JPH112901A - Positive photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance sensitivity and to obtain a superior resist pattern by incorporating a specified compound to be allowed to release a sulfonic acid by irradiation with activated rays or the like and a resin comprising repeating units having groups to be decomposed by action of an acid to increase solubility in an alkaline developing solution. SOLUTION: The positive photosensitive composition contains the compound to be allowed to release a sulfonic acid by irradiation with activated rays or the like and represented by formula I and the resin comprising the repeating units having the groups to be decomposed by action of an acid to increase solubility in the alkaline developing solution, and each of the repeating units is represented by formula II or III, and in formulae I-II, Y is an optionally substituted straight or branched or cyclic alkyl or optionally substituted aralkyl group or the like; R22 is an H atom or an optionally substituted straight or branched or cyclic alkyl or optionally substituted aralkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a lithographic printing plate or an IC.
The present invention relates to a positive photosensitive composition used in a semiconductor manufacturing process such as the above, a circuit substrate such as a liquid crystal and a thermal head, and other photofabrication processes.

[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. / Trihydroxybenzophenone-1,2-naphthoquinonediazidosulfonic acid ester ”is an example of Thompson's“ Introduction to Microlithography ”(LFThompson
"Introduction to Microlithography") (ACS Publishing, No. 2, 19, pp. 112-121). 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. And naphthoquinonediazide loses dissolution inhibiting ability by generating carboxylic acid when irradiated with light,
It has the property of increasing the alkali solubility of novolak resins.

[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. In order to achieve the required resolution, the wavelength of an exposure apparatus used for photolithography is becoming shorter and shorter, and now far ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) have been studied. ing. When a conventional resist consisting of novolak and naphthoquinonediazide compound is used for lithographic pattern formation using far ultraviolet light or excimer laser light, light is strongly absorbed in the far ultraviolet region of novolak and naphthoquinonediazide. It is difficult to reach, 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 area by irradiation with radiation such as deep ultraviolet light, and the reaction using the acid as a catalyst dissolves the active radiation irradiated area and the non-irradiated area in the developing solution. This 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 that generates 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-5120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-1)
No. 33429), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236), a combination with a polymer having an orthoester group in the main chain. (JP-A-56-17345), a combination with a tertiary alkyl ester compound (JP-A-60-3625), and a combination with a silyl ester compound (JP-A-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, systems which are stable under aging at room temperature but are decomposed by heating in the presence of an acid and solubilized in alkali are disclosed in, for example, JP-A-59-45439, JP-A-60-3625, JP-A-62-2229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250642, Polym.Eng.Sce., Volume 23, 10
12 (1983); ACS.Sym. 242, 11 (1984); Semico
nductor World, 1987, November, p. 91; Macromolecule
s, Volume 21, p. 1475 (1988); SPIE, Volume 920, p. 42 (1988)
A compound that generates an acid upon exposure described in, for example,
Combination systems with esters or carbonate compounds of tertiary or secondary carbons (eg t-butyl, 2-cyclohexenyl). These systems also have high sensitivity and have a deep-U compared to the naphthoquinonediazide / novolak resin system.
Since the absorption in the V region is small, it can be an effective system for shortening the wavelength of the light source.

The above-mentioned positive chemically amplified resist comprises three components comprising an alkali-soluble resin, a compound capable of generating an acid upon exposure to radiation (photoacid generator), and a compound inhibiting dissolution of the alkali-soluble resin having an acid-decomposable group. It can be roughly classified into a two-component system comprising a resin having a group which is decomposed by the reaction with an acid and becomes alkali-soluble and a photoacid generator. In these two-component or three-component positive chemically amplified resists, a resist pattern is obtained by heat treatment and development with an acid from a photoacid generator being exposed by exposure. Here, as the photoacid generator used in the positive chemically amplified resist as described above, N-oxime sulfonate, o-nitrobenzyl sulfonate, trismethane sulfonate of pyrogallol, and the like are known, but the photolysis efficiency is high. As a material having a large image forming property, typically, JP-A-59-45439, Polym. En
g. Sci., 23 , 1012 (1983). and the like, sulfonium and iodonium PF ₆ −, AsF ₆ −, SbF ₆ −
Perfluoro Lewis acid salts have been used. However, when used for a resist material for semiconductors, there is a problem of contamination of phosphorus, arsenic, antimony and the like from a counter anion of the photoacid generator.

[0008] Therefore, these contamination-free sulfonium,
As an iodonium compound, JP-A-63-27829
JP-A-2-25850, JP-A-2-150848
JP-A-5-134414, JP-A-5-23270
A salt having a trifluoromethanesulfonic acid anion as a counter anion described in No. 5, etc. is used. However, in the case of this compound, there has been a problem that the resist pattern becomes thinner with the passage of time from the exposure to the heat treatment, or that the surface of the resist pattern exhibits a T-type (T-top). As a method for solving this problem, JP-A-5-242682 describes a photosensitive composition using a hydroxystyrene resin protected with an acetal group and a specific acid generator. These are T-To over time after exposure to heat treatment.
Although effective in suppressing p formation, it was not sufficient in suppressing thinning of the resist pattern. JP-A-7-140666 describes a resist composition using an acid labile compound containing a ketal component and a photoacid generator. This is also effective in suppressing the formation of T-top, but it cannot be said that a sufficient effect can be obtained with respect to thinning of the resist pattern. In addition, there was a significant problem in storage stability.

[0009]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to solve the above-mentioned problems of the prior art, and more specifically, it is possible to obtain an excellent resist pattern having high photolysis efficiency, high sensitivity, and high sensitivity. An object of the present invention is to provide a positive photosensitive composition. Another object of the present invention is to provide a positive resist excellent in storage stability without causing a thinning of the resist pattern or a T-type (T-top) of the resist pattern surface with the passage of time from the exposure to the heat treatment. It is an object of the present invention to provide a photosensitive composition.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies while paying attention to the above-mentioned characteristics, and as a result, the object of the present invention is to provide the following compound in a positive-type chemical amplification system with a specific compound that generates a sulfonic acid. It has been found that this can be achieved by using a resin having a specific structure. That is, the present invention has the following configuration. (1) (a) a compound represented by the following general formula (I), which generates a sulfonic acid upon irradiation with actinic rays or radiation;
And (b) a resin containing a repeating unit having a structure represented by the following general formulas (II) and (III) having a group which is decomposed by the action of an acid and increases the solubility in an alkaline developer. A positive-type photosensitive composition, comprising:

[0011]

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In the formula (I), Y is a linear, branched or cyclic alkyl group which may have a substituent, an aralkyl group which may be substituted,

[0013]

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(R)₁~ R_{twenty one}Are the same
And may have a hydrogen atom or a substituent.
Good linear, branched, cyclic alkyl, alkoxy, acyl
Group, acylamino group, sulfonylamino group, aryl
Group, acyloxy group, aralkyl group or alkoxyca
Rubonyl group, or formyl group, nitro group, chlorine atom, odor
Represents an atom, iodine atom, hydroxyl group, or cyano group
Then R₁~ R_Five, R₆~ R ₁₂And R₁₃~ R_{twenty one}Are each
Two of the groups are bonded to form carbon and / or heteroatoms
May form a 5- to 8-membered ring). Also, Y
Even when bonded to the residue of another imide sulfonate compound
Good. X represents a linear or branched alkyl which may have a substituent;
Len group, which may have a substituent, including a hetero atom
An optionally substituted monocyclic or polycyclic alkylene group,
Optionally straight-chain, branched alkenylene, substituted
Monocyclic or polycyclic, optionally containing heteroatoms
Alkenylene group, an optionally substituted arylene group,
It represents an aralkylene group which may be substituted. Also, X
May be bonded to another imidosulfonate residue.

