JP2002122994A - Positive type photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve a problem on a technique for enhancing performance peculiar to microphotofabrication using far ultraviolet light, particularly ArF excimer laser light and to provide a positive type photosensitive composition excellent in density dependence and excellent also in exposure margin. SOLUTION: The positive type photosensitive composition contains (A) a compound which generates an acid when irradiated with active light or radiation, (B) a resin which is decomposed by the action of the acid to increase its solubility in an alkali developing solution and (C) an onium salt of a carboxylic acid. The resin (B) has a monocyclic or polycyclic alicyclic hydrocarbon structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive composition used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal and a thermal head, and other photofabrication processes. .

[0002]

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.

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 (Japanese Patent Laid-Open No. 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.

[0005] 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 a 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.

JP-A-9-43837 describes the use of a photoacid generator and a base which can be decomposed into a neutral compound by exposure to radiation.
-125907 describes the use of a compound that generates a carboxylic acid having a boiling point of 150 ° C. or higher and a compound that generates an acid other than the carboxylic acid.

However, even in the above-mentioned technology, there is room for improvement in the density dependency. Since various patterns are included as a tendency of recent devices, various performances are required for resists. One of them is sparse / dense dependency. The device has a pattern in which the space is wider than the line, and an isolated line, as opposed to a portion where the line is dense.
Therefore, it is important to resolve various lines with high reproducibility. However, it is not always easy to reproduce various lines due to optical factors, and the solution at present is not clear. Further, there has been a strong demand for further improving the exposure margin. Here, the exposure margin refers to a phenomenon in which when the exposure amount changes, the line width of the obtained pattern changes.

[0011]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the problem of the performance improvement technology inherent in microphotofabrication using far ultraviolet light, particularly ArF excimer laser light. It is an object of the present invention to provide a positive photosensitive composition which is excellent in density dependence and exposure margin.

[0012]

Means for Solving the Problems The present invention is a positive photosensitive composition having the following constitution, thereby achieving the above object of the present invention.

(1) (A) a compound which generates an acid upon irradiation with actinic rays or radiation; (B) a resin which is decomposed by the action of an acid to increase the solubility in an alkaline developer; and (C) an onium carboxylate. (B) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, wherein the resin which is decomposed by the action of an acid and has increased solubility in an alkali developing solution is a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure. Composition.

(2) (D) A low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, which has a group decomposable by an acid and whose dissolution rate in an alkali developing solution is increased by the action of an acid. The positive photosensitive composition according to the above (1), which is characterized in that: (3) The positive photosensitive composition according to (1) or (2), wherein the resin (B) is a resin further having a lactone structure.

(4) (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation, (C) an onium carboxylate, (D) a group having a group decomposable by an acid, and having a dissolution rate in an alkaline developer. Molecular weight 300 increased by the action of acid
0 or less low molecular weight dissolution inhibiting compound (E) The above-mentioned (1), which comprises a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, being insoluble in water and soluble in an alkali developing solution. The positive photosensitive composition according to any one of (1) to (3).

(5) The method according to any one of (1) to (4), wherein the (C) onium carboxylate is at least one selected from sulfonium carboxylate and iodonium carboxylate. The positive photosensitive composition as described in the above.

(6) The method according to any one of (1) to (5), wherein the carboxylate residue of the onium carboxylate (C) does not contain an aromatic group or a carbon-carbon double bond. The positive photosensitive composition as described in the above.

(7) The above-mentioned (1) to (6), wherein the carboxylate residue of the onium carboxylate (C) is a fluorine-substituted linear, branched or cyclic alkyl carboxylate anion. The positive photosensitive composition according to any one of the above.

(8) The composition according to (1), which is a composition for exposure with far ultraviolet light having a wavelength of 220 nm or less.
The positive photosensitive composition according to any one of (1) to (7).

[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 camphor sulfonic acid. Preferred are alkanesulfonic acid, perfluoroalkanesulfonic acid, alkyl-substituted benzenesulfonic acid, and pentafluorobenzenesulfonic acid.

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

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

[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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The onium salts represented by the general formulas (PAG3) and (PAG4) are known. 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 formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0049]

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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.

[0051]

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[0052]

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[0053]

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[0054]

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

[0056]

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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.

[0058]

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Among the compounds which decompose upon irradiation with actinic rays or radiation to generate an acid according to the present invention, particularly preferred examples are given below.

