JP2000241977A - Positive type photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive type photosensitive composition suitable for exposure with a light source of <=250 nm, particularly <=220 nm by incorporating a compound which produces acid when irradiated with active light or radiation and a specified resin. SOLUTION: The photosensitive composition contains a compound which produces acid when irradiated with active light or radiation and a resin which has at least one structure of the formula, is decomposed by the action of acid and increases its solubility in an alkali developer. In the formula, R' and R" are each straight, branched or cyclicalkyl or a group having a monocyclic or poplycyclic hydrocarbon structure, at least one of R' and R" is the group having a monocyclic or polycyclic hydrocarbon structure, R' and R" may bond to each other to form a group having a monocyclic or polycyclic hydrocarbon structure, X is a single bond or a divalent combining group and R is a group of the formula -OR1, -NR2COR3 or the like.

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 process for producing semiconductors such as ICs, a circuit substrate for liquid crystals and thermal heads, and other photofabrication processes. . More specifically, the present invention relates to a positive-type photosensitive composition suitable for using far ultraviolet rays having a wavelength of 250 nm or less as an exposure light source.

[0002]

2. Description of the Related Art Positive photoresist compositions include:
In general, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is used. For example, US Pat. No. 3,666,473, US Pat. No. 4,115,128 and US Pat. No. 4,173,470 as “Novolak-type phenol resin / naphthoquinonediazide-substituted compound”
As the most typical composition, "Novolak resin composed of cresol-formaldehyde / trihydroxybenzophenone-1,2-naphthoquinonediazidesulfonic acid ester" is exemplified by Thompson "Introduction to Microlithography" (LFThompson "Intr
oduction to Microlithography ") (ACS Publishing, N
o. 2, 19, p112-121). In such a positive photoresist consisting essentially of a novolak resin and a quinonediazide compound, the novolak resin gives high resistance to plasma etching, and the naphthoquinonediazide compound acts as a dissolution inhibitor. Then, naphthoquinonediazide has the property of losing its dissolution inhibiting ability by generating carboxylic acid upon irradiation with light, and increasing the alkali solubility of the novolak resin.

[0003] From this point of view, many positive photoresists containing a novolak resin and a naphthoquinonediazide-based photosensitive material have been developed and put into practical use.
Sufficient results have been achieved in line width processing down to about 2 μm. However, the degree of integration of integrated circuits has been increasing more and more, and in the manufacture of semiconductor substrates such as VLSIs, processing of ultrafine patterns having a line width of half a micron or less has been required.

[0004] As one of means for miniaturizing a pattern, it is known to shorten the wavelength of an exposure light source used for forming a resist pattern. This means Rayleigh's equation representing the resolution (line width) R of the optical system, R = k · λ / NA (where λ is the wavelength of the exposure light source, NA is the numerical aperture of the lens,
k is a process constant). From this equation, it can be seen that in order to achieve higher resolution, that is, to reduce the value of R, it is sufficient to shorten the wavelength λ of the exposure light source. For example, in the manufacture of a DRAM having a degree of integration of up to 64 Mbits, the i-line (365 nm) of a high-pressure mercury lamp has been used as a light source until now. In a mass production process of a 256 Mbit DRAM, use of a KrF excimer laser (248 nm) as an exposure light source instead of i-line is being studied. Further, for the purpose of manufacturing a DRAM having an integration degree of 1 Gbit or more, a light source having a shorter wavelength has been studied.
It is considered that the use of rF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-rays, electron beams, etc. is effective (Takumi Ueno et al., “Short Wavelength Photoresist Material-Fine Processing for ULSI” − ”, Bunshin Publishing, 1988).

When a conventional resist composed of a novolak and a naphthoquinonediazide compound is used for lithography pattern formation using deep ultraviolet light or excimer laser light,
Because of the strong absorption of novolak and naphthoquinonediazide in the far ultraviolet region, 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.
It is a chemically amplified resist composition described in U.S. Pat. No. 4,491,628 and European Patent No. 249,139. 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.

[0007] Examples of such a combination include a combination of a compound that generates an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Application Laid-Open No. 48-89003), a combination of an orthoester or an amide acetal compound ( Combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-172014).
3429), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236),
Combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), combination with a tertiary alkyl ester compound (JP-A-60-3625), combination with a silyl ester compound (JP-A-60-3625) Showa 60-10247
No.) and a combination with a silyl ether compound (Japanese Unexamined Patent Publication No.
0-37549, JP-A-60-112446) and the like. These have high photosensitivity because the quantum yield exceeds 1 in principle.

Similarly, as a system which is decomposed by heating in the presence of an acid and solubilized in an alkali, for example, JP-A-59
-45439, JP-A-60-3625, JP-A-62
JP-A-229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250642, JP-A-5-181279, Polym.Eng.Sce., Vol. 23, 1012
Page (1983); ACS. Sym. 242, 11 (1984); Semicondu
ctor World 1987, November, p. 91; Macromolecules, 21,
Vol., P. 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). )
And JP-A-4-219775, JP-A-5-249682, and JP-A-6-219572.
Combination systems with acetal compounds described in JP-A-65332 and JP-A-4-21258 and JP-A-6-65.
No. 333, etc., in combination with a t-butyl ether compound.

These systems mainly use a resin having a low absorption in the 248 nm region and having poly (hydroxystyrene) as a main skeleton, so that 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 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. Vac. Sci. Technol., B9, 3357 (1991).
However, this polymer has a problem in that 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 exhibits the same dry etching resistance as an aromatic group and has a small absorption in the 193 nm region.
SPIE, 1672, 66 (1992). In recent years, the use of this polymer has been vigorously studied. Specifically, JP-A-4-39665, JP-A-5-80515, and 5-2
No. 65212, No. 5-297591, No. 5-3466
No. 68, No. 6-289615, No. 6-324494
No. 7-49568, No. 7-185046, No. 7
191463, 7-199467, 7-23
Polymers described in JP-A Nos. 4511 and 7-252324 are exemplified. However, these polymers do not always have sufficient dry etching resistance,
Even though the dry etching resistance is good, film peeling due to insufficient adhesion to the substrate occurs, but the acid decomposability is insufficient, and the exposed discrimination-unexposed part dissolution discrimination is small,
As a result, the resolution was low.