[0015]

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In the formula (II), R ₂₂ represents a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aralkyl group. A represents an optionally substituted linear, branched, or cyclic alkyl group, or an optionally substituted aralkyl group. It is also possible to form a 5- or 6-membered ring A and R ₂₂ have. (2) having a group that can be decomposed by an acid, and having a molecular weight of 300 whose solubility in an alkaline developer is increased by the action of an acid.
The positive photosensitive composition according to the above (1), which contains 0 or less low molecular acid decomposable dissolution inhibiting compound.

As described above, by using the compound represented by the above general formula (I) and a resin having a specific repeating unit as the photoacid generator, in a chemically amplified resist, the post-exposure heat treatment is excellent. Over time, and the photolysis efficiency is high, so the photosensitivity is high,
An excellent resist pattern was obtained.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. [I] Acid-generating compound represented by the general formula (I) As the linear, branched or cyclic alkyl group of Y and R _{1 to} R ₂₁ in the general formula (I), a methyl group, an ethyl group, a propyl group, and an isopropyl Group, n-butyl group, sec-butyl group,
1 carbon atoms such as t-butyl group, hexyl group and octyl group
And up to 20 linear or branched alkyl groups and cyclic alkyl groups such as cyclopropyl, cyclopentyl or cyclohexyl groups. Preferred substituents of the alkyl group include an alkoxy group, an acyl group, an acyloxy group, a chlorine atom, a bromine atom, an iodine atom and the like. Also, Y
Examples of the aralkyl group include a aralkyl group having 7 to 12 carbon atoms such as a benzyl group or a phenethyl group. Preferred substituents of the aralkyl group include those having 1 carbon atom.
And a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetylamino group, and a halogen atom.

The alkoxy groups represented by R _{1 to} R ₂₁ include methoxy, ethoxy, propoxy, isopropoxy,
An alkoxy group having a substituent such as an alkoxy group having 1 to 20 carbon atoms such as an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, an octyloxy group, or a dodecyloxy group, or an ethoxyethoxy group. No.
Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group. Examples of the acylamino group include an acetylamino group, a propionylamino group and a benzoylamino group. Examples of the sulfonylamino group include a substituted or unsubstituted benzenesulfonylamino group such as a sulfonylamino group having 1 to 4 carbon atoms, such as a methanesulfonylamino group and an ethanesulfonylamino group, and a p-toluenesulfonylamino group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Examples of the alkoxycarbonyl group include an alkoxycarbonyl group having 2 to 20 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, an ethoxyethoxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group. As an acyloxy group, an acetoxy group, a propanoyloxy group, an octanoyloxy group,
An acyloxy group having 2 to 20 carbon atoms such as a benzoyloxy group is exemplified. Examples of the aralkyl group include an aralkyl group having 7 to 15 carbon atoms such as a substituted or unsubstituted benzyl group and a substituted or unsubstituted phenethyl group. Preferred substituents on the aralkyl group are the same as those described above. In R ₁ to R ₂₁ is, R ₁ ~
R ₅ , R _{6 to} R ₁₂ and R _{13 to} R ₂₁ are each a group consisting of carbon and / or heteroatom which is bonded to two members of each group.
It may form a to 8-membered ring. Examples of such a 5- to 8-membered ring include cyclohexane, pyridine, furan and pyrrolidine. X and Y may be bonded to a residue of another imide sulfonate compound, or may form a dimer or a trimer. Another example of the imidosulfonate includes a compound represented by the general formula (I) of the present invention, which is a monovalent group at X or Y.

Examples of the alkylene group X include a linear or branched alkylene group having 1 to 10 carbon atoms or a monocyclic or polycyclic alkylene group which may contain a hetero atom. Examples of the linear or branched alkylene group include a methylene group, an ethylene group, a propylene group, and an octylene group. Preferred substituents on the alkylene group include an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonylamino group, a halogen atom, an aryl group, and an alkoxycarbonyl group. The alkoxy group, acyl group, nitro group, acylamino group, sulfonylamino group, aryl group, and alkoxycarbonyl group mentioned herein have the same meanings as those described for R _{1 to} R ₂₁ .
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the cyclic alkylene group include a monocyclic cycloalkylene group having 4 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group, and 7-oxabicyclo [2,2,
1] a polycyclic cycloalkylene group having 5 to 15 carbon atoms such as a heptylene group; a preferable substituent of the cycloalkylene group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, an acyl group, a formyl group; , A nitro group, an acylamino group, a sulfonylamino group, a halogen atom, an aryl group, and an alkoxycarbonyl group. The alkoxy group, acyl group, nitro group, acylamino group, sulfonylamino group, aryl group, and alkoxycarbonyl group mentioned herein have the same meanings as those described for R _{1 to} R ₂₁ . Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the arylene group include a phenylene group and a naphthylene group. Preferred substituents of the arylene group include an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonylamino group, a halogen atom, an aryl group,
An alkoxycarbonyl group. The alkyl group, cycloalkyl group, alkoxy group, acyl group, formyl group, nitro group, acylamino group, sulfonylamino group, aryl group and alkoxycarbonyl group
₁ have the same meanings as those mentioned to R _21. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkenylene group include alkenylene groups having 2 to 4 carbon atoms, such as an ethenylene group and a butenylene group. Preferred substituents of the alkenylene group are an alkyl group, a cycloalkyl group, an alkoxy group and an acyl group. Group, formyl group, nitro group, acylamino group, sulfonylamino group, halogen atom, aryl group,
An alkoxycarbonyl group. The alkyl group, cycloalkyl group, alkoxy group, acyl group, formyl group, nitro group, acylamino group, sulfonylamino group, aryl group and alkoxycarbonyl group
₁ have the same meanings as those mentioned to R _21. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the cyclic alkenylene group include a monocyclic cycloalkenylene group having 4 to 8 carbon atoms such as cyclopentenylene group and cyclohexenylene group, and a carbon number such as 7-oxabicyclo [2,2,1] heptenylene group and norbornenylene group. 5 to 15 polycyclic cycloalkenylene groups are included. As the aralkylene group, a tolylene group,
Examples include a xylylene group, and examples of the substituent include the substituents described for the arylene group. The content of the compound represented by the general formula (I) is suitably from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, more preferably from 1 to 20% by weight, based on the solid content of the whole composition. 7% by weight. Hereinafter, specific examples (I-1) to (I-38) of the compound represented by the general formula (I) are shown, but the invention is not limited thereto.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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The compound represented by the general formula (I) is GFJa
ubert, Ber., 28, 360 (1895), DEAmes et al.,
J. Chem. Soc .. 3518 (1955) or MAStolberg
79, 2615 (1957), etc., under basic conditions, under the basic conditions, using an sulfonic acid chloride and an N-hydroxyimide compound, for example, L. Bauer et al., J. Am. Org.
Chem .. 24, 1294 (1959).