[0060]

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[0061]

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[0062]

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[0063]

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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 which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.001 to the total composition (excluding the solvent) of the positive photosensitive composition of the present invention. To 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.01 to 5% by weight.
Used in the range of weight percent. The amount of the compound that generates an acid when decomposed by irradiation with actinic rays or radiation is 0.0
If the amount is less than 1% by weight, the sensitivity is lowered, and the addition amount is
If it exceeds 0% by weight, the light absorption of the resist becomes too high,
It is not preferable because the profile is deteriorated and the process (especially baking) margin is narrowed.

<< (B) Resin whose solubility in an alkali developing solution is increased by the action of an acid >> In the present invention, (B)
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.

[0067]

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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, a sec-butyl group, which may have a substituent,
Examples thereof include those having 1 to 8 carbon atoms such as a hexyl group, a 2-ethylhexyl group and an octyl group. 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 may have a substituent,
Examples thereof include those having 2 to 6 carbon atoms such as vinyl group, propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group and cyclohexenyl group.

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.

[0072]

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[0073]

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[0074]

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[0075]

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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 preferably contains a lactone structure. As described above, each of the alicyclic hydrocarbon structure and the lactone structure may or may not have acid-decomposability. As a repeating unit having such a lactone structure,
It is preferably a structural unit represented by the following general formula (IV ′).

[0078]

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[0079] In the general formula (IV '), R ₁ a represents a hydrogen atom or a methyl group. W ₁ represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, or a combination of two or more groups selected from the group consisting of an ester group. Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ , Re ₁
Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3;
n is 2 or more and 6 or less.

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

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

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

Hereinafter, specific examples of the repeating structural unit having a lactone structure will be shown, but the present invention is not limited thereto.

[0084]

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[0085]

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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 acid-decomposable resin of the present invention may further contain a repeating unit having a group represented by any of the following formulas (V-1) to (V-4).

[0088]

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In the general formulas (V-1) to (V-4),
R _{1b to} R _5b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. Two of R _{1b to} R _5b may combine to form a ring.

In the general formulas (V-1) to (V-4),
Examples of the alkyl group for R _{1b to} R _5b include a linear or branched alkyl group, and may have a substituent. The linear or branched alkyl group has 1 to 1 carbon atoms.
Twelve linear or branched alkyl groups are preferred,
More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms, and still more preferably, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and t -Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group. The cycloalkyl group in R _{1b to} R _5b is preferably a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. The alkenyl group in R _{1b to} R _5b is preferably an alkenyl group having 2 to 6 carbon atoms such as a vinyl group, a propenyl group, a butenyl group, and a hexenyl group. Examples of the ring formed by combining two members out of R _{1b to} R _5b include a 3- to 8-membered ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring. The general formula (V-1)
R _{1b to} R _5b in (V-4) may be connected to any of the carbon atoms constituting the cyclic skeleton.

Preferred substituents which the alkyl group, cycloalkyl group and alkenyl group may have are an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). Atom), an acyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, a cyano group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group having 2 to 5 carbon atoms, and a nitro group.

The repeating units having groups represented by formulas (V-1) to (V-4) include those represented by formula (II-
A) or (II-B) wherein at least one of R ₁₃ ′ to R ₁₆ ′ has a group represented by the above general formulas (V-1) to (V-4) (for example, -COOR ₅ R ₅ is a group represented by the general formula (V-
1) to (V-4)), or a repeating unit represented by the following general formula (AI).

[0093]

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In the general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Preferred substituents which the alkyl group of _Rb0 may have are those represented by the general formulas (V-1) to (V-1).
Preferred examples of the substituent which may be possessed by the alkyl group as R _1b in (V-4) include those exemplified above. Examples of the halogen atom for R _b0 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R
_b0 is preferably a hydrogen atom. A ′ represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group obtained by combining these. B ₂ represents a group represented by any one of formulas (V-1) to (V-4). In A ′, examples of the combined divalent group include those represented by the following formula.

[0095]

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

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

[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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Further, the acid-decomposable resin of the present invention can further contain a repeating unit represented by the following general formula (VI).

[0106]

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In the general formula (VI), A ₆ represents a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, an ester group, or a combination of two or more groups. Represents R _6a represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, or a halogen atom.

In formula (VI), examples of the alkylene group represented by A ₆ include groups represented by the following formula. -[C (Rnf) (Rng)] r- In the above formula, Rnf and Rng are a hydrogen atom, an alkyl group,
Represents a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, which may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r is an integer of 1 to 10. General formula (VI)
In the above, examples of the cycloalkylene group for A ₆ include those having 3 to 10 carbon atoms, and a cyclopentylene group,
Examples thereof include a cyclohexylene group and a cyclooctylene group.