Japanese Patent Application Laid-Open No. Hei 8-259626 discloses a polymer having a carboxyl group and an acid-decomposable group at the terminal of an alicyclic group in order to achieve both adhesion to a substrate, dry etching resistance and acid-decomposability. However, in this polymer, even if the acid-decomposable group in the side chain is decomposed by the acid generated by the exposure, an extremely hydrophobic alicyclic hydrocarbon group remains in the polymer main chain, so that the exposed portion of Since the alkali solubility is reduced and the alkali-dissolution discrimination between the unexposed portion and the exposed portion is reduced, there have been problems such as low sensitivity and low resolving power.

[0013]

SUMMARY OF THE INVENTION The object of the present invention is to
An object of the present invention is to provide a positive photosensitive composition suitable for use with an exposure light source of 0 nm or less, particularly 220 nm or less. Another object of the present invention is to provide a positive photosensitive composition which gives good sensitivity, resolution, adhesion and a resist pattern when using an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, and further exhibits a sufficient dry etching resistance. Is to provide.

[0014]

According to the present invention, the following positive photosensitive composition is provided to achieve the above object of the present invention. (1) (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (B) a side chain having at least one structure represented by the following general formula (I), which is decomposed by the action of an acid. And a resin having an increased solubility in an alkali developing solution.

[0015]

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In the general formula (I), R ′ and R ″ are the same or different and each represent a linear, branched, or cyclic alkyl group or a group having a monocyclic or polycyclic hydrocarbon structure; At least one of R ″ represents a group having a monocyclic or polycyclic hydrocarbon structure, or a group having a monocyclic or polycyclic hydrocarbon structure formed by combining R ′ and R ″. X is a single bond or 2
Represents a valent linking group. R represents —OR ₁ , —NR ₂ COR ₃ ,
-NR ₂ SO ₂ R _3, or a group represented by -NHR _2.
Here, R ₁ and R ₂ represent a hydrogen atom, a linear, branched, or cyclic alkyl group which may contain a hetero atom, or an acid-decomposable group, and R ₃ may contain a hetero atom. Represents a linear, branched, or cyclic alkyl group. (2) Further, (C) a molecular weight of 30 having a group which is decomposed by the action of an acid and increases the solubility in an alkaline developer.
The positive photosensitive composition according to the above (1), comprising a low molecular compound of not more than 00. (3) The positive photosensitive composition as described in (1) or (2) above, wherein far-ultraviolet light having a wavelength of 250 nm or less is used as an exposure light source. (4) The positive photosensitive composition as described in (3) above, wherein far-ultraviolet light having a wavelength of 220 nm or less is used as an exposure light source.

In the positive photosensitive composition of the present invention, even when the acid-decomposable group in the side chain is decomposed by the acid generated by exposure, a very hydrophobic alicyclic hydrocarbon group remains in the polymer main chain. As a result, a large alkali-dissolution discrimination of an unexposed portion-exposed portion is obtained. Furthermore, when the side chain alicyclic group contains an acid-decomposable group, the alicyclic hydrocarbon group cleaved from the main chain by acid decomposition is also acid-decomposed and becomes alkali-soluble, resulting in a larger discrimination. Can be As a result, high sensitivity and high resolution are obtained.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the positive photosensitive composition of the present invention will be described in detail. First, (A) a compound that generates an acid upon irradiation with actinic rays or radiation (photoacid generator) 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. Known light (ultraviolet light of 400 to 200 nm, far ultraviolet light, particularly preferably g-ray, h-ray, i-ray, KrF excimer laser light), ArF excimer laser light, electron beam , An X-ray, a molecular beam or an ion beam to generate an acid and a mixture thereof can be appropriately selected and used.

Other compounds that generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, SI Schlesinger, Photogr. Sci. Eng., 18, 3
87 (1974), TSBetal, Polymer, 21,423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,06
9,056, the same Re 27,992, ammonium salts described in JP-A-3-140,140, etc., DCNecker et al., Macromolecules, 1,
7,2468 (1984), CSWenetal, Teh, Proc.Conf.Rad.Curing
ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055
No. 4,069,056, etc.
vello etal, Macromorecules, 10 (6), 1307 (1977), Chem.
& Eng.News, Nov. 28, p31 (1988), EP 104,143,
No. 339,049, No. 410,201, JP-A-2-150,848,
Iodonium salts described in JP-A-2-296,514, etc., JVCr
ivello etal, Polymer J. 17, 73 (1985), JVCrivello
etal.J.Org.Chem., 43, 3055 (1978), WRWatt etal, J. Po.
lymerSci., Polymer Chem. Ed., 22, 1789 (1984), JVCriv
ello etal, Polymer Bull., 14,279 (1985), JVCrivello
etal, Macromorecules, 14 (5), 1141 (1981), JVCrivell
o etal, J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (197
9), European Patent Nos. 370,693, 161,811, 410,201
Nos. 339,049, 233,567, 297,443, 297,4
No. 42, U.S. Pat.Nos. 3,902,114, 4,933,377, 4,76
No. 0,013, 4,734,444, 2,833,827, Dokoku Patent No.
2,904,626, 3,604,580, 3,604,581, JP-A-7-28237, 8-27102, etc., sulfonium salts, JVCrivello et al., Macromorecules, 10
(6), 1307 (1977), JVCrivello etal, J. PolymerSci., Po
selmerium salts described in lymer Chem.Ed., 17, 1047 (1979), CSwen et al., Teh, Proc. Conf. Rad. Curing ASIA, p.
Onium salts such as arsonium salts described in 478 Tokyo, Oct (1988), U.S. Pat.No. 3,905,815, JP-B-46-4605,
JP-A-48-36281, JP-A-55-32070, JP-A-60-23973
No. 6, JP-A-61-169835, JP-A-61-169837, JP-A-61-69837
2-58241, JP-A-62-212401, JP-A-63-70243, Organic halogen compounds described in JP-A-63-298339, etc., K. Mei
er et al, J. Rad. Curing, 13 (4), 26 (1986), TPGill et
al, Inorg.Chem., 19,3007 (1980), D.Astruc, Acc.Chem.R
es., 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-14145, S. Hayase et al., J. Polymer
Sci., 25, 753 (1987), E. Reichmanis et al., J. Phlymer Sc
i., Polymer Chem. Ed., 23, 1 (1985), QQ Zhu et al., J. Phot
ochem., 36, 85, 39, 317 (1987), B. Amit etal, Tetrahedron
Lett., (24) 2205 (1973), DHR Barton et al., J. Chem So
c., 3571 (1965), PMCollins et al, J. Chem.SoC., Perkin
I, 1695 (1975), M. Rudinstein et al., Tetrahedron Lett.,
(17), 1445 (1975), JWWalkeretal J. Am. Chem. Soc., 110, 7
170 (1988), SCBusman et al., J. Imaging Technol., 11
(4), 191 (1985), HM Houlihan et al, Macormolecules, 21,
2001 (1988), PMCollinsetal, J. Chem. Soc., Chem. Commu
n., 532 (1972), S. Hayase etal, Macromolecules, 18, 1799
(1985), E. Reichmanis et al., J. Electrochem. Soc., Solid
State Sci.Technol., 130 (6), FMHoulihan et al, Macrom
olcules, 21, 2001 (1988), European Patent Nos. 0290,750 and 04
6,083, 156,535, 271,851, 0,388,343,
U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-198
No. 538, JP-A-53-133022 and the like, a photoacid generator having an O-nitrobenzyl-type protecting group, M. TUNOOKA et al., Poly
mer Preprints Japan, 35 (8), G. Berner et al., J. Rad. Curi
ng, 13 (4), WJMijs etal, Coating Technol., 55 (697), 4
5 (1983), Akzo, H. Adachi et al, Polymer Preprints, Japa
n, 37 (3), European Patent Nos. 0199,672, 84515, 044,115
No. 618,564, No. 0101,122, U.S. Pat.No. 4,371,6
No. 05, 4,431,774, JP-A-64-18143, JP-A-2-24
No. 5,756, JP-A-3-140109, etc., compounds which generate sulfonic acid by photodecomposition represented by iminosulfonate and the like, described in JP-A-61-166544, JP-A-2-71270, etc. Disulfone compound, JP-A-3-103854
And diazoketosulfone and diazodisulfone compounds described in JP-A Nos. 3-103856 and 4-210960.

