than a hydrogen atom. Rd represents an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. Further, two groups out of Ra, Rb and Rc in the formula (x) or two groups out of Ra, Rb and Rd in the formula (y) are bonded to each other to form a ring composed of 3 to 8 carbon atoms. A structure may be formed, or a ring structure containing a hetero atom may be formed. Specific examples of such a ring include a cyclopropyl group, a cyclopentyl group,
Examples thereof include a cyclohexyl group, a cycloheptyl group, a 1-cyclohexenyl group, a 2-tetrahydrofuranyl group, and a 2-tetrahydropyranyl group. Za and Zb each independently represent an oxygen atom or a sulfur atom. As the alkyl group of Ra to Rd, preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, which may have a substituent,
Those having 1 to 8 carbon atoms such as sec-butyl group, hexyl group, 2-ethylhexyl group and octyl group are exemplified. The cycloalkyl group preferably has 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group, which may have a substituent. The alkenyl group preferably has 2 to 6 carbon atoms such as a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a cyclohexenyl group which may have a substituent. No.

Further substituents in each of the above-mentioned substituents are preferably a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, a methyl group. , Ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, alkyl group such as octyl group, methoxy group, ethoxy group, hydroxyethoxy group,
Propoxy group, hydroxypropoxy group, alkoxy group such as butoxy group, methoxycarbonyl group, alkoxycarbonyl group such as ethoxycarbonyl group, formyl group, acetyl group, acyl group such as benzoyl group, acetoxy group,
Examples include an acyloxy group such as a butyryloxy group and a carboxy group.

Specific examples of the repeating unit having an acid-decomposable group are shown below, but the present invention is not limited thereto.

[0066]

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[0067]

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[0068]

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[0069]

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Among the above, (c1), (c7), (c
11) is particularly excellent in acid decomposability. In the present invention, the acid-decomposable resin contains a monocyclic or polycyclic alicyclic hydrocarbon structure in a main chain or a side chain. Further, it may contain a lactone structure. Here, the lactone structure is preferably one having a lactone structure in the side chain of the resin, and specific examples thereof include repeating units (a1) to (a20) having a lactone structure in the side chain shown below. Both the alicyclic hydrocarbon structure and the lactone structure here may have acid-decomposability, and may not necessarily have. The acid-decomposable group that may be contained in the alicyclic hydrocarbon group may be linked by an acid-decomposable structure, decomposed by the action of an acid to leave the alicyclic hydrocarbon group, or an alicyclic hydrocarbon group. The group represented by the formula (x) or (y) may be bonded to the hydrocarbon group directly or via a linking group. When having a monocyclic or polycyclic alicyclic hydrocarbon group in the side chain of the resin,
It is preferable that the resin main chain and the alicyclic hydrocarbon group are connected by a tertiary ester group.

[0071]

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[0072]

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Of the above-mentioned (a1) to (a20), for example, (a1), (a12), (a15) and the like are usually preferred because of their acid decomposability. The monocyclic or polycyclic alicyclic hydrocarbon structure contained in the acid-decomposable resin has a monocyclic alicyclic skeleton having 3 or more carbon atoms, preferably 3 to 8 carbon atoms, as a monocyclic type. And a cyclic hydrocarbon skeleton such as cyclopropane, cyclobutane, cyclopentane and cyclohexane.
The polycyclic type has 5 or more carbon atoms, preferably 7 carbon atoms.
Those having up to 25 alicyclic skeletons can be mentioned. For example, an alicyclic cyclic hydrocarbon skeleton such as bicyclo, tricyclo and tetracyclo may be mentioned. More specifically, those exemplified in the structure described later are exemplified. As such a repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure, the following general formulas (II) to (II) are preferable.
It is a structural unit represented by (V).

[0074]

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[0075]

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Formulas (II) to (IV) will be described, and then formula (V) will be described. In the formulas (II) to (IV), a substituent bonded to the main chain of the repeating unit, that is, R ¹¹ ,
R ¹² , R ^{14 to} R ¹⁶ represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group. R ¹¹ ,
R ¹² and R ^{14 to} R ¹⁶ may be the same or different. Examples of the alkyl group represented by R ¹¹ , R ¹² , and R ^{14 to} R ¹⁶ include a methyl group, an ethyl group, a propyl group,
1-4 carbon atoms such as n-butyl group and sec-butyl group
Hydrocarbon groups. Examples of the haloalkyl group include groups in which a part or all of an alkyl group having 1 to 4 carbon atoms is substituted with a halogen atom. Here, the halogen atom preferably includes a fluorine atom, a chlorine atom or a bromine atom. Specific examples of the haloalkyl group include, for example, a fluoromethyl group, a chloromethyl group, a bromomethyl group, a fluoroethyl group, a chloroethyl group, a bromoethyl group, and the like.
These alkyl groups and haloalkyl groups may further have a substituent other than a halogen atom.