The bridged alicyclic ring containing Z ₆ may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), an alkoxycarbonyl group (preferably having 1 to 5 carbon atoms), an acyl group (eg, a formyl group and a benzoyl group), and an acyloxy group ( For example, a propylcarbonyloxy group, a benzoyloxy group), an alkyl group (preferably having 1 to 4 carbon atoms), a carboxyl group, a hydroxyl group, an alkylsulfonylsulfamoyl group (such as —CONHSO ₂ CH ₃ ) are exemplified. still,
The alkyl group as a substituent may be further substituted with a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), or the like.

In the general formula (VI), the oxygen atom of the ester group bonded to A ₆ may be bonded at any position of the carbon atom constituting the bridged alicyclic ring structure including Z _6. Good.

The following are specific examples of the repeating unit represented by the general formula (VI), but the invention is not limited thereto.

[0112]

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[0113]

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The dry etching resistance is improved by containing a repeating unit having a group represented by the above formulas (V-1) to (V-4) or a repeating unit represented by the above formula (VI). Can be done.

The monocyclic or polycyclic alicyclic hydrocarbon structure contained in the acid-decomposable resin is a monocyclic alicyclic hydrocarbon having 3 or more carbon atoms, preferably 3 to 8 carbon atoms. Groups having a skeleton can be mentioned, for example, cyclopropane,
Examples thereof include cyclic hydrocarbon skeletons such as cyclobutane, cyclopentane, and cyclohexane. Examples of the polycyclic type include those 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. More specifically,
Examples of the structure described below are given.

On the other hand, the acid-decomposable group which may be contained in the alicyclic hydrocarbon group may be linked by an acid-decomposition structure, decomposed by the action of an acid, and the alicyclic hydrocarbon group may be eliminated. ,
Alternatively, the group represented by the above formula (x) or (y) may be bonded to the alicyclic hydrocarbon group directly or via a linking group. When a monocyclic or polycyclic alicyclic hydrocarbon group is provided on 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.

The repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure is preferably a structural unit represented by the following general formulas (II) to (V).

[0118]

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[0119]

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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.

The alkyl groups represented by R ¹¹ , R ¹² and R ^{14 to} R ¹⁶ include methyl, ethyl, propyl, n-
Examples thereof include a hydrocarbon group having 1 to 4 carbon atoms such as a butyl group and a sec-butyl group. 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.

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.

-CO-NR ²⁸ -R ²⁹ -in X ₁ -X ₃
The substituents R ^28, 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 examples of the substituent 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.

Representative examples of the polycyclic or monocyclic alicyclic moiety of the polycyclic or monocyclic cyclic hydrocarbon group, that is, A, are as follows. .

[0131]

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[0132]

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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.

[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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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 above-mentioned acid-decomposable resin 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 units having a carboxyl group in the acid-decomposable resin contained in the positive photosensitive composition of the present invention depends on the performance such as alkali developability, substrate adhesion, and sensitivity. Although it is adjusted, it is preferably 0 to 6 with respect to all repeating structural units of the acid-decomposable resin.
The range is 0 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.

[0148]

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[0149]

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

[0151]

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[0152] In the general formula _{(VII), R 2 c~R 4} c represents a hydrogen atom or a hydroxyl group independently. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group.

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

The repeating unit having a group represented by the general formula (VII) includes the above-mentioned general formula (II-A) or (II-
B) wherein at least one of R ₁₃ ′ to R ₁₆ ′ has a group represented by the general formula (VII) (for example, —COO
R ₅ of R ₅ represents a group represented by formulas (V-1) to (V-4)), or a repeating unit represented by the following formula (AII).

[0155]

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[0156] In formula (AII), R ₁ c represents a hydrogen atom or a methyl group. R ₂ c to R ₄ c represents a hydrogen atom or a hydroxyl group independently. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group.

Specific examples of the repeating unit having the structure represented by formula (AII) are shown below, but it should not be construed that the invention is limited thereto.

[0158]

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

[0160]

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

In the general formula (VIII), Z ₂ represents-
Represents O- or -N ( _R41 )-. Here, R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OS
Represents O ₂ -R ₄₂ . R ₄₂ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

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

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

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

[0166]

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[0167]

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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 such as alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) acrylate (eg, 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, (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group Octyl group, 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 the balance between dry etching resistance, alkali developability and the like. At least 20 mol%. The content is more preferably 30 to 80 mol%, further preferably 35 to 70 mol%.
Mol%, and more preferably in the range of 40 to 60 mol%.

In the present invention, the content of the resin whose solubility in an alkali developing solution is increased by the action of an acid (B) is 20 to the total composition or the solid content excluding the solvent.
99.8% by weight, preferably 50 to 99.5% by weight.