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, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondo et al., Makromol.Chem., Ra.
pid Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Che
m., 152, 153, 163 (1972), JVCrivello etal, J. PolymerS
ci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
No. 9,137, Dokoku Patent No. 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038
JP-A-63-163452, JP-A-62-153853, JP-A-63-163452
Compounds described in No. 146029 can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
Compounds that generate an acid by light described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

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

[0023]

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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
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0025]

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[0026]

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[0027]

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

[0029]

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

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, an aryl group having 6 to 14 carbon atoms, 1 to 8 carbon atoms
And substituted derivatives thereof. Preferred substituents include an aryl group, 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, and an alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group and an alkoxycarbonyl group.

[0032] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

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.

[0035]

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[0036]

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[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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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKnapczyk
etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok eta
l, J. Org. Chem., 35, 2532, (1970), E. Goethas et al., Bul
l.Soc.Chem.Belg., 73,546, (1964), HM Leicester, JA
me.Chem.Soc., 51,3587 (1929), JVCrivello etal, J.Po
Chem. Ed., 18,2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

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

[0047]

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

[0049]

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[0050]

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[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, but are not limited thereto.

[0058]

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The amount of the compound capable of decomposing upon irradiation with actinic rays or radiation to generate an acid is generally 0.001 to 0.001 to the solid content of the total composition of the photosensitive composition of the present invention.
It is used in the range of 40% by weight, preferably 0.01 to 2%.
0% by weight, more preferably 0.1 to 5% by weight. If the amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid is less than 0.001% by weight, the sensitivity becomes low. If the amount is more than 40% by weight, the light absorption of the resist becomes high. This is not preferable because the profile is deteriorated and the process (especially baking) margin is narrowed.

Next, (B) a resin having at least one of the structures represented by the above general formula (I) in the side chain and decomposing by the action of an acid to increase the solubility in an alkali developing solution (hereinafter referred to as a resin)
The “(B) resin of the present invention” or “(B) acid-decomposable resin of the present invention”) will be described. The structure represented by the general formula (I) can be bonded to any position as long as it is a side chain of the resin (B) of the present invention. That is, the structure represented by the general formula (I) and the acid-decomposable group are
It may be bonded to the side chain of a different repeating unit in the base resin, or may be bonded to the side chain of the same repeating unit,
Further, the case where both cases coexist in the resin is also included. Further, the case where the structure represented by the general formula (I) contains an acid-decomposable group is also included.

R ′ and R ″ in the general formula (I) may be the same or different and each may be a linear, branched or cyclic alkyl group, a group having a monocyclic or polycyclic hydrocarbon structure, or R ′ and R ′ 'Represents a group having a monocyclic or polycyclic hydrocarbon structure formed by bonding, R', at least one of R '' has a monocyclic or polycyclic hydrocarbon structure, or R ', R ″ represents a group having a monocyclic or polycyclic hydrocarbon structure formed by bonding.
The linear, branched, or cyclic alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group,
Examples include a hexyl group, a 2-ethylhexyl group, an octyl group, a cyclopropyl group, and a cyclopentyl group. The monocyclic hydrocarbon structure is preferably a cyclopropane having 3 or more carbon atoms which may have a substituent, cyclobutane,
Cycloaliphatic groups such as cyclopentane and cyclohexane,
More preferably, it may have 3 to 8 carbon atoms which may have a substituent.
Is an alicyclic group. As the polycyclic hydrocarbon structure,
It is preferably an alicyclic group such as bicyclo, tricyclo, tetracyclo or the like having 5 or more carbon atoms which may have a substituent, and more preferably 6 carbon atoms which may have a substituent.
A polycyclic alicyclic group having a carbon number of 7 to 25, which may have a substituent; Preferred substituents of the above monocyclic or polycyclic alicyclic group include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, an alkyl group, and a methoxy group. , An ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an alkoxycarbonyl group having 1 to 8 carbon atoms such as a butoxy group, a methoxycarbonyl group, an alkoxycarbonyl group such as an ethoxycarbonyl group, a formyl group, an acetyl group, a benzoyl group, etc. And an acyloxy group such as an acyl group, an acetoxy group and a butyryloxy group, and a carboxy group.

Typical examples of the polycyclic hydrocarbon structure are shown below.

[0063]

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[0064]

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X in the above formula (I) represents a single bond or a divalent linking group. Examples of the divalent linking group include an oxygen atom, a sulfur atom, -NH-, and a divalent organic group. 2
Examples of the valent organic group include, for example, a linear, branched, or cyclic alkylene group, an alkenylene group, and -COO-
Group, -CO- group, -SO ₂ - group, -SO ₂ NH- groups, -C
ONH- group, -CONHSO ₂ - group, -N (alkyl) - group, (the alkyl group preferably having 1 to 8 carbon atoms, represented for example, methyl, ethyl, propyl, butyl, octyl.) - COS- And a linking group containing two or more of these groups. Among them, an alkyne group is preferable. In X, the alkylene group preferably has 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group which may have a substituent. . As the cyclic alkylene group, preferably may have a substituent,
5 carbon atoms such as cyclopentylene and cyclohexylene
To 8 items. Alkenylene groups include
Preferably an ethenylene group which may have a substituent,
Those having 2 to 6 carbon atoms such as a propenylene group and a butenylene group are exemplified.