The substituent R ¹³ is a cyano group, —CO—OR ²³
Or an -CO-NR ²⁴ R ^25. Here, R ²³ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group, or an acid-decomposable group. Examples of the acid-decomposable group include the same groups as described above. For example, a compound having the same repeating structural unit as described above is preferable. Of the R ^23,
The alkyl group, cycloalkyl group and alkenyl group may further have a substituent.

The above R ²⁴ and R ²⁵ are each a hydrogen atom or
Represents an alkyl group, a cycloalkyl group or an alkenyl group. The alkyl group, cycloalkyl group, and alkenyl group may have a substituent. R ²⁴ and R ²⁵ may be the same or different. Combine with each other,
A ring may be formed together with the nitrogen atom. In such a case, the ring structure is preferably a 5- to 8-membered ring, and specific examples include pyrrolidine, piperidine, and piperazine skeletons.

The alkyl group represented by R ^{23 to} R ²⁵ is preferably an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group. Group, 2-ethylhexyl group, octyl group and the like. As the cycloalkyl group, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and specific examples include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. The alkenyl group has 2 to 2 carbon atoms.
The alkenyl group of 6 is preferable, and specific examples include a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a cyclohexenyl group. The alkyl group, cycloalkyl group, and alkenyl group may have a substituent.

In the formulas (II) to (IV), X ₁ -A, X ₂
-A or X ₃ -A, X _{1 to} X ₃
Represents a single bond or a divalent group. Examples of the divalent group, such as an alkylene group, an alkenylene group, a cycloalkylene _{group, -O -, - SO 2 -} , - O-CO-R 26 -, - CO
—O—R ²⁷ — and —CO—NR ²⁸ —R ²⁹ — and the like. X _{1 to} X ₃ may be the same or different.

Among X _{1 to} X ₃ , an alkylene group, alkenylene group and cycloalkylene group are represented by R ¹¹ , R ¹² , R ^{14 to} R
^Examples of the alkyl group, alkenyl group, and cycloalkyl group represented by ¹⁶ include divalent groups having the same carbon skeleton. The above-mentioned —O—CO—R ²⁶ — and —CO— of X _{1 to} X ₃ ;
O-R ²⁷ - and -CO-NR ^{2 8} -R ²⁹ - in R ^26,
R ²⁷ and R ²⁹ each represent a single bond or a divalent group. 2
Examples of the valent group include an alkylene group, an alkenylene group, and a cycloalkylene group. In this case, the alkylene group, alkenylene group, and cycloalkylene group also include divalent groups having the same carbon skeleton as the alkyl group, alkenyl group, and cycloalkyl group represented by R ¹¹ , R ¹² , and R ^{14 to} R ^16. Can be. These groups may further be bonded to an ether group, an ester group, an amide group, a urethane group or a ureide group to form a divalent group as a whole. Tripartite R ^26, R ^27, R ²⁹ may be the same or may be different from one another. X _{1 to} X
-CO-NR ²⁸ -R ²⁹ of the ₃ - substituents R ²⁸ are, similarly to the above R ²³ to R ^25, represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an alkenyl group. These alkyl group, cycloalkyl group and alkenyl group may have a substituent. R ²⁸ may be the same as or different from any of R ²⁴ and R ²⁵ . Alkyl group represented by R ^28, a cycloalkyl group, etc. Specific examples of the alkenyl groups are each an alkyl group represented by R ²³ to R ^25, a cycloalkyl group, the same as for the alkenyl group.

The substituent A indirectly bonded to the main chain of the repeating unit via X ₁ or the like represents a monocyclic or polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group represented by A include groups having an alicyclic skeleton having 3 or more carbon atoms, preferably 3 to 8 carbon atoms. For example, a cyclic hydrocarbon skeleton such as cyclopropane, cyclobutane, cyclopentane and cyclohexane can be mentioned. Examples of the polycyclic hydrocarbon group include a group having an alicyclic skeleton having 5 or more carbon atoms, preferably 7 to 25 carbon atoms. For example, an alicyclic cyclic hydrocarbon skeleton such as bicyclo, tricyclo and tetracyclo may be mentioned. These monocyclic or polycyclic cyclic hydrocarbon skeleton groups may further have a substituent to increase the number of carbon atoms.