[II] Other acid-generating compounds that can be used in combination In the present invention, in addition to the compound represented by the general formula (I) that generates the above-mentioned sulfonic acid, the acid can be decomposed by irradiation with other actinic rays or radiation to convert the acid. The compound generated may be used in combination. The ratio of the photoacid generator that can be used in combination with the compound represented by the general formula (I) of the present invention when used together with another photoacid generator is 95/5 to 20/80, preferably 90 / molar. 10/40/60, more preferably 80 / 20-
60/40. Such photoacid generators that can be used together are used in photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, or microresists. A known compound that generates an acid by light and a mixture thereof can be appropriately selected and used.

For example, SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) etc., U.S. Pat.No.4,069,055
No. 4,069,056, Re 27,992, Japanese Patent Application No. 3-140,140
Salt, DCNecker etal, Macrom
olecules, 17, 2468 (1984), CSwen et al, Teh, Proc. Con
f.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, 4,069,056, etc.
(1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent No. 339,049, No. 410,201.
Iodonium salts described in JP-A-2-150,848, JP-A-2-296,514, etc., JVCrivello et al., Polymer J. 17,7
3 (1985), JVCrivello et al. J. Org.Chem., 43, 3055 (19
78), WRWatt et al, J. Polymer Sci., Polymer Chem. E
d., 22, 1789 (1984), JVCrivello etal, Polymer Bul
l., 14,279 (1985), JVCrivello etal, Macromorecules,
14 (5), 1141 (1981), JVCrivello etal, J. PolymerSc
i., Polymer Chem. Ed., 17, 2877 (1979), EP 370,6
No. 93, No. 3,902,114, No. 233,567, No. 297,443
Nos. 297,442; U.S. Pat.Nos. 4,933,377; 161,81
No. 1, 410,201, 339,049, 4,760,013,
Nos. 4,734,444 and 2,833,827, Dokoku Patent No. 2,904,62
No. 6, 3,604,580, 3,604,581, etc., sulfonium salts, JVCrivello et al., Macromorecules, 10
(6), 1307 (1977), JVCrivello etal, J. PolymerSci., P
olymer Chem.Ed., 17,1047 (1979), etc., selenonium salts, CSWen et al, Teh, Proc. Conf. Rad. CuringASIA,
Onium salts such as arsonium salts described in p478 Tokyo, Oct (1988), etc., U.S. Patent No. 3,905,815, JP-B-46-4605
No., JP-A-48-36281, JP-A-55-32070, JP-A-60-2
39736, JP-A-61-169835, JP-A-61-169837,
JP-A-62-58241, JP-A-62-212401, JP-A-63-702
No. 43, organic halogen compounds described in JP-A-63-298339, etc., K. Meier et al., J. Rad.Curing, 13 (4), 26 (1986), TP
Gilletal, Inorg.Chem., 19,3007 (1980), D. Astruc, Acc. C
hem.Res., 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-14145, S. Hayase et al., JP
olymer Sci., 25, 753 (1987), E. Reichmanis et al., J. Phol
ymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQZhueta
l, J. Photochem., 36, 85, 39, 317 (1987), B. Amitetal, Tetr
ahedron Lett., (24) 2205 (1973), DHR Barton et al., JC
hem Soc., 3571 (1965), PMCollins et al., J. Chem. SoC.,
Perkin I, 1695 (1975), M. Rudinstein et al, Tetrahedron
Lett., (17), 1445 (1975), JWWalker etal J. Am. Chem. S
oc., 110, 7170 (1988), SCBusman et al., J. Imaging Tech
nol., 11 (4), 191 (1985), HMHoulihan et al, Macormolec
ules, 21, 2001 (1988), PM Collins et al., J. Chem. Soc., Ch.
em. Commun., 532 (1972), S. Hayase et al, Macromolecules,
18,1799 (1985), E. Reichmanis et al., J. Electrochem. So
c., Solid State Sci.Technol., 130 (6), FMHoulihan e
tal, Macromolcules, 21, 2001 (1988), European Patent No. 0290,750
Nos. 046,083, 156,535, 271,851, 0,
U.S. Pat.Nos. 3,901,710 and 4,181,531
, A photoacid generator having an o-nitrobenzyl-type protecting group described in JP-A-60-198538 and JP-A-53-133022, and a disulfone compound described in JP-A-61-166544. be able to.

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into a main chain or a side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas et al, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Ra
pid Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Che
m., 152, 153, 163 (1972), JVCrivello etal, J. Polymer
Sci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
3,849,137, Dokoku Patent No. 3914407, JP-A-63-26653
No., JP-A-55-164824, JP-A-62-69263, JP-A-63
-146038, JP-A-63-163452, JP-A-62-153853
And the compounds described in JP-A-63-146029 and the like can be used.

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

Among the compounds which can be used together and 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 (PA)
An S-triazine derivative represented by G2).

[0039]

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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.

[0041]

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[0042]

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[0043]

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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).

[0045]

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In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Here, 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,
And mercapto groups and halogen atoms.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, an aryl group having 6 to 14 carbon atoms, 1 to 8 carbon atoms
And substituted derivatives thereof. Preferred substituents are those having 1 to 8 carbon atoms for the aryl group.
And 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. .

[0048] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
Substituted or unsubstituted alkylsulfonic acid anions such as methanesulfonic acid anion and trifluoromethanesulfonic acid anion, substituted or unsubstituted benzenesulfonic acid anions such as toluenesulfonic acid anion and pentafluorobenzenesulfonic acid anion, naphthalenesulfonic acid anion, anthraquinone Examples thereof include, but are not limited to, condensed polynuclear aromatic sulfonic acid anions such as sulfonic acid anions, and sulfonic acid group-containing dyes.

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.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKnapcz
yk etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycoke
tal, J. Org.Chem., 35, 2532, (1970), E. Goethas et al, Bu
ll.Soc.Chem.Belg., 73,546, (1964), HM Leicester,
J. Ame. Chem. Soc., 51, 3587 (1929), JVCrivello etal,
J. Polym. Chem. Ed., 18,2677 (1980), U.S. Pat.
It can be synthesized by the methods described in JP-A Nos. 8 and 4,247,473 and JP-A-53-101,331.

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

[0064]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. Specific examples include the following compounds, but are not limited thereto.

[0066]

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[0067]

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(B) A resin having a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer and contains a repeating unit having a structure represented by the above general formula (II) or (III) a group in formula (II), straight-chain R _22, branched, cyclic alkyl groups, and substituted Y and R ₁ in the general formula (I) can be aralkyl group optionally to R ₂₁ and the alkyl synonymous And aralkyl group which may be substituted, and preferred substituents of the aralkyl group have the same meaning.
Examples of A and R ₂₂ forms a 5- or 6-membered ring may be exemplified tetrahydropyran ring, and a furan ring. In the present invention, the resin having a group that is decomposed by the action of an acid to increase the solubility in an alkaline developer is used as a copolymer component in addition to the structural units represented by the general formulas (II) and (III). May be included. Other monomer units include hydrogenated hydroxystyrene, halogen, alkoxy, or alkyl-substituted hydroxystyrene, styrene, halogen, alkoxy, acyloxy, or alkyl-substituted styrene, maleic anhydride, acrylic acid derivative, methacrylic acid derivative, N-substituted maleimide But are not limited to these. When other monomers are used in combination, the ratio of the components of the general formulas (II) and (III) to the other monomers is [(II) +
(III)] / [Other monomer components] = 99/1 to 50/5
0, preferably 95/5 to 60/40, more preferably 90/10 to 70/30.