In the general formula (I), R is -OR ₁ , -N
Represents a group represented by R ₂ COR ₃ , —NR ₂ SO ₂ R ₃ , or —NHR ₂ . Here, R ₁ and R ₂ represent a hydrogen atom, a linear, branched, or cyclic alkyl group which may contain a hetero atom, or an acid-decomposable group, and R ₃ may contain a hetero atom. Represents a good linear, branched or cyclic alkyl group. Examples of the above hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and the like. The alkyl group of R ₁ , R ₂ and R ₃ is preferably an alkyl group having 1 to 12 carbon atoms,
Examples include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a cyclopropyl group, and a cyclopentyl group. Examples of the alkyl group containing a hetero atom include, for example, a group having an ethyleneoxy structure such as a 2-methoxyethyl group and a methoxyethoxyethyl group,
A group having a propyleneoxy structure is exemplified. Examples thereof include groups in which part or all of these oxygen atoms are replaced with sulfur atoms or nitrogen atoms.

As described above, the acid-decomposable group in R ₁ and R ₂ is a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer, and (B) the acid-decomposable resin of the present invention. It has the same meaning as the acid-decomposable group in the side chain. Examples of the acid-decomposable group include a group which is hydrolyzed by the action of an acid to form an acid, and a group which forms an acid by elimination of a carbon cation by the action of an acid. Preferably, the following general formula (XII
These are groups represented by (I) and (XIV). Thereby, the stability over time becomes excellent.

[0068]

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Here, R₄₇~ R₄₉Are the same or
Differently, may have a hydrogen atom, or a substituent,
Alkyl, cycloalkyl, or alkenyl groups
Represents However, R in the formula (XIII)₄₇~ R₄₉At least
One is a group other than a hydrogen atom. R₅₀Has a substituent
An alkyl group, a cycloalkyl group or an
Represents a phenyl group. In addition, R of the formula (XIII)₄₇~ R₄₉2 of
Or R of the formula (XIV) ₄₇~ R₄₈, R₅₀Two of the groups
A ring system consisting of 3 to 8 carbon atoms or heteroatoms
The structure may be formed. Specifically, such a ring is
Cyclopropyl group, cyclopentyl group, cyclohexyl
Group, cycloheptyl group, 1-cyclohexenyl group, 2-
Tetrahydrofuranyl group, 2-tetrahydropyranyl group
And the like. Z₁~ Z_TwoAre the same or different
Represents an elementary atom or a sulfur atom. As the above alkyl group
Is preferably a methyl group which may have a substituent,
Ethyl group, propyl group, n-butyl group, sec-butyl
Group, hexyl group, 2-ethylhexyl group, octyl group
Those having 1 to 8 carbon atoms are exemplified. The above cyclo
The alkyl group preferably has a substituent
Good, cyclopropyl, cyclopentyl, cyclohexyl
Examples include those having 3 to 8 carbon atoms such as a xyl group.
The alkenyl group preferably has a substituent
Vinyl, propenyl, allyl, butene
Nyl, pentenyl, hexenyl, cyclohexenyl
And those having 2 to 6 carbon atoms such as

Further, as the further substituent in each of the above substituents, a hydroxyl group, a halogen atom (fluorine,
Chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamide group, alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, alkoxy group such as butoxy group, methoxycarbonyl group And alkoxycarbonyl groups such as ethoxycarbonyl group; acyl groups such as formyl group, acetyl group and benzoyl group; acyloxy groups such as acetoxy group and butyryloxy group; and carboxy groups.

(B) The group (acid-decomposable group) which is present in the side chain of the acid-decomposable resin of the present invention and which is decomposed by the action of an acid and increases the solubility in an alkali developer is as described above for R ₁ , R ₂ have the same structure as the acid-decomposable group, and may be contained in the structure represented by the general formula (I);
(B) It may be contained in another structural unit constituting the acid-decomposable resin of the present invention.

(B) The content of the repeating structural unit having the structure represented by the above general formula (I) in the resin of the present invention is adjusted by the balance between dry etching resistance, alkali developability and the like. , 2 for all repeating units
The content is preferably 0 mol% or more, more preferably 30 to 80 mol%, and still more preferably 40 to 70 mol%. Specific examples (a1) to (a18) of the repeating structural unit having the structure represented by the general formula (I) are shown below, but the present invention is not limited thereto.

[0073]

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[0074]

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[0075]

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Among them, as the most preferred structural unit of the present invention, those having the following structure linked by a tertiary ester group are excellent in acid decomposability, and are particularly preferable in view of sensitivity.

[0077]

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In the formula, R, R ′, R ″, and X have the same meanings as described above. R ₄ represents a hydrogen atom, a linear, branched, or cyclic alkyl group which may have a substituent, and the alkyl group has the same meaning as the alkyl group in R ₁ .

(B) The resin of the present invention has the following general formula (I)
May have at least one of the repeating structural units represented by the general formulas (X), (XI) and (XII).

[0080]

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In the formulas (X) to (XII), R₅₅, R₅₆, R₅₈~
R₆₀Are the same or different and are a hydrogen atom, a halogen atom,
Represents a cyano group, an alkyl group or a haloalkyl group. R₅₇
Is a cyano group, -CO-OR₆₇Or -CO-NR₆₈R₆₉
Represents X₇~ X₉Are the same or different and are a single bond
Or a divalent alkylene which may have a substituent
Group, alkenylene group or cycloalkylene group, -C
O-, -SO_Two-, -O-CO-R₇₀-, -CO-O-
R₇₁-Or -CO-NR ₇₂-R₇₃Represents-. R₆₇Is
A hydrogen atom, an optionally substituted alkyl group,
For the action of chloroalkyl or alkenyl groups or acids
Groups that decompose more to increase solubility in alkaline developers
Represents R₆₈, R₆₉, R₇₂Is the same or different and is hydrogen
Atom, optionally substituted alkyl group, cyclo
Represents an alkyl group or an alkenyl group. Also R₆₈And R
₆₉May combine with each other to form a ring. R₇₀~ R₇₁, R
₇₃Are the same or different and are a single bond or a divalent alkyl
Represents a len group, alkenylene group or cycloalkylene group.
Further, these groups are ether groups, ester groups,
Divalent with a mid group, urethane group or ureide group
Groups may be formed. B is an acid-decomposable group, and (B)
Same as the acid-decomposable group present in the side chain of the acid-decomposable resin of the present invention.
And the details have already been described.