(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) Onium carboxylate} As the onium carboxylate (C) in the present invention, sulfonium carboxylate, iodonium carboxylate, ammonium carboxylate and the like can be mentioned. Examples of the onium carboxylate (C) that can be used in the present invention include compounds represented by the following general formulas (AI) to (AVI).

[0179]

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[0180]

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[0181]

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In the above formula, R _{301 to} R ₃₃₇ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group;
Linear, branched or cyclic alkoxy groups, hydroxy groups,
Represents a halogen atom or a —S—R ₀ group. R ₀ is a straight chain,
Represents a branched, cyclic alkyl or aryl group. R _s1 ~
R _s2 independently represents a linear, branched or cyclic alkyl group. R _{N1 to} R _N4 each independently represent a linear, branched or cyclic alkyl group which may have a substituent. R _N1 ~
Any two substituents of R _N4 may combine to form a ring. Further, in the general formula (AV), R _{N1 to} R _N1
Any one of the _N4 X ^- may be linked intramolecularly.

Each of R _{s3 to} R _s5 independently represents a linear, branched or cyclic alkyl group or aryl group which may have a substituent. Further, two or more of R _{s3 to} R _s5 may combine to form a ring. The general formula (AVI)
Also includes those containing two or more sulfonium structures.

The above X ^- represents a carboxylic acid compound represented by the following formula converted to an anion.

[0185]

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[0186]

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In the above formula, R ₃₃₈ represents a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms (here, alkyl Group or cycloalkyl group may contain an oxygen atom or a nitrogen atom in the chain), having 1 to 20 carbon atoms
A linear, branched or cyclic alkenyl group, a linear, branched or cyclic alkynyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms, carbon The substituted or unsubstituted aryl group, halogen atom, nitro group, and camphor residue represented by Formulas 6 to 20 are shown. At least a part of the hydrogen atoms of the alkyl group or the cycloalkyl group may be substituted with a halogen atom and / or a hydroxyl group. Further, at least a part of the hydrogen atoms of the alkenyl group may be substituted with a halogen atom and / or a hydroxyl group. Here, examples of the substituent of the aryl group include an alkyl group, a nitro group, a hydroxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, and a halogen atom.

R ₃₃₉ is a single bond or a group having 1 to 2 carbon atoms.
0 linear, branched or cyclic alkylene group (here, the chain of the alkylene group may contain an oxygen atom or a nitrogen atom); a linear, branched or cyclic C 1-20 alkyl group; shows the alkenylene group or alkoxide alkylene group having 2 to 20 carbon atoms,, R ₃₃₈ there are a plurality, R _{3 39}
May be the same or different from each other. At least a part of the hydrogen atoms of the alkylene group may be substituted with a halogen atom and / or a hydroxyl group, and at least a part of the hydrogen atoms of the alkenylene group may be substituted with a halogen atom.

R ₃₄₀ represents a hydroxyl group or a halogen atom, and a plurality of R ₃₄₀ may be the same or different. m, n, p and q are each independently an integer of 0 to 3, and m + n ≦ 5 and p + q ≦ 5. z is 0 or 1.

In the general formulas (AI) to (AVI), the linear or branched alkyl group in R _{301 to} R ₃₃₇ , R _{s1 to} R _s5 , and R _{N1 to} R _N4 may have a substituent. ,
Methyl group, ethyl group, propyl group, n-butyl group, se
Those having 1 to 4 carbon atoms such as a c-butyl group and a t-butyl group are exemplified. The cyclic alkyl group may have a substituent, a cyclopropyl group, a cyclopentyl group,
Those having 3 to 8 carbon atoms such as a cyclohexyl group are exemplified.

Examples of the alkoxy group represented by R _{301 to} R ₃₃₇ include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group. To four. Examples of the halogen atom of R _{301 to} R ₃₃₇ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As the aryl group for R ₀ and R _{s3 to} R _s5 ,
Examples thereof include those having 6 to 14 carbon atoms which may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group. Preferred as these substituents are alkoxy groups having 1 to 4 carbon atoms, halogen atoms (fluorine atom, chlorine atom, iodine atom), aryl groups having 6 to 10 carbon atoms, and alkenyl groups having 2 to 6 carbon atoms. , A cyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, a nitro group and the like.

Aromatic, monocyclic or polycyclic hydrocarbons formed by bonding any two substituents out of R _{N1 to} R _N4 (including an oxygen atom and a nitrogen atom in these rings) Benzene structure, naphthalene structure, cyclohexane structure, norbornene structure, oxabicyclo structure and the like.