The resin used in the present invention can be prepared by adding a polyhydroxy compound at the synthesis stage to adjust the alkali dissolution rate and improve the heat resistance, and introduce a cross-linking site connecting the polymer main chain with a polyfunctional acetal group. good. The amount of polyhydroxy compound added to the number of hydroxyl groups of the resin,
0.01 to 10 mol%, preferably 0.05 to 8 mol
%, More preferably 0.1 to 5 mol%. Examples of the polyhydroxy compound include those having 2 to 6 phenolic hydroxyl groups or alcoholic hydroxyl groups, preferably 2 to 4 hydroxyl groups, and more preferably 2 or 3 hydroxyl groups. is there. Specific examples are shown below,
The present invention is not limited to these.

[0070]

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Specific examples of the resin having a group decomposable by an acid used in the present invention are shown below, but the present invention is not limited to these.

[0072]

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[0073]

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[0074]

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[0075]

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The content of the group which can be decomposed by an acid is represented by the general formula (I
The number of acid-decomposable groups (B) in the resin represented by I) and the number of alkali-soluble groups not protected by acid-decomposable groups in the resin represented by formula (III) ( S)
It is represented by B / (B + S). The content is preferably 0.0
It is 1-0.7, more preferably 0.05-0.6, even more preferably 0.1-0.6. B / (B + S)> 0.
No. 7 is not preferred because it causes film shrinkage after PEB, poor adhesion to the substrate, and scum. On the other hand, B / (B + S) <0.
A value of 01 is not preferable because standing waves may remarkably remain on the pattern side walls.

The weight average molecular weight (Mw) of the resin having an acid-decomposable group is preferably in the range of 2,000 to 200,000. If the molecular weight is less than 2,000, the film loss is large due to the development of the unexposed portion. If the molecular weight exceeds 200,000, the dissolution rate of the alkali-soluble resin itself in alkali becomes slow and the sensitivity is lowered. More preferably, 5,
The range is from 000 to 150,000, and more preferably from 8,000 to 150,000. Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.

In the present invention, two or more resins having a group decomposable with an acid may be used in combination. The amount of these resins used in the present invention is 40 to 99% by weight, preferably 60 to 95% by weight, based on the total weight of the photosensitive composition (excluding the solvent).

The acid-decomposable resin other than the resin according to the present invention is used.
A resin having a group may be used in combination. Chemistry in the present invention
Degraded by other acids used in amplified resist
And has a group that increases solubility in alkaline developers
The main chain or side chain of the resin or the main resin
Resin having acid-decomposable groups on both chain and side chain
is there. Among them, a resin having a group which can be decomposed by an acid in a side chain is used.
More preferred. Preferred groups that can be decomposed with an acid are
-COOA⁰, -OB⁰And further include these
As a group, -R⁰-COOA⁰Or -A_r-OB
⁰The group shown by these is mentioned. Where A⁰Is -C (R
⁰¹) (R⁰²) (R⁰³), -Si (R⁰¹) (R⁰²)
(R ⁰³) Or -C (R⁰⁴) (R⁰⁵) -OR⁰⁶Base
Show. B⁰Is -A⁰Or -CO-OA⁰Indicates a group
(R⁰, R⁰¹~ R⁰⁶, And Ar are as defined below).

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, a tetrahydropyranyl ester group, an enol ether group, an enol ester group,
And a tertiary alkyl ester group and a tertiary alkyl carbonate group. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, an acetal group, and a tetrahydropyranyl ether group.

Next, the groups decomposable by these acids form side chains.
When the base resin is bonded with --OH in the side chain,
Or -COOH, preferably -R⁰-COOH or
-A _rIt is an alkali-soluble resin having an -OH group. An example
For example, the alkali-soluble resin described below can be mentioned.
You.

The alkali dissolution rate of these alkali-soluble resins was determined by measuring with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.) to be 170.
A / sec or more is preferable. Particularly preferably 330A
/ Sec or more (A is angstroms). From the viewpoint of achieving a rectangular profile, an alkali-soluble resin having a high transmittance to far ultraviolet light or excimer laser light is preferable. Preferably, the transmittance at a wavelength of 248 nm with a thickness of 1 μm is 20 to 90%. From this perspective,
Particularly preferred alkali-soluble resins are o-, m-, p-
Poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen- or alkyl-substituted poly (hydroxystyrene), part of poly (hydroxystyrene), O-alkylated or O-acylated product, styrene -Hydroxystyrene copolymer, α
-Methylstyrene-hydroxystyrene copolymer and hydrogenated novolak resin.

The resin having an acid-decomposable group used in the present invention may be obtained by reacting an alkali-soluble resin with a precursor of an acid-decomposable group, or by reacting an acid-decomposable group with an alkali-soluble resin. It can be obtained by copolymerizing a monomer with various monomers.

An acid-decomposable low-molecular-weight dissolution-inhibiting compound described later may be mixed with the acid generator and the resin having an acid-decomposable group. The acid-decomposable dissolution inhibiting compound used in the present invention has at least two acid-decomposable groups in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, the acid-decomposable group Is a compound having at least 8 bonding atoms excluding. In the present invention, the acid-decomposable dissolution-inhibiting compound preferably has at least two groups capable of being decomposed by an acid in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, the acid-decomposable group A compound having at least 10, preferably at least 11, and more preferably at least 12 bonding atoms excluding the above, or a position where the distance between the acid-decomposable groups is the longest, having at least three acid-decomposable groups Is a compound having at least 9, preferably at least 10, and more preferably at least 11 bonding atoms excluding an acid-decomposable group. or,
The preferred upper limit of the number of the bonding atoms is 50, more preferably 30. In the present invention, when the acid-decomposable dissolution-inhibiting compound has three or more, preferably four or more acid-decomposable groups, and even when the compound has two acid-decomposable groups, the acid-decomposable groups are mutually present. If they are separated by a certain distance or more, the dissolution inhibiting property with respect to the alkali-soluble resin is significantly improved. Incidentally, the distance between the acid-decomposable groups in the present invention,
It is indicated by the number of via bond atoms excluding the acid-decomposable group. For example, in the case of the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonding atoms, and in the compound (3), the bonding atom is 12 bonding atoms.

[0085]

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Further, the acid-decomposable dissolution-inhibiting compound of the present invention may have a plurality of acid-decomposable groups on one benzene ring, but preferably, one compound on one benzene ring. It is a compound composed of a skeleton having an acid-decomposable group. Further, the molecular weight of the acid-decomposable dissolution-inhibiting compound of the present invention is 3,000 or less, preferably 500 to 3,000.
0, more preferably 1,000 to 2,500.