As the alkyl group for R _{67 to} R ₆₉ and R ₇₂ ,
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 has 2 to 6 carbon atoms such as a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a cyclohexenyl group which may have a substituent. Can be

The alkyl group represented by R ₅₅ , R ₅₆ , R _{58 to} R ₆₀ is preferably an optionally substituted methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group. And those having 1 to 4 carbon atoms. As the haloalkyl group, preferably a fluorine atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms substituted by a bromine atom,
For example, a fluoromethyl group, a chloromethyl group, a bromomethyl group, a fluoroethyl group, a chloroethyl group, a bromoethyl group and the like can be mentioned.

The alkylene group represented by X _{7 to} X ₉ is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group which may have a substituent. Individual ones. The alkenylene group preferably has 2 to 6 carbon atoms such as an ethenylene group, a propenylene group and a butenylene group which may have a substituent. The cycloalkylene group preferably has 5 to 5 carbon atoms such as a cyclopentylene group and a cyclohexylene group which may have a substituent.
There are eight.

The alkylene group, alkenylene group, and cycloalkylene group represented by R _{70 to} R ₇₁ and R ₇₃ include the same groups as those described above, and further include those groups, ether groups, ester groups, and amide groups. , A urethane group and a ureido group together form a divalent group. As the ring and R ₆₈ and R ₆₉ form together with the bond to the nitrogen atom, preferably one to form a 5- to 8-membered ring, in particular pyrrolidine, piperidine, piperazine and the like. R ₆₇ represents an acid-decomposable group.

The general formula in the resin according to the present invention
The content of the repeating structural units represented by formulas (X) to (XII) is adjusted depending on the performance such as alkali developability and substrate adhesion, but is preferably from 0 to 80 mol% based on all repeating units. It is preferably used in the range of 0 to 70 mol%, and more preferably in the range of 0 to 60 mol%. The general formula below
Specific examples of the repeating structural units represented by (X) to (XII) are shown below, but the present invention is not limited thereto.

[0087]

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[0088]

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[0089]

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[0090]

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(B) The resin of the present invention may further contain a carboxyl group. The carboxyl group may be contained in the repeating structural units having the group represented by the general formula (I), or in the repeating structural units of the general formulas (X) to (XII), or may be a different repeating unit. It may be contained in a structural unit. Furthermore, these structural units may be included in a plurality of positions. As the repeating structural unit having a carboxyl group, repeating structural units represented by formulas (XV) to (XVII) are preferable.

[0092]

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In the formulas (XV) to (XVII), R₇₅, R₇₆, R₇₈~ R
₈₀Are the same or different and represent a hydrogen atom, a halogen atom,
Represents an ano group, an alkyl group or a haloalkyl group. R
₇₇Is a cyano group, -CO-OR₈₇Or -CO-NR₈₈R
₈₉Represents X_Ten~ X₁₂Are the same or different and are a single bond
A divalent alkylene which may or may have a substituent
Group, alkenylene group or cycloalkylene group, -C
O-, -SO_Two-, -O-CO-R₉₀-, -CO-O-
R₉₁-Or -CO-NR ₉₂-R₉₃Represents-. R₈₇Is
A hydrogen atom, an optionally substituted alkyl group,
For the action of chloroalkyl or alkenyl groups or acids
Groups that decompose more to increase solubility in alkaline developers
Represents R₈₈, R₈₉, R₉₂Is the same or different and is hydrogen
Atom, optionally substituted alkyl group, cyclo
Represents an alkyl group or an alkenyl group. Also R₈₈And R
₈₉May combine with each other to form a ring. R₉₀~ R₉₁, R
₉₃Are the same or different and are a single bond or a divalent alkyl
Represents a len group, alkenylene group or cycloalkylene group.
Further, these groups are ether groups, ester groups,
Divalent with a mid group, urethane group or ureide group
Groups may be formed.

The details of the substituents of R _{75 to} R ₈₀ , R _{87 to} R ₉₃ , and X _{10 to} X ₁₂ are the same as those of the above-mentioned general formulas (X) to (XII).
_{55 ~R 60, R 67 ~R 73} , X 7 ~X 9 in the above formula is preferred group also synonymous.

The content of all the repeating structural units having a carboxyl group in the positive photosensitive composition of the present invention, preferably the repeating structural units represented by the general formulas (XV) to (XVII), is selected from the group consisting of alkali developability, It is adjusted according to performance such as substrate adhesion and sensitivity, but it is preferably in the range of 0 to 60 mol%, more preferably 0 to 40 mol%, and still more preferably 0 to 20 mol%, based on all repeating units. It is.
Specific examples of the repeating structural units represented by formulas (XV) to (XVII) are shown below, but the present invention is not limited thereto.

[0096]

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[0097]

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(B) For the purpose of improving the performance of the resin of the present invention, another polymerizable monomer may be further copolymerized as long as the transmittance of 220 nm or less and the dry etching resistance of the resin are not significantly impaired. Good. 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, for example, acrylates such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (eg, methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate) , Chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2
-Dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) aryl acrylate (for example, phenyl acrylate) , Hydroxyphenyl acrylate, etc.);

Methacrylic esters, for example, alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate,
Amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
Chlorbenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate , Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.), aryl methacrylates (eg, phenyl methacrylate, hydroxyphenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.); acrylamides such as acrylamide, N-alkylacrylamide, , Having 1 to 10 carbon atoms
Such as methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, benzyl, hydroxyethyl and benzyl groups. ), N-arylacrylamides (aryl groups include, for example, phenyl, tolyl, nitrophenyl, naphthyl, cyanophenyl, hydroxyphenyl, carboxyphenyl, etc.),
N, N-dialkylacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a butyl group, an isobutyl group, an ethylhexyl group,
And a cyclohexyl group. ), N, N-arylacrylamide (aryl group includes, for example, phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a t-butyl group, an ethylhexyl group; A hydroxyethyl group, a cyclohexyl group, etc.), N-
Aryl methacrylamide (aryl group includes phenyl group, hydroxyphenyl group, carboxyphenyl group, etc.), N, N-dialkylmethacrylamide (alkyl group includes ethyl group, propyl group, butyl group, etc.) ), N, N-diarylmethacrylamide (an aryl group includes a phenyl group and the like), N-
Hydroxyethyl-N-methylmethacrylamide, N-
Methyl-N-phenylmethacrylamide, N-ethyl-
N-phenylmethacrylamide and the like; allyl compounds, for example, allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl acetoacetate) Allyl, etc.), allyloxyethanol, etc .;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether,
Ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, Tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ethers (eg, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,
4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.); vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, and vinyl chloride Acetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl aceto acetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate,
Vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like;