The general formulas (AI) to (A) used in the present invention
The sulfonium, iodonium and ammonium compounds represented by VI) have, as a counter anion X ⁻ , a carboxyl group (—COO) of at least one of the carboxylic acid compounds represented by the above formulas (C1) to (C10).
H) as an anion (—COO ⁻ ).

Examples of the linear or branched alkyl group having 1 to 30 carbon atoms in R ₃₃₈ (where the chain of the alkyl group may contain an oxygen atom or a nitrogen atom) include a methyl group and an ethyl group. Group, propyl group, butyl group, pentyl group,
Hexyl group, dodecyl group, 2-ethoxyethyl group, 2-
And a hydroxyethyl group.

Examples of the cycloalkyl group having 1 to 30 carbon atoms include a monocyclic or polycyclic alicyclic group such as a cyclohexyl group, an adamantyl group, a cyclopentyl group, a bicyclo ring, an oxabicyclo ring and a tricyclo ring. No. Representative structural examples of the monocyclic or polycyclic alicyclic moiety include, for example, those shown below.

[0197]

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[0198]

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Examples of the linear, branched or cyclic alkenyl group having 1 to 20 carbon atoms include ethenyl, propenyl,
Isopropenyl, cyclohexene and the like. Examples of the linear, branched or cyclic alkynyl group having 1 to 20 carbon atoms include acetylene and propenylene. Examples of the linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, propyloxy, butoxy, cyclohexyloxy, isobutoxy, dodecyloxy and the like. As the substituted or unsubstituted aryl group having 6 to 20 carbon atoms, phenyl,
Naphthyl, anthranil and the like can be mentioned.

Examples of the substituent for the linear, branched alkyl, cycloalkyl and aryl groups include an alkyl group, a nitro group, a hydroxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group and a halogen atom.

Examples of the linear, branched or cyclic alkylene group having 1 to 20 carbon atoms for R ₃₃₉ (here, the chain of the alkylene group may contain an oxygen atom or a nitrogen atom) include: Examples include methylene, ethylene, propylene, butylene, isobutylene, ethoxyethylene, cyclohexylene and the like. As a linear, branched or cyclic alkenylene group having 1 to 20 carbon atoms, vinylene,
Arylene and the like.

In the present invention, the onium carboxylate (C) is preferably an iodonium salt or a sulfonium salt. Further, it is preferable that the carboxylate residue of the onium carboxylate (C) of the present invention does not contain an aromatic group and a carbon-carbon double bond. Particularly preferred X ⁻ is a linear, branched, monocyclic or polycyclic alkyl carboxylate anion having 1 to 30 carbon atoms. More preferably, an anion of a carboxylic acid in which some or all of these alkyl groups are substituted with fluorine is preferred. An oxygen atom may be contained in the alkyl chain. This allows 220 nm
Transparency with respect to the following light is secured, sensitivity and resolution are improved, dependency on density is improved, and exposure margin is improved.

Examples of the anion of the fluorine-substituted carboxylic acid include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid,
Pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorocyclohexanecarboxylic acid,
Anion of 2,2-bistrifluoromethylpropionic acid and the like can be mentioned.

Hereinafter, specific examples of the onium carboxylate (C) will be shown, but the present invention is not limited thereto.

[0205]

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[0206]

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[0207]

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[0208]

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[0209]

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[0210]

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[0211]

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[0212]

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[0213]

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In the above general formula, Me is a methyl group, E
t represents an ethyl group. The above general formulas (AI) to (AVI)
Can be used alone or in combination of two or more.

The compounds represented by formulas (AI) to (AVI) can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid in a suitable solvent. Sulfonium hydroxide, iodonium hydroxide and ammonium hydroxide can be obtained by reacting sulfonium iodide, iodonium iodide and ammonium iodide with silver oxide in a suitable solvent.

The content of the onium carboxylate (C) in the composition is 0.1 to 20% by weight based on the total solid content of the composition.
Is suitable, preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight.

{(D) Acid-Decomposable Dissolution Inhibiting Compound} The positive photosensitive 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. ,
Dissolution inhibiting low molecular weight compounds having a molecular weight of 3000 or less (hereinafter, referred to as
"(D) acid-decomposable dissolution inhibiting compound"). Proceeding of SPIE, 2724,355 (1996)
As the acid-decomposable dissolution inhibiting compound (D), an alicyclic or aliphatic compound having an acid-decomposable group, such as the cholic acid derivative containing an acid-decomposable group described in (1), is preferred. 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 photosensitive composition. . Specific examples of the acid-decomposable dissolution inhibiting compound (D) are shown below, but the invention is not limited thereto.