In a preferred embodiment of the present invention,
A group which can be decomposed by, ie, -COO-A⁰, -OB⁰
As a group containing a group, -R⁰-COO-A⁰Or -A
r-OB⁰The group shown by these is mentioned. Where A
⁰Is -C (R⁰¹) (R⁰²) (R⁰³), -Si (R⁰¹)
(R⁰²) (R ⁰³) Or -C (R⁰⁴) (R⁰⁵) -O-
R⁰⁶Represents a group. B⁰Is A⁰Or -CO-OA⁰Base
Show. R⁰¹, R⁰², R⁰³, R⁰⁴And R⁰⁵Are the same
May be different from each other, and may include a hydrogen atom, an alkyl group,
Represents a chloroalkyl, alkenyl, or aryl group
Then R⁰⁶Represents an alkyl group or an aryl group. However
Then R⁰¹~ R⁰³At least two are groups other than hydrogen atoms
And R⁰¹~ R⁰³, And R⁰⁴~ R⁰⁶Two of
The groups may combine to form a ring. R⁰Has a substituent
Divalent or higher aliphatic or aromatic hydrocarbons
Represents a group, -Ar- has a monocyclic or polycyclic substituent
And a divalent or higher aromatic group which may be present.

Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Preferred are those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl groups having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Preferably, the aryl group has 6 to 1 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl and anthracenyl.
Four are preferred. Further, as a substituent, a hydroxyl group,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group and a t-butoxy group,
Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, aralkyloxy groups, acyl groups such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, and valeryl group. Group, an acyloxy group such as a butyryloxy group, the above alkenyl group, a vinyloxy group.
Examples thereof include an alkenyloxy group such as a propenyloxy group, an allyloxy group, and a butenyloxy group, an aryloxy group such as the above-described aryl group and phenoxy group, and an aryloxycarbonyl group such as a benzoyloxy group.

The group which can be decomposed by an acid is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group, or a tertiary alkyl ether group. Alkyl ester groups, tertiary alkyl carbonate groups and the like. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

As the acid-decomposable dissolution-inhibiting compound, those described in JP-A-1-289946 and JP-A-1-2899 are preferred.
No. 47, JP-A-2-2560, JP-A-3-12895
9, JP-A-3-158855, JP-A-3-1793
No. 53, JP-A-3-191351, JP-A-3-200
No. 251, JP-A-3-200252, JP-A-3-20
0253, JP-A-3-200254, JP-A-3-2
0255, JP-A-3-259149, JP-A-3-259
279958, JP-A-3-279959, JP-A-4
JP-A-1650, JP-A-4-1651, JP-A-4-11
No. 260, JP-A-4-12356, JP-A-4-123
No. 57, Japanese Patent Application No. 3-33229, Japanese Patent Application No. 3-2307
No. 90, Japanese Patent Application No. 3-320438, Japanese Patent Application No. 4-251
No. 57, Japanese Patent Application No. 4-52732, Japanese Patent Application No. 4-1032
No. 15, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-107
No. 885, Japanese Patent Application No. 4-107889 and No. 4-1521
Compounds in which some or all of the phenolic OH groups of the polyhydroxy compound described in the specification such as No. 95 are bonded and protected by the above-mentioned groups, -R ⁰ -COO-A ⁰ or B ⁰ groups, included.

More preferably, JP-A-1-289946.
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
255, JP-A-3-259149, JP-A-3-27
9958, JP-A-4-1650, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
7, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
No. 5 using the polyhydroxy compound described in the specification.

More specifically, general formulas [I] to [XV]
The compound represented by I] is mentioned.

[0093]

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[0094]

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[0095]

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[0096]

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R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ , R ¹³⁰ : may be the same or different, and represent a hydrogen atom, —R ⁰ —COO—C
( ^R01 ) ( ^R02 ) ( ^R03 ) or -CO-OC ( ^R01 )
^{(R 0 2) (R 03} ), provided that the definition of R ^0, R ^01, R ⁰² and R ⁰³ are as defined above.

R ¹⁰⁰ : -CO-, -COO-, -NHC
ONH-, -NHCOO-, -O-, -S-, -SO
-, -SO _2- , -SO _3- , or

[0099]

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[0100] Here, G = 2 to 6, provided that at least one alkyl group of R ^0.99, R ¹⁵¹ when the ^{G = 2, R 150, R} 151: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH,
-CN, halogen atom, -R ¹⁵² -COOR ^{15 3} or ^{-R 154 -OH, R 152, R} 154: an alkylene group, R ^153: a hydrogen atom, an alkyl group, an aryl group or an aralkyl group,, R ^99, R ¹⁰³ To R ¹⁰⁷ , R ¹⁰⁹ , R ^{111 to} R ¹¹⁸ , R
^{121 to} R ¹²³ , R ^{128 to} R ¹²⁹ , R ^{131 to} R ¹³⁴ , R
^{138 to} R ¹⁴¹ and R ¹⁴³ may be the same or different and include a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a halogen atom, nitro Group, carboxyl group, cyano group, or -N ( ^R155 )
(R ¹⁵⁶ ) (R ¹⁵⁵ , R ¹⁵⁶ : H, alkyl group or aryl group) R ¹¹⁰ : single bond, alkylene group, or

[0101]

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R ¹⁵⁷ and R ¹⁵⁹ may be the same or different, and represent a single bond, an alkylene group, —O—, —S—, —CO
— Or a carboxyl group, R ¹⁵⁸ : a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, a nitro group, a hydroxyl group, a cyano group, or a carboxyl group, provided that the hydroxyl group is an acid-decomposable group (for example, t-butoxycarbonylmethyl group, tetrahydropyranyl group, 1-ethoxy-1-ethyl group,
(1-t-butoxy-1-ethyl group).

R ¹¹⁹ and R ¹²⁰ may be the same or different and are each a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkylene group, provided that the lower alkyl group is an alkyl group having 1 to 4 carbon atoms. R ^{124 to} R ¹²⁷ may be the same or different and may be a hydrogen atom or an alkyl group; R ^{135 to} R ¹³⁷ may be the same or different and a hydrogen atom;
An alkyl group, an alkoxy group, an acyl group, or an acyloxy group, R ¹⁴² : a hydrogen atom, —R ⁰ —COO—C (R ⁰¹ )
( ^R02 ) ( ^R03 ) or -CO-OC ( ^R01 ) ( ^R02 )
(R ⁰³ ), or

[0104]

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R ¹⁴⁴ and R ¹⁴⁵ may be the same or different and represent a hydrogen atom, a lower alkyl group, a lower haloalkyl group,
Or an aryl group, R ^{146 to} R ¹⁴⁹ : may be the same or different and represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carbonyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aralkyl group, and an aralkyloxy group. A group, an acyl group, an acyloxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group, provided that the four substituents having the same symbol need not be the same group. : —CO— or —SO ₂ —, Z, B: single bond or —O—, A: methylene group, lower alkyl-substituted methylene group, halomethylene group, or haloalkylene group; E: single bond or oxymethylene Groups, a to z, a1 to y1: when plural, the groups in parentheses may be the same or different; a to q, s, t, v, g1 to i1, k 1 to m1, o1, q1, s1, u1: 0 or an integer of 1 to 5, r, u, w, x, y, z, a1 to f1, p1, r1, t1, v1 to x1: 0 or 1
An integer of 4, j1, n1, z1, a2, b2, c2, d2: an integer of 0 or 1 to 3, at least one of z1, a2, c2, d2 is 1 or more, y1: an integer of 3 to 8, (a + b), (e + f + g), (k + l + m), (q + r + s), (w + x + y), (c1 + d1), (g1 +
h1 + i1 + j1), (o1 + p1), (s1 + t1) ≧ 2, (j1 + n1) ≦ 3, (r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1 + f1), (p1 + r1),
(t1 + v1), (x1 + w1) ≦ 4, provided that (w +
z), (x + a1) ≦ 5, (a + c), (b + d), (e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q
+ t), (s + v), (g1 + k1), (h1 + l1), (i1 + m1), (o1 + q1), (s1 + u1)
≦ 5.