Preferred substituents of the polycyclic alicyclic group include a hydroxyl group, a halogen atom, a nitro group, a cyano group, an amide group, a sulfonamide group, and the alkyl group described for R ²³ as they are. it can. Halogen is fluorine, chlorine, bromine or iodine. As a substituent, an alkoxy group, an alkoxycarbonyl group,
Examples include an acyl group, an acyloxy group, and a carboxy group.
Examples of the alkoxy group include an alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group. As the alkoxycarbonyl group,
Examples thereof include an alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group. Examples of the acyl group include a formyl group, an acetyl group and a benzoyl group. Examples of the acyloxy group include an acetoxy group and a butyryloxy group.

Typical examples of the polycyclic or monocyclic alicyclic moiety of the above-mentioned polycyclic or monocyclic cyclic hydrocarbon group, that is, A, are as follows. .

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[0086]

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Next, the general formula (V) will be described. In the general formula (V), n is 0 or 1. X
a and Xb represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Ya and Yb represent a hydrogen atom, a hydroxyl group, or -COO
Represents a group represented by Xc. Here, Xc represents, in one embodiment, a hydrogen atom or an alkyl group. Examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a tert group -Butyl group and the like. These alkyl groups are a hydroxyl group, a halogen group or a cyano group,
Some or all of the hydrogen atoms may be substituted. In another embodiment of Xc, -COOXc represents a group constituting an acid-decomposable group as a whole. Specifically, the above equation (x),
The group represented by (y) can be mentioned. In addition, a group containing an acid-decomposable lactone structure and a group containing an acid-decomposable alicyclic structure can also be mentioned.

Specific examples of the repeating structural units represented by formulas (II) to (V) are shown below, but the present invention is not limited to these.

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[0090]

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Among these specific examples, for example, (b1)
(B2), (b5), (b9), (b47), (b4)
8), (b49), (b50), (b54), (b5)
8), (b60) and the like are usually preferred because of their acid decomposability. In particular, (b1), (b47), and (b4) in which an adamantyl group is linked to the resin main chain by an acid-decomposable structure.
8) and (b49) are preferred. When these are used, dry etching resistance and resolution are improved.

The acid-decomposable resin as described above may further contain a carboxyl group. The carboxyl group may be contained in each of the above repeating structural units, or may be contained in another repeating structural unit other than these. Furthermore, these structural units may be included in a plurality of positions.

The content of all the repeating structural units having a carboxyl group in the acid-decomposable resin contained in the positive resist composition of the present invention is adjusted by performance such as alkali developability, substrate adhesion, and sensitivity. However, it is preferably 0 to all repeating structural units of the acid-decomposable resin.
The range is 60 mol%, more preferably 0 to 40 mol%, and still more preferably 0 to 20 mol%.

Specific examples of the repeating structural unit having a carboxyl group are shown below, but the present invention is not limited thereto.

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[0103]

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For the purpose of improving the performance of the acid-decomposable resin,
Other polymerizable monomers may be further copolymerized within a range that does not significantly impair the transmittance of the resin at 220 nm or less and the dry etching resistance. Copolymerizable monomers that can be used include those shown below. For example, it has one addition-polymerizable unsaturated bond selected from acrylates, acrylamides, methacrylates, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonates, and the like. Compound.

Specifically: acrylates, for example, alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) acrylate (for example, methyl acrylate, ethyl acrylate, propyl acrylate, t-acrylate)
Butyl, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate,
Acrylic acid-t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl Acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate, methoxyethoxyethyl acrylate;

Methacrylic esters, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms)
Methacrylate (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, Hydroxypentyl methacrylate, 2,2-dimethyl-3
-Hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like, aryl methacrylate (for example, phenyl methacrylate, naphthyl methacrylate and the like), methoxyethoxyethyl methacrylate;

Acrylamides, for example, acrylamide, N-alkylacrylamide, (where the alkyl group has 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a heptyl group Octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-arylacrylamide, N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, Ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group, etc., N, N-arylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, etc .; methacrylamides, For example, methacrylamide, N- The Le Kill methacrylamide (the alkyl group, those having 1 to 10 carbon atoms, e.g., methyl, ethyl, t- butyl group, ethylhexyl group,
Hydroxyethyl group, cyclohexyl group, etc.), N-aryl methacrylamide, N, N-dialkyl methacrylamide (alkyl group is ethyl group, propyl group, butyl group, etc.), N-hydroxyethyl-N-methyl methacrylamide , N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide and the like; allyl compounds such as allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, palmitic acid) Allyl, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxyethanol and the like;

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

Among them, methoxyethoxyethyl methacrylate and methoxyethoxyethyl acrylate are particularly preferred. (B) The content of the repeating structural unit derived from another polymerizable monomer in the acid-decomposable resin is preferably 50 mol% or less based on all repeating structural units,
It is more preferably at most 30 mol%. From the viewpoint of ensuring transparency to actinic rays or radiation, it is preferred that the acid-decomposable resin (B) does not contain an aromatic ring. This is because, when the transparency to the irradiation light is reduced due to the introduction of the aromatic ring, the exposure light hardly reaches the bottom of the resist film, resulting in a pattern profile called a taper.