[0218]

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{(F) Nitrogen-containing basic compound} The positive photosensitive 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).

[0220]

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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.

[0222]

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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.

Particularly preferred compounds are 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 nitrogen-containing basic compounds (F) are used alone or in combination of two or more. (F) The amount of the nitrogen-containing basic compound to be used is generally 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content of the photosensitive resin composition. 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 photosensitive resin composition of the present invention comprises a fluorine and / or silicon surfactant (a fluorine surfactant and a silicon surfactant). Surfactant or a surfactant containing both a fluorine atom and a silicon atom), or two or more kinds. When the positive photosensitive 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, excellent sensitivity and resolution, adhesion and development defects can be obtained. It is possible to provide a small number of resist patterns. 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
No., U.S. Pat.No. 5,405,720, No. 5,306,692, No. 5,529,881,
No. 5296330, No. 5436098, No. 5576143, No. 5294511
And No. 5824451. The following commercially available surfactants can also be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC
430, 431 (Sumitomo 3M Limited), Mega Fuck F171,
F173, F176, F189, R08 (manufactured by Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (Troy Chemical Co., Ltd.) )) Or a silicon-based surfactant. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

The amount of the surfactant used is preferably 0.000 to the total amount of the positive photosensitive composition (excluding the solvent).
The content is 1 to 2% by weight, more preferably 0.001 to 1% by weight.

{(E) Alkali-Soluble Resin} The positive photoresist composition of the present invention contains (E) a resin which is insoluble in water and soluble in an alkali developing solution and which does not contain an acid-decomposable group. And thus the sensitivity is improved. In the present invention, a novolak resin having a molecular weight of about 1,000 to 20,000 and a polyhydroxystyrene derivative having a molecular weight of about 3,000 to 50,000 can be used as such a resin. However, these resins have large absorption for light having a wavelength of 250 nm or less. It is preferable to use a partially hydrogenated product 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 for improving dry etching resistance. 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 photosensitive 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 or the like which promotes solubility 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 photosensitive composition dissolved in a solvent 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 (193n)
m), F ₂ excimer laser (157 nm), X-ray, 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.

[0235]

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 of Resin> Synthesis Example (1) [Synthesis of Resin (P1) (a1) / (b1)
= 50/50] 2-methyl-2-adamantane methacrylate 5.0 g, mevalonic lactone methacrylate 4.23 g, polymerization initiator 2,2 in 7.0 g of N, N-dimethylacetamide heated to 60 ° C. under a nitrogen stream. '-Azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical; V-65)
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.

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

[0238]

[Table 1]

Synthesis Example (2) Synthesis of Resin (1) (Side chain type) 2-Ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were charged at a ratio of 55/45, dissolved in methyl ethyl ketone / tetrahydrofuran = 5/5, and solidified. 100 mL of a 20% concentration solution was prepared. To this solution, 2 mol% of V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added, and this was added dropwise to 10 mL of methyl ethyl ketone heated to 60 ° C. over 4 hours under a nitrogen atmosphere. After the addition was completed, the reaction solution was heated for 4 hours, 1 mol% of V-65 was added again, and the mixture was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 3 L of a mixed solvent of distilled water / ISO propyl alcohol = 1/1 was used.
The resin (1) as a white powder crystallized and precipitated was recovered. The polymer composition ratio determined from C ¹³ NMR was 46/54.
Met. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 10,700.

Resins (2) to (15) were synthesized in the same manner as in Synthesis Example (2). The following resin (2) to
The composition ratio and molecular weight of (15) are shown. (Repeat unit 1,
2, 3, and 4 are the order from the left of the structural formula. )

[0241]

[Table 2]

The structures of the resins (1) to (15) are shown below.

[0243]

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[0244]

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[0245]

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[0246]

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Synthesis Example (3) Synthesis of Resin (16) (Main Chain Type) Norbornenecarboxylic acid t-butyl ester, norbornenecarboxylic acid butyrolactone ester and maleic anhydride (40/10/50 molar ratio) and THF (reaction temperature 6)
0% by weight) was placed in a separable flask and heated at 60 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 2 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. Heat for 12 hours. After diluting the obtained reaction mixture twice with tetrahydrofuran, hexane /
It was poured into a mixed solution of isopropyl alcohol = 1/1 to precipitate a white powder. Filter out the precipitated powder,
Drying yielded the desired resin (16). When the molecular weight analysis of the obtained resin (16) by GPC was attempted, it was 8300 (weight average) in terms of polystyrene. From the NMR spectrum, it was confirmed that the molar ratio of norbornene carboxylic acid t-butyl ester / norbornene carboxylic acid butyrolactone ester / maleic anhydride repeating unit of the resin (1) was 42/8/50.