Styrenes, for example, styrene, alkylstyrene (eg, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethyl Styrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc., alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene) , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorstyrene , Trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc., hydroxystyrene (for example, 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, -Hydroxy-3-methylstyrene, 4-hydroxy-3,5-dimethylstyrene, 4-hydroxy-3-methoxystyrene, 4-hydroxy-3- (2-hydroxybenzyl)
Crotonates; for example, alkyl crotonates (eg, butyl crotonate, hexyl crotonate, glycerin monocrotonate); dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate; 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, monomers having a carboxyl group such as carboxystyrene, N- (carboxyphenyl) acrylamide, N- (carboxyphenyl) methacrylamide, hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- ( Monomers having a phenolic hydroxyl group, such as (hydroxyphenyl) methacrylamide, hydroxyphenyl acrylate, and hydroxyphenyl methacrylate, and monomers that improve alkali solubility, such as maleimide, are preferred as the copolymerization component. (B) The content of the repeating unit derived from another polymerizable monomer in the resin of the present invention is preferably 50 mol% or less, more preferably 3 mol% or less, based on all repeating units.
0 mol% or less.

The positive photosensitive composition of the present invention comprises (C) a low molecular weight compound having a group which is decomposed by the action of an acid to increase the solubility in an alkali developing solution and has a molecular weight of 3,000 or less (hereinafter, referred to as “C”). "(C) Acid-decomposable dissolution inhibiting compound")
Is preferable. In particular, Proceeding of SPIE, 2724, 35
5 (1996), alicyclic or aliphatic compounds such as the cholic acid derivative are preferred as (C) acid-decomposable dissolution inhibiting compounds. (C) 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, and still more preferably the solid content of the whole photosensitive composition. 10 to 35% by weight. Specific examples of the acid-decomposable dissolution inhibiting compound (C) are shown below, but the invention is not limited thereto.

[0105]

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The resin (B) having an acid-decomposable group and the structure represented by the general formula (I) is synthesized by radical, cationic or anionic polymerization of an unsaturated monomer having such a group or structure. More specifically, each monomer is blended based on the preferred composition shown above, and is mixed in an appropriate solvent with about 1%.
A polymerization catalyst is added at a monomer concentration of 0 to 40% by weight,
It is synthesized by heating and polymerizing as needed.

(B) The molecular weight of the resin of the present invention is 2,000 or more, preferably 3,000 to 1,000,000, more preferably 3,000 to 200,000 by weight average (Mw: polystyrene standard). , More preferably 4,000.
The range is from 0 to 100,000. The larger the value, the higher the heat resistance and the like, while the lower the developability and the like. Also, the degree of dispersion (Mw
/ Mn) is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0, and the smaller the ratio, the better the heat resistance and image performance (pattern profile, defocus latitude, etc.). In the positive photosensitive composition of the present invention, the amount of the resin added is preferably 50 to the total solid content.
９９99.7% by weight, preferably 70-99% by weight.

The photosensitive resin composition of the present invention preferably contains a surfactant. 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 Sorbitan such as polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Te -
G, polyoxyethylene sorbitan monostearate,
Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, EFTOP EF301, EF303, EF
352 (manufactured by Shin-Akita Chemical Co., Ltd.), MegaFac F17
1, F173, F176, F189, R08 (manufactured by Dainippon Ink Co., Ltd.), Florade FC430, FC431
(Manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC101, SC102,
Fluorinated surfactants such as SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic (co) polymerized polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and Troysol S-366 (manufactured by Troy Chemical Co., Ltd.). Among these surfactants, a fluorine-based or silicon-based surfactant is preferable in terms of coating properties and reduction of development defects. The amount of the surfactant is usually 0.01% by weight to 2% by weight, preferably 0.01% by weight to 1% by weight, based on the solid content of the entire composition in the composition of the present invention. These surfactants can be used alone or in combination of two or more.

The positive photosensitive composition of the present invention may further contain, if necessary, an acid-decomposable dissolution-promoting compound, a dye, a plasticizer, a surfactant, a photosensitizer, an organic basic compound, 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 the compound 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 (B) 2 to 50% by weight, more preferably 5 to 30% by weight, based on the resin of the present invention. 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.

Such a phenol compound having a molecular weight of 1,000 or less can be obtained by, for example, referring to the methods described in JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, EP 219294, and the like. ,
Those skilled in the art can easily synthesize. Specific examples of the phenol compound are shown below, but are not limited thereto.

Resorcin, phloroglucin, 2, 3, 4
-Trihydroxybenzophenone, 2,3,4,4'-
Tetrahydroxybenzophenone, 2,3,4,3 ',
4 ', 5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, fluoroglucoside,
4,2 ', 4'-biphenyltetrol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2',
4,4'-tetrahydroxydiphenyl ether, 2,
2 ', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2', 4,4'-tetrahydroxydiphenylsulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 4,4- (α-methylbenzylidene) bisphenol, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene,
α, α ', α "-tris (4-hydroxyphenyl)-
1-ethyl-4-isopropylbenzene, 1,2,2-
Tris (hydroxyphenyl) propane, 1,1,2-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) butane, para [α, α , Α ', α'-tetrakis (4-hydroxyphenyl)]-xylene.

Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound is preferable. Preferred chemical environments include the structures of the following formulas (A) to (E).

[0113]

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Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted 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 aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group,
An aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, and a cyano group. As particularly preferred compounds, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-
Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino -4-methylpyridine, 2-amino-5
-Methylpyridine, 2-amino-6-methylpyridine,
3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 -Tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p- Tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline,
N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4,0]
Examples include, but are not limited to, undec-7-ene, 2,4,5-triphenylimidazole and the like. Among them, 1,5-diazabicyclo [4,3,0] non-5-ene and 1,8-diazabicyclo [5,4,0]
Undec-7-ene and 2,4,5-triphenylimidazole are preferred from the viewpoint of resolving power or suppressing a change in performance over time from exposure to post-heating.