(B) In the acid-decomposable resin, the content of the repeating structural unit having an acid-decomposable group is adjusted by the balance between dry etching resistance, alkali developability and the like. The content is preferably at least 20 mol%, more preferably at least 30 mol%, further preferably at least 40 mol%. The structural unit having the cyclic hydrocarbon group (preferably, any of the general formulas (II) to (IV)
The content of the repeating structural unit represented by the formula (I) is adjusted according to the balance between dry etching resistance, alkali developability, and the like, but is preferably 20 mol% or more based on all repeating structural units. The content is more preferably 3
0-80 mol%, more preferably 35-70 mol%,
More preferably, it is in the range of 40 to 60 mol%.
The content of the repeating structural unit having a lactone structure in the acid-decomposable resin (B) is adjusted by a balance between dry etching resistance, alkali developability, and the like. % Is preferable. The content is more preferably 30 to
The range is 80 mol%, more preferably 35 to 70 mol%, and still more preferably 40 to 60 mol%. In the present invention, the content of the resin (B) whose solubility in an alkaline developer is increased by the action of an acid (B) is from 20 to 99.8% by weight, preferably 50%, based on the total composition or the solid content excluding the solvent. ９９99.5% by weight is good.

(B) The weight-average molecular weight of the acid-decomposable resin is
As a polystyrene conversion value measured by the GPC method, 100
It is preferably in the range of 0 to 100,000, more preferably 2000 to 50,000, and still more preferably 300 to 50,000.
The range is from 0 to 30,000. Also, the degree of dispersion is 1.0 to
5.0 is preferred, and more preferably 1.0 to 3.0.

{(C) Compound Represented by the Structure of the General Formula (I) "Component (C)"} In the general formula (I), R represents a hydrocarbon group containing a fluorine atom. X represents a single bond or a divalent linking group containing no fluorine atom.

In R, the fluorine atom-containing hydrocarbon group generally has 1 to 15 carbon atoms, preferably 1 to 11 carbon atoms, and generally has 1 to 31 fluorine atoms, preferably 1 to 23 carbon atoms. It is. Examples of the hydrocarbon group having a fluorine atom include those in which a hydrogen atom of an optionally substituted alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or the like is substituted with a fluorine atom. Can be.

As the alkyl group, an alkyl group having 1 to 8 carbon atoms is preferable. Specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a hexyl group, Examples thereof include a 2-ethylhexyl group and an octyl group. Examples of the cycloalkyl group include those having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the aryl group include phenyl, tolyl, methoxyphenyl, and naphthyl groups having 6 to 1 carbon atoms.
There are four. Examples of the aralkyl group include those having 7 to 15 carbon atoms such as a substituted or unsubstituted benzyl group and a substituted or unsubstituted phenethyl group.

As these substituents, an alkyl group, a cycloalkyl group, a halogen atom (a fluorine atom,
(Chlorine atom, iodine atom), aryl group, cyano group, hydroxy group, carboxy group, alkoxycarbonyl group, nitro group and the like. The alkyl group, cycloalkyl group, and aryl group include those described above. Further, the alkyl group, cycloalkyl group and aryl group may be further substituted with a halogen atom.