Resins (17) to (27) were synthesized in the same manner as in Synthesis Example (3). The following resin (1)
The composition ratios and molecular weights of 7) to (27) are shown. (Alicyclic olefin units 1, 2, and 3 are in order from the left in the structural formula.)

[0249]

[Table 3]

The following resins (16) to (27)
The structure of is shown.

[0251]

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[0252]

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Synthesis Example (4) Synthesis of Resin (28) (Hybrid Type) Norbornene, maleic anhydride, tbutyl acrylate, and 2-methylcyclohexyl-2-propyl acrylate were reacted at a molar ratio of 35/35/20/10. The solution was charged in a container and dissolved in tetrahydrofuran to prepare a solution having a solid content of 60%. This was heated at 65 ° C. under a stream of nitrogen. When the reaction temperature was stabilized, 1 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 8 hours, the reaction mixture was diluted twice with tetrahydrofuran, and then poured into 5 times the volume of hexane of the reaction mixture to precipitate a white powder. The precipitated powder was taken out by filtration, dissolved in methyl ethyl ketone, reprecipitated in a 5-fold volume hexane / t-butyl methyl ether = 1/1 mixed solvent, and the precipitated white powder was collected by filtration, dried, and dried. As a result, a resin (28) was obtained. When the molecular weight analysis of the obtained resin (28) by GPC was tried, it was 1 in terms of polystyrene.
2,100 (weight average). From the NMR spectrum, the composition of the resin (1) was as follows: norbornene / maleic anhydride / t-butyl acrylate / 2-methylcyclohexyl-2-propyl acrylate of the present invention in a molar ratio of 32 /
39/19/10.

Resins (29) to (41) were synthesized in the same manner as in Synthesis Example (4). The following resin (2)
The composition ratios and molecular weights of 9) to (41) are shown.

[0255]

[Table 4]

The following resins (28) to (41)
The structure of is shown.

[0257]

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[0258]

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[0259]

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[0260]

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Synthesis Example (5) Synthesis of Resin (42) (Hybrid Type) Norbornene carboxylic acid t-butyl ester, maleic anhydride, 2-methyl-2-adamantyl acrylate, norbornene lactone acrylate in a molar ratio of 20/20.
/ 35/25, dissolve in methyl ethyl ketone / tetrahydrofuran = 1/1 solvent, solid content 6
A 0% solution was prepared. This was heated at 65 ° C. under a stream of nitrogen. When the reaction temperature was stabilized, 3 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 12 hours, the reaction mixture was poured into 5 times the amount of hexane to precipitate a white powder. The precipitated powder was dissolved again in a solvent of methyl ethyl ketone / tetrahydrofuran = 1/1 and poured into a 5-fold amount of hexane / methyl tBu ether to precipitate a white powder, which was filtered and taken out. This operation was repeated again to obtain the desired resin (42) by drying. When the molecular weight analysis (RI analysis) of the obtained resin (42) by GPC was attempted, it was 11 in terms of polystyrene.
600 (weight average) and the amount of residual monomer was 0.4%. From the NMR spectrum, the composition of the resin (1) was found to be the norbornene / maleic anhydride / 2-methyl-
The molar ratio of 2-adamantyl acrylate / norbornene lactone acrylate was 18/23/34/25.

In the same manner as in Synthesis Example (5), Resins (43) to (66) were synthesized. The following resin (4)
The composition ratios and molecular weights of 3) to (66) are shown.

[0263]

[Table 5]

The following resins (42) to (66)
The structure of is shown.

[0265]

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[0266]

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[0267]

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[0268]

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[0269]

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<Adjustment of resist> [Examples 1 to 86 and Comparative examples 1 to 3] The components shown in Table 6 were dissolved in propylene glycol monomethyl ether acetate to prepare a solution having a solid content of 15%.
The mixture was filtered through a 1 μm Teflon (registered trademark) filter to prepare a photosensitive composition. The components shown in Tables 7 to 9 were dissolved in the solvents shown in Tables 7 to 9 to prepare a solution having a solid content of 15%, and this was filtered through a 0.1 μm Teflon filter to prepare a photosensitive composition. did. The prepared compositions were evaluated by the following methods, and the results are shown in Tables 10 to 13.