These nitrogen-containing basic compounds are used alone or in combination of two or more. 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 entire 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.

Suitable dyes include oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 60
3. Oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B
(CI45170B), malachite green (CI42
000), methylene blue (CI52015) and the like.

In order to improve the acid generation rate by exposure, the following photosensitizers can be further added. Examples of suitable photosensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone,
p, p'-tetraethylethylaminobenzophenone,
2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, setoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitro Fluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1,2-benzanthraquinone, 3-methyl-1,3-diaza-
1,9-benzanthrone, dibenzalacetone, 1,
2-naphthoquinone, 3,3′-carbonyl-bis (5,
7-dimethoxycarbonylcoumarin) and coronene, but are not limited thereto. These photosensitizers can also be used as a light absorbing agent for far ultraviolet light as a light source. In this case, the light absorbing agent exerts the effect of improving the standing wave by reducing the reflected light from the substrate and reducing the influence of multiple reflection in the resist film.

The positive photosensitive composition of the present invention is dissolved in a solvent in which each of the above components is dissolved, and coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ
-Butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate , Methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-
Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

The positive photosensitive composition of the present invention can be used for a substrate (for example, silicon / silicon) which is used for manufacturing a dense integrated circuit device.
A good resist pattern can be obtained by applying a suitable coating method such as a spinner, a coater or the like on a silicon dioxide coating), exposing through a predetermined mask, baking and developing. 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), an ArF excimer laser (193 nm), and an F ₂ excimer laser (157 n)
m), X-rays, electron beams and the like.

The developer of the photosensitive composition of the present invention includes:
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and triethylamine and methyldiethylamine Use alkaline aqueous solutions such as triamines, alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pichelidine. be able to. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0121]

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

Synthesis Example 1 (Repeating unit (a1), (a
2) Synthesis of raw material monomers of (a8) and (a18)) Synthesis of raw material monomer of (a1) Under a nitrogen atmosphere, 23.7 ml of 2M-lithium diisopropylamide (47.3 mmol) was placed in 100 ml of dry THF under a nitrogen atmosphere.
1) was added and the solution was cooled to -78 ° C. To this, 5 g (43.0 mmol) of t-butyl acetate was added dropwise over 30 minutes. After stirring for 30 minutes, a THF solution of 6.46 g (43.0 mmol) of 2-adamantanone was added thereto for 30 minutes.
Dropped over minutes. After the mixture was allowed to stand at room temperature and stirred for 1 hour, the reaction solution was cooled to 0 ° C., and 6.74 g (64.5 mmol) of methacrylic chloride was added dropwise thereto over 30 minutes. After reacting at room temperature for 10 hours, water 100
ml was slowly added. The reaction solution was extracted with ethyl acetate,
The organic phase was washed with water, dried and concentrated to obtain a crude product.
This was purified by column chromatography to obtain 4.3 g of a starting monomer of the repeating unit (a1). By using a similar method, the repeating unit (a
2) to (a8) and (a18) as raw material monomers were obtained.

Synthesis Example 2 (Repeating unit (a9), (a1
Synthesis of Raw Material Monomers of (0) to (a16)) Synthesis of Raw Material Monomers of (a9) Under a nitrogen atmosphere, 13.0 g (0.20 mol) of zinc and 150 ml of toluene were mixed, and 10.0 g of 2-adamantanone was added thereto. 0.067 mol) and methyl bromoacetate 3
0.6 g (0.20 mol) of the mixture was added in small portions until the exotherm started. Slowly add the remaining solution to maintain the reflux, and when the exotherm subsides, heat to 100 ° C.
Allowed to react for hours. Cool the reaction to 0 ° C. and add 10%
200 ml of a sulfuric acid aqueous solution was slowly added. The reaction solution was extracted with ethyl acetate, and the organic phase was washed with water, dried and concentrated to obtain a crude product. This was purified by column chromatography to obtain 13.7 g of 2-methoxycarbonylmethyl-2-adamantanol. 10. The obtained alcohol body
0 g (47.6 mmol) was dissolved in 100 ml of THF, and 9.69 (95.1 mmol) of triethylamine was added thereto.
1) 0.1 g of 4-dimethylaminopyridine was added.
7.5 g of methacrylic acid chloride (71.4) was added to this solution.
mmo1) was slowly added dropwise and reacted at room temperature for 10 hours. Thereafter, 10 g of lithium hydroxide was added to the reaction solution in distilled water 1.
An aqueous solution dissolved in 00 ml was added and reacted at room temperature for 5 hours. The reaction solution was made weakly acidic with a 10% aqueous hydrochloric acid solution, extracted with ethyl acetate, and the organic phase was washed with water, dried and concentrated to obtain a crude product. This was purified by column chromatography to obtain 3.2 g of a starting monomer of the repeating unit (a9). The raw material monomers (a10) to (a16) were obtained by using the same method.

Synthesis Example 3 (Synthesis of Starting Monomer of Repeating Unit (a17)) The starting monomer of (a9) was ethyl vinyl ether, p-
By reacting with toluenesulfonic acid (a1
The starting monomer of 7) was obtained.

Synthesis Example 4 ((B) Resin (P1) of the Present Invention)
(Synthesis of (P9)) 5 g (14.9 m) of the raw material monomer of the repeating unit (a1)
mo1), a raw material monomer of the repeating unit (a9) 4.1.
6 g (14.9 mmol), 0.224 g of polymerization initiator 2,2'-azobis (2,4-dimethylpareronitrile) (manufactured by Wako Pure Chemical Industries, Ltd .; V-65), 0.11 mercaptoacetic acid
g, N, N-dimethylacetamide 25 ml, THF3
m1, and added dropwise to 8 ml of N, N-dimethylacetamide heated at 60 ° C. in a nitrogen stream over 4 hours. Two hours after the completion of the dropwise addition, 0.11 g of V-65 was added, and a heating reaction was performed for another two hours. After allowing the reaction solution to cool, it was poured into 1 L of ion-exchanged water, and the precipitated powder was collected by filtration. This powder was dissolved in 100 ml of THF, poured into 2 L of hexane, and the precipitated powder was collected by filtration to obtain (B) a polymer (P1) as the resin of the present invention. (A1) /
The molar ratio of (a9) was 50/50, the weight average molecular weight was 6,800, and the degree of dispersion was 1.9. In the same manner, the resin (P) of the present invention (P
2) to (P10) were synthesized.