Specific examples of the group having a fluorine atom are shown below, but it should not be construed that the invention is limited thereto. Fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2
-Fluoroethyl group, 2,2-difluoroethyl group,
2,2,2-trifluoroethyl group, 1-fluoroethyl group, 1,1-difluoroethyl group, 1,2-difluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 3- Fluoropropyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, 2,
2,3,3,3-pentafluoropropyl group, 1,1,
2,2,3,3,3-heptafluoropropyl group, 1-
Fluorobutyl group, 2-fluorobutyl group, 3-fluorobutyl group, 4-fluorobutyl group, 1,1-difluorobutyl group, 1,2-difluorobutyl group, 1,3-difluorobutyl group, 1,4- Difluorobutyl group, 1,
1,1-trifluorobutyl group, 1,1,1,2,2-
Pentafluorobutyl group, 1,1,1,2,2,3,3
-Heptafluorobutyl group, 1,1,1,2,2,3
3,4,4-nonafluorobutyl group, 1-fluoropentyl group, 2-fluoropentyl group, 3-fluoropentyl group, 4-fluoropentyl group, 5-fluoropentyl group, 1,1,1-trifluoropentyl Group, 1,1,
1,2,2-pentafluoropentyl group, 1,1,1,1
2,2,3,3-heptafluoropentyl group, 1,1,
1,2,2,3,3,4,4-nonafluoropentyl group, 1,1,1,2,2,3,4,4,5,5-undecafluoropentyl group and more carbon Long-numbered perfluoroalkyl groups, fluorocyclohexyl groups, difluorocyclohexyl groups, perfluorocyclohexyl groups, pentafluorophenyl groups, trifluorophenyl groups, pentafluorobenzyl groups, perfluorobenzyl groups, and the like can be mentioned.

The divalent linking group for X is preferably a divalent group represented by the following formula (W1). General formula (W1)-(A) _n- (D) _m- (A) _{p- In the} formula (W1), A may have a substituent,
Represents a branched or cyclic alkylene group, an arylene group, a heteroarylene group, or an aralkylene group. D is -O
-, - S -, - C (= O) -, - N (R 4) -, - SO
—, —SO ₂ —, —CO ₂ —, —N (R ₄ ) SO ₂ — (R ₄ represents a hydrogen atom or an alkyl group. Here, examples of the alkyl group include those described above for R. ). n is an integer of 0 to 5, m is an integer of 0 to 5, p is 0
Represents an integer of 5 to 5. In the formula (W1), when there are a plurality of A, each A may be the same or different. However, general formula (W1) does not contain a fluorine atom.

In the above, examples of the linear, branched or cyclic alkylene group include those having 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group, a 1,4-butylene group and a 1,4-cyclohexylene group. Can be mentioned. In the above, examples of the arylene group include a phenylene group, a naphthylene group, and an anthrylene group. In the above, examples of the aralkylene group include a toluylene group, a xylylene group, and a phenethylene group. In the above, examples of the heteroarylene group include those having a divalent group in the structures represented by the following formulas (A1) to (A4).

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Here, X is an oxygen atom, a sulfur atom or-
Represents NH-, Y ₁ ~Y ₆ are each, -CH = or -
N =, and in formula (A3), at least one of Y _{1 to} Y ₆ represents -N =. Y ₇ to Y ₁₄ are each, -C
H = or represents -N =, at least one of Y ₇ to Y ₁₄ represents -N =.

Further substituents of the above groups include an alkyl group, a cycloalkyl group, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), an amino group, a nitro group, a cyano group, a methoxy group and an ethoxy group.・ Hydroxyethoxy group ・ Propoxy group ・ Hydroxypropoxy group ・ n
-Butoxy group, isobutoxy group, sec-butoxy group
and alkoxy groups such as t-butoxy group. X is preferably an alkylene group which may have a substituent.

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

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The content of the compound (C) in the positive resist composition of the present invention is preferably 0.1 to 40% by weight, more preferably 0.5 to 40% by weight, based on the solid content of the composition. It is 30% by weight, more preferably 1 to 25% by weight.

{(D) Acid-Decomposable Dissolution Inhibiting Compound} The positive resist composition of the present invention has a group (D) which is decomposed by the action of an acid to increase the solubility in an alkaline developer, It is preferable to contain a dissolution-inhibiting low-molecular compound having a molecular weight of 3000 or less (hereinafter, also referred to as “(D) acid-decomposable dissolution-inhibiting compound”). In particular, in order not to lower the transmittance at 220 nm or less, Proceeding of SPIE, 2724,355 (19
An alicyclic or aliphatic compound containing an acid-decomposable group, such as the cholic acid derivative containing an acid-decomposable group described in 96), is preferred as the acid-decomposable dissolution inhibiting compound (D). Examples of the acid-decomposable group and the alicyclic structure include the same as those described for the acid-decomposable resin. (D) The amount of the acid-decomposable dissolution-inhibiting compound to be added is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, based on the solid content of the whole positive resist composition. Specific examples of the acid-decomposable dissolution inhibiting compound (D) are shown below, but the invention is not limited thereto.

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(F) Nitrogen-containing basic compound The positive resist composition of the present invention contains (F) a nitrogen-containing basic compound in order to reduce a change in performance over time from exposure to heating. Is preferred. Preferred structures include those represented by the following formulas (A) to (E).