[0106]

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[0107]

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[0108]

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[0109]

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Specific examples of preferred compound skeletons are shown below.

[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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R in the compounds (1) to (63) is a hydrogen atom,

[0131]

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Represents the following. However, at least two or three depending on the structure are groups other than hydrogen atoms, and each substituent R
Need not be the same group.

In this case, the content of the dissolution inhibiting compound is 3 to 4 based on the total weight of the photosensitive composition (excluding the solvent).
It is 5% by weight, preferably 5 to 30% by weight, more preferably 10 to 20% by weight.

Further, in order to adjust the alkali solubility,
An alkali-soluble resin having no acid-decomposable group may be mixed. As such an alkali-soluble resin,
For example, novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene,
m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m
/ P-hydroxystyrene copolymer, partially O-alkylated product (for example, 5 to 30 mol% of O-methylated product) to the hydroxyl group of polyhydroxystyrene or O-
Acylated product (for example, 5 to 30 mol% o-acetylated product), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-
Hydroxystyrene copolymer, carboxyl group-containing methacrylic resin and its derivatives can be mentioned,
It is not limited to these. Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partial O-alkylation of polyhydroxystyrene, Or O-acylated product, styrene-
Hydroxystyrene copolymer and α-methylstyrene-hydroxystyrene copolymer. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

Examples of the predetermined monomer include phenol and m
Cresols such as -cresol, p-cresol and o-cresol, xylenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and 2,3-xylenol, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, Alkoxyphenols such as -methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol, 2-methyl-4-isopropyl Fenault Bis-alkylphenols etc., m
Hydroxychloro compounds such as -chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or as a mixture of two or more, but are not limited thereto. It is not something to be done.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-
Phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o -Methylbenzaldehyde, m-methylbenzaldehyde,
p-Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde and their acetal forms, for example, chloroacetaldehyde diethyl acetal, among which formaldehyde is used Is preferred. These aldehydes are used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

The weight average molecular weight of the novolak resin thus obtained is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred are 2,000-20,
000. In addition, the weight average molecular weight of the polyhydroxystyrene other than the novolak resin, its derivative, and the copolymer is 2,000 or more, preferably 5,000.
~ 200,000, more preferably 10,000-1000
00. Further, from the viewpoint of improving the heat resistance of the resist film, 25,000 or more is preferable. here,
The weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography. In the present invention, these alkali-soluble resins may be used as a mixture of two or more kinds.

Other Components Used in the Present Invention The photosensitive composition of the present invention may further contain a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, an organic basic compound, and a developer, if necessary. Phenolic O that promotes solubility in water
A compound having two or more H groups can be contained.

The compound having two or more phenolic OH groups that can be used in the present invention is preferably a phenol compound having a molecular weight of 1,000 or less. Further, it is necessary to have at least two phenolic hydroxyl groups in the molecule. If the number exceeds 10, the effect of improving the development latitude is lost. When the ratio of the phenolic hydroxyl group to the aromatic ring is less than 0.5, the film thickness dependency is large, and the development latitude tends to be narrow. If this ratio exceeds 1.4, the stability of the composition deteriorates, and it becomes difficult to obtain high resolution and good film thickness dependency, which is not preferable.

The preferable addition amount of the phenol compound is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the alkali-soluble resin. 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 phenol compounds 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 at Specific examples of the phenol compound are shown below, but the compounds that can be used in the present invention are not limited to these.

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).

[0144]

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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,
Examples include, but are not limited to, N-aminomorpholine and N- (2-aminoethyl) morpholine.

These nitrogen-containing basic compounds may be used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001-10 parts by weight, preferably 0.01-5 parts by weight, per 100 parts by weight of the photosensitive resin composition (excluding the solvent). If the amount is less than 0.001 part by weight, the effects of the present invention cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the unexposed part 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.

Further, a spectral sensitizer as described below is added to sensitize the photosensitive composition of the present invention to a longer wavelength region than the deep ultraviolet where the photoacid generator used has no absorption. Sensitivity can be given to the i or g line. Suitable spectral sensitizers include, specifically, 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-nitrofluorene, 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. Further, these spectral sensitizers can also be used as a light absorbing agent for far ultraviolet light of 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 photosensitive composition of the present invention is dissolved in a solvent capable of dissolving each of the above components and applied on a support. Examples of the solvent used herein include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, and 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.

A surfactant may be added to the above solvents. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, 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, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants such as polyoxyethylene sorbitan fatty acid esters such as acrylates and the like, F-top EF301, E 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora - de FC430, FC43
1 (manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC101, SC102,
Fluorinated surfactants such as SC103, SC104, SC105 and 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 the like. The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. These surfactants may be added alone or in some combination.

The photosensitive composition is applied on a substrate (eg, silicon / silicon dioxide coating) to be used in the production of precision integrated circuit devices by a suitable application method such as a spinner or a coater, and then passed through a predetermined mask. By exposing, baking and developing, a good resist pattern can be obtained.

Examples of the developer for the photosensitive composition of the present invention include:
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.

[0153]

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 (Synthesis of Compound I-1) 10.0 g of N-hydroxyphthalimide and 10.8 g of benzenesulfonyl chloride were dissolved in 100 ml of acetone, and 6.5 g of triethylamine was added dropwise to this solution over 20 minutes. After stirring at room temperature for 2 hours, the mixture was poured into 500 ml of distilled water. The precipitated powder was collected by filtration, washed with water, and dried to obtain compound I-1.
8.2 g were obtained.

Synthesis Example 2 (Synthesis of Compound I-2) 10.0 g of N-hydroxyphthalimide and 11.7 g of p-toluenesulfonyl chloride were dissolved in 100 ml of acetone, and 6.5 g of triethylamine was added dropwise to this solution over 20 minutes.
After stirring at room temperature for 2 hours, the mixture was poured into 500 ml of distilled water.
The precipitated powder was collected by filtration, washed with water, and dried to obtain a crude crystal. When this was recrystallized from ethanol / toluene, the compound (I)
-2) was obtained 17.3 g.