[0126]

[Table 1]

[0127]

Embedded image

Example 1 (Measurement of Optical Density) 1.0 g of the resin (B) of the present invention obtained in the above synthesis example and 0.03 g of triphenylsulfonium triflate salt were added to 4.5 g of propylene glycol monomethyl ether acetate. Dissolved and filtered through a 0.2 μm Teflon filter. The composition was uniformly applied on a quartz glass substrate by a spin coater, and dried by heating on a hot plate at 100 ° C. for 90 seconds to form a 1 μm resist film. When the optical absorption of the obtained film was measured by an ultraviolet spectrophotometer, the optical density at 193 nm was as shown in Table 2.

[0129]

[Table 2]

From the results shown in Table 2, it can be seen that the measured optical density of the resin obtained in the above synthesis example was smaller than the value of the comparative poly (hydroxystyrene), and that the resin had sufficient transmittance to light of 193 nm.

Example 2 (Measurement of dry etching resistance) 1.0 g of the resin obtained in the above synthesis example was dissolved in 4.5 g of propylene glycol monomethyl ether acetate,
The solution was filtered through a 0.2 μm Teflon filter. Apply evenly on silicon substrate with spin coater, 100
Heat drying on a hot plate at 90 ° C for 90 seconds.
A 7 μm resist film was formed. The obtained membrane is ULV
AC reactive ion etching system (CSE-1)
110), the etching rate for CF ₄ / O ₂ (8/2) gas was measured. The result was as shown in Table 3 (etching conditions: Power = 500 W, P
response = 4.6 Pa, Gas Flow Ra
te = 10 sccm).

[0132]

[Table 3]

From the results shown in Table 3, it can be seen that the etching rate of the resin obtained in the above synthesis example is sufficiently smaller than the values of the comparative poly (methyl methacrylate) and the polymer (1), and that the resin has sufficient dry etching resistance. I understand.

Example 3 (Evaluation of image) 1.0 g of the resin of the present invention obtained in the above synthesis example, 0.03 g of triphenylsulfonium triflate salt and 1,5
-Diazabicyclo [4.3.0] non-5-ene 0.0
04g, Megafac R08 (Dai Nippon Ink Co., Ltd.)
0.00006 g was dissolved in 4.5 g of propylene glycol monomethyl ether acetate and filtered with a 0.2 μm Teflon filter. It was uniformly applied on a silicon substrate that had been subjected to hexamethyldisilazane treatment by a spin coater, and was dried by heating on a hot plate at 100 ° C. for 90 seconds to form a 0.4 μm resist film.
This resist film was subjected to pattern exposure using a KrF excimer laser stepper (NA = 0.42; 248 nm), and immediately after exposure, heated at 110 ° C. for 60 seconds on a hot plate. The film was further immersed and developed in a 2.38% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and dried.
Here, as for the pattern shape, the obtained pattern was observed with a scanning electron microscope, and a rectangular shape was determined to be good. Here, the sensitivity was defined as an exposure amount for reproducing a 0.35 μm mask pattern. The resolution was defined as a critical resolution at an exposure amount for reproducing a 0.35 μm mask pattern. As a result, with the sensitivity and resolution shown in Table 4, a favorable positive pattern was formed in which only the exposed portions of the resist film were dissolved and removed.

[0135]

[Table 4]

From the results shown in Table 4, the resist using the resin of the present invention has high sensitivity and good resolution. Also, it can be seen that the pattern shape is good.

Example 4 (Evaluation of Image) The resist film of 0.4 μm obtained in Example 3
Pattern exposure was carried out using an rF excimer laser stepper (NA = 0.55).
Heated on hot plate for seconds. Furthermore, 2.38%
23 with aqueous solution of tetramethylammonium hydroxide
After immersion development at 60 ° C. for 60 seconds, rinsing with pure water for 30 seconds, and drying. As a result, a good positive pattern having the exposed portions of the resist film removed at the sensitivities and resolutions shown in Table 5 was formed. Here, the sensitivity was defined as an exposure amount for reproducing a mask pattern of 0.20 μm. The resolution was defined as a critical resolution at an exposure amount for reproducing a 0.20 μm mask pattern.

[0138]

[Table 5]

From the results shown in Table 5, it can be seen that the resist using the resin obtained in the above synthesis example exhibits good sensitivity and resolution to ArF excimer laser light and can form a good positive pattern. I understand.

[0140]

The positive-working photosensitive composition of the present invention is particularly suitable for
It had high transparency to far ultraviolet light of 20 nm or less, and good dry etching resistance and adhesion. Also 2
When far ultraviolet light (especially ArF excimer laser light) of 50 nm or less, further 220 nm or less is used as an exposure light source,
It has high sensitivity, high resolution, and shows a good pattern profile, and can be effectively used for forming a fine pattern required for manufacturing a semiconductor device.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshiaki Aoi 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd. CB41 CB52 CC20

Claims (4)

[Claims] 1. A compound which (A) generates an acid upon irradiation with actinic rays or radiation, and (B) has at least one structure represented by the following general formula (I) in a side chain thereof, and A positive photosensitive composition comprising a resin that decomposes and increases the solubility in an alkaline developer. Embedded image In the general formula (I), R ′ and R ″ are the same or different and each represent a linear, branched, or cyclic alkyl group or a group having a monocyclic or polycyclic hydrocarbon structure; Represents a group having a monocyclic or polycyclic hydrocarbon structure, or a group having a monocyclic or polycyclic hydrocarbon structure formed by combining R ′ and R ″. X represents a single bond or a divalent linking group. R _{is, -OR 1, -NR 2 COR 3} , -NR 2 SO
₂ represents a group represented by R ₃ or —NHR ₂ . here,
R ₁ and R _{2 each} represent a hydrogen atom, a linear, branched, or cyclic alkyl group which may contain a hetero atom, or an acid-decomposable group; R ₃ represents a linear atom which may contain a hetero atom; Represents a branched or cyclic alkyl group. 2. The composition further decomposed by the action of (C) an acid,
The positive photosensitive composition according to claim 1, further comprising a low molecular compound having a molecular weight of 3000 or less and having a group that increases the solubility in an alkali developer. 3. The exposure light source according to claim 1, wherein far-ultraviolet light having a wavelength of 250 nm or less is used.
4. The positive photosensitive composition according to item 1. 4. The positive photosensitive composition according to claim 3, wherein far ultraviolet light having a wavelength of 220 nm or less is used as an exposure light source.