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵⁰ and R ²⁵¹ are bonded to each other to form a ring. Good.

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(Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R
²⁵⁶ independently represents an alkyl group having 1 to 6 carbon atoms). Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted amino Examples include morpholine, substituted or unsubstituted aminoalkyl morpholine, and the like, and include mono, di, trialkylamine, substituted or unsubstituted aniline, substituted or unsubstituted piperidine, mono and diethanolamine, and the like. Preferred substituents are an 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 It is.

As particularly preferred compounds, guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylamino Pyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 4
-Aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N-
(2-aminoethyl) piperidine, 4-amino-2,
2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl -1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5
-Methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N-
(2-aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 2,4,4
5-triphenylimidazole, tri (n-butyl) amine, tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine,
Examples include, but are not limited to, 2,6-diisopropylaniline, N-cyclohexyl-N'-morpholinoethylthiourea, and the like. These (F) nitrogen-containing basic compounds may be used alone or in combination of two or more.

The amount of the (F) nitrogen-containing basic compound to be used is generally 0.001% based on the solid content of the photosensitive resin composition.
It is 1 to 10% by weight, preferably 0.01 to 5% by weight. If the amount is less than 0.001% by weight, the effect of the addition of the nitrogen-containing basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

{(G) Fluorine and / or Silicon Surfactant} The positive resist composition of the present invention comprises a fluorine and / or silicon surfactant (a fluorine surfactant and a silicon surfactant). , A surfactant containing both a fluorine atom and a silicon atom) or two or more kinds thereof. When the positive resist composition of the present invention contains the surfactant (G) described above, when using an exposure light source of 250 nm or less, particularly 220 nm or less, it has good sensitivity and resolution, and has little adhesion and little development defects. It becomes possible to provide a resist pattern. These (G) surfactants include, for example, those described in
-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165
No., JP-A-8-62834, JP-A-9-54432, JP-A-9-5988
And the commercially available surfactants described below can be used as they are. Commercially available surfactants that can be used, for example, F-top EF301, EF30
3, (Shin-Akita Chemical Co., Ltd.), Florado FC430, 431 (Sumitomo 3M), MegaFac F171, F173, F176, F18
9, R08 (Dainippon Ink Co., Ltd.), Surflon S-382,
SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants or silicon-based surfactants. In addition, polysiloxane polymer KP-341
(Shin-Etsu Chemical Co., Ltd.) and Troysol S-366 (Troy Chemical Co., Ltd.) can also be used as the silicon-based surfactant.

The amount of the surfactant used is preferably 0.00 to the total amount of the positive resist composition (excluding the solvent).
01 to 2% by weight, more preferably 0.001 to 1% by weight
It is.

<(E) Resin having a monocyclic or polycyclic alicyclic hydrocarbon structure in the main chain or side chain that is insoluble in water and soluble in an alkaline developer> Positive photoresist composition of the present invention Contains (E) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure in a main chain or a side chain, which does not contain an acid-decomposable group and is insoluble in water and soluble in an alkali developing solution. And thereby increase the sensitivity. In the present invention, in the case of a composition containing (A), (C), (D) and (E), the component (E) is an essential component. When the component (E) is an essential component, the amount of the component (E) added to the composition is preferably 20 to 99.8% by weight, more preferably 50 to 99.5% by weight based on the total solid content. % By weight.

In the present invention, the molecular weight is from 1000 to 20.
Novolak resins of about 000, molecular weight 3000 to 50
About 000 polyhydroxystyrene derivatives can be used as such a resin,
Since it has a large absorption for light of m or less, it is preferable to use it by partially hydrogenating it, or to use it in an amount of 30% by weight or less of the total resin amount. Further, a resin containing a carboxyl group as an alkali-soluble group can also be used. The carboxyl group-containing resin preferably has a monocyclic or polycyclic alicyclic hydrocarbon group. Specifically, a copolymer of a methacrylic acid ester having an alicyclic hydrocarbon structure that does not show acid-decomposability and a (meth) acrylic acid or a (meth) acrylic acid ester of an alicyclic hydrocarbon group having a terminal carboxyl group And the like.

{Other Substances} The positive resist composition of the present invention may further contain, if necessary, a dye, a plasticizer, a surfactant other than the above-mentioned component (D), a photosensitizer, and a developer. A compound that promotes the properties can be contained. The compound capable of accelerating dissolution in a developer that can be used in the present invention is a low molecular compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable for the same reason as described above. The preferred addition amount of these dissolution promoting compounds is 2 to 50% by weight, more preferably 5 to 50% by weight, based on the resin which is decomposed by the action of the acid (B) and has increased solubility in an alkali developer.
30% by weight. An addition amount exceeding 50% by weight is not preferable because new development defects such as development residue deterioration and pattern deformation during development occur.