[0271]

[Table 6]

[0272]

[Table 7]

[0273]

[Table 8]

[0274]

[Table 9]

(Description of Tables 6 to 9) TPSTF; Triphenylsulfonium triflate TSPFB; Triphenylsulfonium perfluorobutanesulfonate TPSPFBS; Triphenylsulfonium pentafluorobenzenesulfonate TPSTBTFBS; Triphenylsulfonium 3,5-
Bis (trifluoromethyl) benzene sulfonate BTBPIPFBS; Bis (t-butylphenyl) iodonium perfluorobutane sulfonate BCHSDM; Bis (cyclohexylsulfonyl) diazomethane

DBN; 1,5-diazabicyclo [4.
3.0] -5-Nonene TPI; 2,4,5-triphenylimidazole HEP; N-hydroxyethylpiperidine DIA; 2,6-diisopropylaniline DCMA; dicyclohexylmethylamine TOA; trioctylamine LCB; lithocholic acid t- Butyl

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

The abbreviations for the solvents are as follows. In addition, the ratio in the case of multiple use in Tables 7-9 is a weight ratio. A1; propylene glycol methyl ether acetate A2; 2-heptanone A3; ethyl ethoxypropionate A4; γ-butyrolactone A5; cyclohexanone B1; propylene glycol methyl ether B2;

<Image Evaluation Method> An antireflection film DUV-42 manufactured by Brewer Science Co., Ltd. was coated on a silicon substrate that had been subjected to hexamethyldisilazane treatment by a spin coater.
Angstrom was uniformly applied, dried on a hot plate at 100 ° C. for 90 seconds, and then heated and dried at 190 ° C. for 240 seconds. Thereafter, each photosensitive resin composition was applied by a spin coater, dried at 120 ° C. for 90 seconds,
A μm resist film was formed. The resist film was exposed through a mask with an ArF excimer laser stepper (NA = 0.6, manufactured by ISI), and immediately after the exposure, heated on a hot plate at 120 ° C. for 90 seconds. 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 pattern on the silicon wafer thus obtained was observed with a scanning-scanning electron microscope (CD-SEM).
Resist performances (dependency on density and exposure margin) as shown in Nos. 0 to 13 were obtained. About the obtained result, Tables 10-13
Shown in

[Dependency on coarse / dense]: Dependency on coarse / dense (difference in density)
Means that, at an exposure amount that reproduces a pattern of L / S = 1: 1.5 with a mask dimension of 0.17 μm, L / S =
0.17 when measuring the formation dimension of the pattern of 1: 5
Represents the dimensional difference from μm.

[Exposure Margin]: The exposure margin first determines the optimum exposure amount for reproducing a pattern of L / S = 1: 1 with a mask dimension of 0.15 μm, and secondly, the dimension formed after development is A value is obtained by determining a range of the exposure amount within a range of ± 10% of 150 nm and dividing the exposure amount range by the optimum exposure amount.

[0282]

[Table 10]

[0283]

[Table 11]

[0284]

[Table 12]

[0285]

[Table 13]

The following is clear from the results shown in Tables 10 to 13. The compositions of Examples 1 to 86 have excellent dependency on the density and the exposure margin.

[0287]

As described above, the positive photosensitive composition of the present invention has an excellent density dependency and an excellent exposure margin.

Claims (8)

[Claims] (A) a compound which generates an acid upon irradiation with actinic rays or radiation; (B) a resin which is decomposed by the action of an acid to increase the solubility in an alkali developing solution; and (C) an onium carboxylate. And (B) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, wherein the resin which is decomposed by the action of an acid and has increased solubility in an alkali developing solution is a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure. object. (D) having a group decomposable by an acid, wherein the dissolution rate in an alkaline developer is increased by the action of an acid;
The positive photosensitive composition according to claim 1, further comprising a low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less. 3. The positive photosensitive composition according to claim 1, wherein the resin (B) is a resin further having a lactone structure. (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation; (C) an onium carboxylate; (D) a group having a group decomposable by an acid; Molecular weight increased by the action of
0 or less low molecular dissolution inhibiting compound (E) having a monocyclic or polycyclic alicyclic hydrocarbon structure, containing a resin which is insoluble in water and soluble in an alkali developing solution. 4. The positive photosensitive composition according to any one of 3. 5. The positive type according to claim 1, wherein the (C) onium carboxylate is at least one selected from sulfonium carboxylate and iodonium carboxylate. Photosensitive composition. 6. The positive type according to claim 1, wherein the carboxylate residue of the onium carboxylate (C) does not contain an aromatic group or a carbon-carbon double bond. Photosensitive composition. 7. The method according to claim 1, wherein the carboxylate residue of the onium carboxylate (C) is a fluorine-substituted linear, branched or cyclic alkyl carboxylate anion. Positive photosensitive composition. 8. The positive photosensitive composition according to claim 1, which is a composition for exposure with far ultraviolet light having a wavelength of 220 nm or less.