Synthesis Example 3 (Synthesis of Compound I-21) Hydroxyamine hydrochloride (21.4 g) was dissolved in distilled water (80 ml), and NaOH (12.3 g) was added to distilled water (50 m).
1 was added over 30 minutes under ice cooling. 50.0 g of 4-methylphthalic anhydride was added to this solution, and the mixture was stirred at room temperature for 1 hour, and then refluxed for 4 hours. The reaction was cooled on ice,
The precipitated powder was filtered and washed with water. The obtained crude crystals were recrystallized from acetone / water to obtain 27.0 g of 4-methyl-N-hydroxyphthalimide. 4-methyl-N-
0.53 g of hydroxyphthalimide and 0.62 g of 4-methoxybenzenesulfonyl chloride in 30 ml of acetone
And 0.32 g of triethylamine was added to this solution over 10 minutes. After reacting at room temperature for 2 hours, the reaction solution was poured into 150 ml of distilled water, and the precipitated powder was collected by filtration, washed with water and dried to obtain 1.0 g of compound I-21. Thereafter, the corresponding N-hydroxyimide and sulfonic acid chloride were reacted in the presence of a base in the same manner to obtain a sulfonic acid ester of N-hydroxyimide.

Synthesis Example 4 (Synthesis of Comparative Acid Generator) 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane (PAG-Y) was obtained by the method described in JP-A-5-249682.

Synthesis Example 5 (Synthesis Example 1 of Resin) Poly p-hydroxystyrene (weight average molecular weight 1100)
0) 48 g was dissolved in 250 ml of dehydrated THF. 23.3 g of t-butyl vinyl ether and dehydrated p-
0.1 g of toluenesulfonic acid was added, and the mixture was stirred at room temperature for 4 hours. The reaction solution was deionized water 3 l / triethylamine 3
g, and the precipitated powder was collected by filtration, washed with water, and dried to give p-hydroxystyrene / p- (1-t-butoxyethoxy) styrene copolymer (50/50) (weight average molecular weight 13,000). Obtained.

Synthesis Example 6 (Synthesis Example 2 of Resin) Poly p-hydroxystyrene (weight average molecular weight 1100)
0) 48 g was dissolved in 250 ml of dehydrated THF. 14.0 g of t-butyl vinyl ether and 0.96 of 2,2-bis (4-hydroxycyclohexyl) propane were added to this solution.
g and 0.1 g of dehydrated p-toluenesulfonic acid were added, and the mixture was stirred at room temperature for 24 hours. The reaction solution was poured into a solution of 3 l of ion-exchanged water / 3 g of triethylamine, and the precipitated powder was collected by filtration, washed with water and dried to obtain p-hydroxystyrene / p-
(1-t-butoxyethoxy) styrene copolymer (partially crosslinked) (weight average molecular weight 18,000) was obtained.

Synthesis Example 7 (Synthesis Example 3 of Resin) Instead of t-butyl vinyl ether of Synthesis Example 1, 2,3
P-hydroxystyrene / p- (2-tetrahydropyranyloxy) styrene copolymer (50/50) in the same manner as in Synthesis Example 1 except that -dihydro-4H-pyran was used.
(Weight average molecular weight 13000) was obtained.

Synthesis Example 8 (Synthesis Example 4 of Resin) Poly p-hydroxystyrene (weight average molecular weight 1100)
0) was dissolved in 40 ml of pyridine, and 1.6 g of di-t-butyl dicarbonate was added thereto while stirring at room temperature. After reacting at room temperature for 3 hours, the mixture was added to a solution of 1 l of ion-exchanged water / 20 g of concentrated hydrochloric acid. The precipitated powder is filtered, washed with water, dried and p-
A hydroxystyrene / p- (t-butyloxycarbonyloxy) styrene copolymer (50/50) was obtained.

Synthesis Example 9 (Resin Synthesis Example 5) A p-hydroxystyrene / p- (1-cyclohexyloxyethoxy) styrene copolymer (50/50) (weight average molecular weight) was prepared in the same manner as in Synthesis Example 5. 13000)
And p-hydroxystyrene / p- (1-ethoxyethoxy) styrene copolymer (50/50) (weight average molecular weight 12,000).

Synthesis Example 10 (Synthesis Example 6 of resin) Poly p-hydroxystyrene (VP-800 manufactured by Nippon Soda)
0, weight average molecular weight 11000) 500 g of dehydrated THF
Dissolved in 2000 ml. To this solution were added 176 g of iso-butyl vinyl ether and 0.15 g of dehydrated p-toluenesulfonic acid, and the mixture was stirred at room temperature for 10 hours. After adding 16 g of triethylamine to the reaction mixture, 40 l of deionized water was added.
And the precipitated powder was collected by filtration, washed with water, and dried to obtain a p-hydroxystyrene / p- (1-iso-butoxyethoxy) styrene copolymer (60/40) (weight average molecular weight 12,000). Was.

Synthesis Example 11 (Resin Synthesis Example 7) Poly p-hydroxystyrene (VP-800 manufactured by Nippon Soda)
0, weight average molecular weight 11000) 500 g of dehydrated THF
Dissolved in 2000 ml. 166 g of iso-butyl vinyl ether, 40 g of 2,2-bis (4-hydroxycyclohexyl) propane and 0.15 g of dehydrated p-toluenesulfonic acid were added to this solution, and the mixture was stirred at room temperature for 10 hours. After adding 16 g of triethylamine to the reaction solution, the mixture was poured into a solution of 40 l of ion-exchanged water, and the precipitated powder was collected by filtration, washed with water and dried to obtain p-hydroxystyrene / p- (1-i
so-butoxyethoxy) styrene copolymer (70/3
0 partially crosslinked type) (weight average molecular weight 96,000).

Synthesis Example 12 (Synthesis example of dissolution inhibitor compound—
1) α, α ′, α ″ -tris (4-hydroxyphenyl)-
20 g of 1,3,5-triisopropylbenzene was dissolved in 400 ml of tetrahydrofuran. To this solution was added 14 g of potassium tert-butoxide under a nitrogen atmosphere,
After stirring for 2 minutes, di-tert-butyl dicarbonate 29.2
g was added. The reaction was allowed to proceed at room temperature for 3 hours, the reaction solution was poured into ice water, and the product was extracted with ethyl acetate. The ethyl acetate layer was further washed with water and dried, after which the solvent was distilled off. The obtained crystalline solid was recrystallized (diethyl ether) and dried to obtain 25.6 g of a compound example (31: R are all t-BOC groups).

Synthesis Example 13 (Synthesis example of dissolution inhibitor compound—
2) 1- [α-methyl-α- (4′-hydroxyphenyl)
Ethyl] -4- [α ', α'-bis (4 "-hydroxyphenyl) ethyl] benzene (42.4 g, 0.10 mol) was dissolved in N, N-dimethylacetamide (300 ml), and potassium carbonate was added thereto. 5 g (0.35 mol),
And 84.8 g (0.33 mol) of cumyl bromoacetate. Thereafter, the mixture was stirred at 120 ° C. for 7 hours. The reaction mixture was poured into 2 l of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate. Concentration of the ethyl acetate extract, which was purified by column chromatography, Compound Example (18: R are all -CH ₂ COOC (CH
₃ ) ₂ C ₆ H ₅ groups) 70 g were obtained.

Synthesis Example 14 (Synthesis example of dissolution inhibitor compound—
3) 44 g of 1,3,3,5-tetrakis- (4-hydroxyphenyl) pentane was added to N, N-dimethylacetamide 2
Dissolve in 50 ml, add 70.7 g of potassium carbonate,
Then, 90.3 g of t-butyl bromoacetate was added, and
For 7 hours. The reaction mixture was poured into 2 l of ion-exchanged water, and the obtained viscous material was washed with water. This was purified by column chromatography to obtain 87 g of Compound Example 60 (R was all -CH2COOC4H9t).