A phenol compound having a molecular weight of 1,000 or less can be prepared by those skilled in the art by referring to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. It can be easily synthesized. Specific examples of the alicyclic group having a carboxyl group, or an aliphatic compound include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, and lithocholic acid, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid, cyclohexanecarboxylic acid, and cyclohexane. Examples include, but are not limited to, dicarboxylic acids.

{Method of Use} The photosensitive composition of the present invention is obtained by dissolving the above components in a predetermined solvent in a mixed state. It is used by coating on a predetermined 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 monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl pyruvate, methyl pyruvate , Pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc., and these solvents are used alone or in combination. Among them, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, and ethyl ethoxypropionate are used alone or in a mixture of two kinds in a ratio of 1/9 to 9/1. preferable.

In the present invention, a surfactant other than the (D) fluorine-based and / or silicon-based surfactant may be added. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether and the like Polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate,
Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,
Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate can be exemplified. These surfactants may be added alone or in some combination.

The positive resist composition dissolved in a solvent is
It is applied on a predetermined substrate as follows. That is, the photosensitive composition is applied on a substrate (eg, silicon / silicon dioxide coating) such as used in the production of precision integrated circuit devices by a suitable application method such as a spinner or a coater. After the application, the film is exposed through a predetermined mask, baked and developed. By doing so, a good resist pattern can be obtained. Here, the exposure light is preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less. Specifically, a KrF excimer laser (248 nm) and an ArF excimer laser (19
3 nm), F ₂ excimer laser (157 nm), X
Line, electron beam and the like.

In the developing step, a developing solution is used as follows. As the developer of the photosensitive composition, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as ammonia water, ethylamine, primary amines such as n-propylamine, Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like An alkaline aqueous solution such as a quaternary ammonium salt, a cyclic amine such as pyrrole, or pyrhelidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution for use.

[0146]

EXAMPLES The present invention will now be described in detail with reference to examples, but the scope of the present invention is not at all limited by the examples.

Synthesis Example-1 <Synthesis of (B) Resin> (1) [Synthesis of Resin (P1) (a1) / (b1) = 50
/ 50] 5.0 g of 2-methyl-2-adamantane methacrylate, 4.23 g of mevalonic lactone methacrylate, 7.02 g of N, N-dimethylacetamide heated to 60 ° C. in a nitrogen stream, polymerization initiator 2,2′- Azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries)
A solution of 534 g in 30.0 g of N, N-dimethylacetamide was added dropwise over 4 hours. 60 ° C
After reacting for 2 hours, 0.267 g of V-65 was added,
The reaction was further performed for 2 hours. The reaction solution is deionized water 100
The mixture was poured into 0 ml, and the precipitated powder was collected by filtration. This is THF
, And poured into 1500 ml of hexane, and the resulting powder was dried to obtain a resin (I-1). The weight average molecular weight of the obtained resin was 5,500, and the degree of dispersion (Mw / Mn) was 1.9. Incidentally, the weight average molecular weight and the degree of dispersion,
It is a polystyrene equivalent value measured by the DSC method.

(2) [Synthesis of Resin (P2) to Resin (P12)] Resin (P2) to Resin (P2)
Resin (P12) was synthesized in order. Table 1 shows the molecular weight and the degree of dispersion of these resins.

[0149]

[Table 1]

<Adjustment of resist> [Examples 1 to 14 and Comparative examples 1 to 3] The materials shown in Table 2 were dissolved in propylene glycol monomethyl ether acetate to prepare a solution having a solid content of 15%, and the solution was adjusted to 0.1%.
The solution was filtered through a μm Teflon (registered trademark) filter to prepare a resist composition. The prepared composition was evaluated by the following method, and the results are shown in Table 3.

[0151]

[Table 2]

(Description of Table 2) (C-4) is commercially available 4,
4,5,5,6,6,6-heptafluoropentanoic acid was used. Similarly, various compounds were synthesized using commercially available products in some cases. Examples of the acid generator include TPSTF; triphenylsulfonium triflate TSPFB; triphenylsulfonium perfluorobutanesulfonate TPSPFOS; triphenylsulfonium perfluorooctanesulfonate TBDPIPFBS; bis (4-t-butylphenyl)
Represents iodonium perfluorobutanesulfonate.

Examples of the amine include DBN; 1,5-diazabicyclo [4.3.0] -5-
Nonene DBU; 1,8-diazabicyclo [5.4.0] -7-
Undecene TPI; represents 2,4,5-triphenylimidazole.

As the surfactant, W-1; Megafac F176 (Dainippon Ink Co., Ltd.)
(Fluorine) W-2; Megafac R08 (Dainippon Ink Co., Ltd.)
(Fluorine and silicon type) W-3; Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon type) W-4; Troysol S-366 (Troy Chemical Co., Ltd.)
(Fluorinated).

<Image evaluation method>

(1) Evaluation of Sensitivity, Resolution, Pattern Profile, and Standing Wave An antireflection film DUV-42 manufactured by Brewer Science Co. was uniformly coated on a silicon substrate that had been treated with hexamethyldisilazane by a spin coater for 600 angstroms. Then, after drying on a hot plate at 100 ° C. for 90 seconds, heating and drying were performed at 190 ° C. for 240 seconds. afterwards,
Each resist composition was applied with a spin coater and dried at 120 ° C. for 90 seconds to form a 0.50 μm resist film. An ArF excimer laser stepper (ISI NA = 0.6) is passed through this mask through a mask.
And heated on a hot plate at 120 ° C. for 90 seconds immediately after exposure. Further, the resist was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and dried to obtain a resist line pattern.

The sensitivity indicates an exposure amount for reproducing a mask pattern of 0.20 μm. The resolving power indicates a limit resolving power at an exposure amount for reproducing a mask pattern of 0.20 μm.

For the pattern profile, the pattern shape was observed with a scanning electron microscope.

In the standing wave, the cross-sectional shape of the obtained resist pattern was evaluated as x when the side wall of the pattern was corrugated, and as ○ when the corrugation was not observed.

[0160]

[Table 3]

The following are clear from the results shown in Table 3. The compositions of Examples 1 to 14 were excellent in sensitivity and resolution, reduced in standing waves, and formed excellent pattern profiles. On the other hand, in the case of the compositions of Comparative Examples 1 to 3 in which the compound (C) of the present invention is not blended, the resolution is equivalent to that of the examples, but the sensitivity, standing wave and pattern profile are Inferior to the example composition.

[0162]

The positive resist composition of the present invention has excellent sensitivity and resolution, reduces standing waves, and can form an excellent pattern profile. Therefore, the positive resist composition of the present invention is suitably used for microphotofabrication using far ultraviolet light, particularly ArF excimer laser light.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 504 504 H01L 21/027 H01L 21/30 502R (72) Inventor Nakao Former F-term in Fujisha Shin Film Co., Ltd. 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Pref. EF037 EH038 EH126 EJ028 EN019 ER009 ER029 ES006 EU139 EU186 EU216 EU239 EV047 EV226 EV256 EV296 EV306 EV326 FD206 FD310 GP03

Claims (6)

[Claims] 1. A compound which (A) generates an acid upon irradiation with an actinic ray or radiation, and (B) has a monocyclic or polycyclic alicyclic hydrocarbon structure in a main chain or a side chain, and is acted upon by the action of an acid. A resin that decomposes to increase its solubility in an alkaline developer,
(C) A positive resist composition comprising a compound having a structure represented by the following general formula (I). Embedded image In the general formula (I), R represents a hydrocarbon group containing a fluorine atom. X represents a divalent linking group containing no fluorine atom. 2. It further comprises (D) a low molecular weight dissolution inhibiting compound having a molecular weight of 3,000 or less, which has a group decomposable by an acid and whose dissolution rate in an alkaline developer is increased by the action of an acid. The positive resist composition according to claim 1, wherein 3. A compound which generates an acid upon irradiation with actinic rays or radiation, (C) a compound having a structure represented by the following general formula (I), and (D) a group which can be decomposed by an acid. A low molecular weight dissolution inhibiting compound having a molecular weight of 3,000 or less, whose dissolution rate in an alkali developer is increased by the action of an acid, (E) a monocyclic or polycyclic alicyclic ring which is insoluble in water and soluble in an alkali developer A positive resist composition comprising a resin having a hydrocarbon structure in a main chain or a side chain. Embedded image In the general formula (I), R represents a hydrocarbon group containing a fluorine atom. X represents a divalent linking group containing no fluorine atom. 4. The positive resist composition according to claim 1, further comprising (F) a nitrogen-containing basic compound. 5. The method according to claim 1, further comprising (G) a fluorine-based and / or silicon-based surfactant.
5. The positive resist composition according to any one of 4. 6. The positive resist composition according to claim 1, wherein the irradiation light is far ultraviolet light having a wavelength of 220 nm or less.