Synthesis Example 15 (Synthesis example of dissolution inhibitor compound—
4) α, α, α ′, α ′, α ″, α ″,-hexakis (4-
20 g of (hydroxyphenyl) -1,3,5-triethylbenzene was dissolved in 400 ml of diethyl ether.
Under a nitrogen atmosphere, 42.4 g of 3,4-dihydro-2H-pyran and a catalytic amount of hydrochloric acid were added to the solution, and the mixture was refluxed for 24 hours. After the completion of the reaction, a small amount of sodium hydroxide was added, followed by filtration. The filtrate was concentrated and purified by column chromatography to obtain 55.3 g of Compound Example 62 (R is all THP groups).

Examples 1 to 11 and Comparative Examples 1 and 2 Resists were prepared using the compounds of the present invention shown in the above Synthesis Examples. The prescription at that time is shown in Table 1 below.

[0169]

[Table 1] The abbreviations used in Table 1 indicate the following contents. <Polymer> In parentheses, the molar ratio is PHS / iBES p-hydroxystyrene / p-
(1-iso-butoxyethoxy) styrene copolymer (60/40) PHS / iBESB p-hydroxystyrene / p-
(1-iso-butoxyethoxy) styrene copolymer (70/30 partially crosslinked) PHS / tBES p-hydroxystyrene / p-
(1-t-butoxyethoxy) styrene copolymer (60
/ 40) PHS / tBESB p-hydroxystyrene / p-
(1-t-butoxyethoxy) styrene copolymer (70
/ 30 partially crosslinked type) PHS / EES p-hydroxystyrene / p-
(1-ethoxyethoxy) styrene copolymer (55/4
5) PHS / EESB p-hydroxystyrene / p-
(1-ethoxyethoxy) styrene copolymer (55/4
PHS / THPS p-hydroxystyrene / p-
(2-tetrahydropyranyloxy) styrene copolymer (60/40) PHS / tBOCS p-hydroxystyrene / p-
(T-butyloxycarbonyloxy) styrene copolymer (60/40) PHS / CHES p-hydroxystyrene / p-
(1-cyclohexyloxyethoxy) styrene copolymer (50/50)

<Acid-decomposable group in dissolution inhibitor>

[0171]

Embedded image

[Preparation and Evaluation of Photosensitive Composition] To each material shown in Table 1 was added 0.02 g of 4-dimethylaminopyridine, dissolved in 9.5 g of propylene glycol monomethyl ether acetate, and filtered through a 0.2 μm filter. Thus, a resist solution was prepared. This resist solution is applied on a silicon wafer using a spin coater,
The resist film was dried on a vacuum adsorption type hot plate at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 0.83 μm. This resist film was exposed using a 248 nm KrF excimer laser stepper (NA = 0.42). Immediately after the exposure, each was heated for 60 seconds on a vacuum adsorption type hot plate at 100 ° C., immediately immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The profile, sensitivity, and resolution of the pattern on the silicon wafer thus obtained were evaluated and compared as follows. The results are shown in Table 2 below.

[Profile] The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist profile. [Sensitivity] Sensitivity was defined as an exposure amount that reproduced a mask pattern of 0.40 μm. [Resolving power] The resolving power indicates a limit resolving power at an exposure amount for reproducing a mask pattern of 0.40 μm.

Further, after a lapse of 2 hours from the exposure in the same manner,
Heat as above and immediately with 2.38% aqueous tetramethylammonium hydroxide (TMAH)
It was immersed for 0 second, rinsed with water for 30 seconds and dried. The line width of the 0.35 μm mask pattern thus obtained was measured, and the rate of change from the value immediately after exposure was calculated. Table 2 shows the results. In the table, “change in line width over time of 2 hours after exposure” is based on the following equation. That is, change in line width over time after exposure for 2 hours = ｛[(line width when developed immediately after exposure) − (line width when developed after 2 hours after exposure)] / (line width when developed immediately after exposure) )｝ × 100

[0175]

[Table 2]

[Storage stability] The p-hydroxystyrene / p- (1-ethoxyethoxy) styrene copolymer (50/50) (PHS / EE) obtained in Resin Synthesis Example 5
S) and p-hydroxystyrene / p-synthesized using the same method as described in JP-A-7-140666.
Using (2- (2-methoxy) -propyloxy) styrene copolymer (50/50) (PHS / MPS), a resist solution was prepared according to the following formulation. The sensitivity and the resolving power were evaluated by using the same method as in the above example immediately after preparing the solution and storing the resist solution at 5 ° C. for 3 months with nitrogen sealed.

[0177]

[Table 3]

From the results shown in Tables 2 and 3, the resist of the present invention has a good profile, high sensitivity and high resolution, a small change in the line width of the pattern over time after exposure, and excellent storage stability. It turns out that it is a positive photosensitive composition.

[0179]

EFFECTS OF THE INVENTION The chemically amplified positive photosensitive composition of the present invention has good profile, high sensitivity and high resolution, has little change in performance over time after exposure, and has excellent storage stability. Type photosensitive composition can be provided.

Claims (2)

[Claims] (1) by irradiation with actinic rays or radiation;
Represented by the following general formula (I) which generates sulfonic acid
Decomposes by the action of the compound and (b) the acid
The following general formula having a group that increases solubility in an image solution
(II) and a repeating unit of the structure represented by the general formula (III)
Positive photosensitivity, characterized by containing a resin containing
Composition. Embedded imageIn the formula (I), Y represents a linear group which may have a substituent;
Branch, cyclic alkyl group, aralkyl which may be substituted
Group,Represents a group represented by (R₁~ R_{twenty one}Are the same but different
Or a hydrogen atom, a linear group which may have a substituent,
Branch, cyclic alkyl group, alkoxy group, acyl group, acyl group
Amino group, sulfonylamino group, aryl group, acyloxy
Si group, aralkyl group or alkoxycarbonyl group,
Or formyl group, nitro group, chlorine atom, bromine atom, iodine
A hydrogen atom, a hydroxyl group, or a cyano group;₁~
R_Five, R₆~ R ₁₂And R₁₃~ R_{twenty one}Is in each group
Are bonded to each other by carbon and / or heteroatom 5
Or an 8-membered ring). Y is another imide
It may be bonded to the residue of the sulfonate compound. X is
Linear or branched alkylene group which may have a substituent,
It may have a substituent or may contain a hetero atom
Monocyclic or polycyclic alkylene group, which may be substituted
Straight-chain, branched alkenylene, optionally substituted
Monocyclic or polycyclic alkenylene optionally containing
Group, an optionally substituted arylene group,
The aralkylene group which may be present is shown. Also, X is another imi
It may be bonded to a dosulfonate residue. Embedded imageIn the formula (II), R_{twenty two}Is a hydrogen atom,
Chain, branched, cyclic alkyl group or
Represents an aralkyl group. A is an optionally substituted straight chain,
A branched or cyclic alkyl group or an optionally substituted ara
Represents a alkyl group. A and R_{twenty two}Is a 5- or 6-membered ring
May be formed. 2. A low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less, which has a group decomposable by an acid and whose solubility in an alkaline developer is increased by the action of an acid. The positive photosensitive composition according to claim 1.