JPH11109631A - Positive photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive compsn. which enhances the resolution of a fine pattern, suppresses reduction in the film thickness of an unexposed part and without accompanying reduction insensitivity by using a resin having a specified partial structure which is decomposed by an acid as a constituent component of the photosensitive compsn. SOLUTION: A photosensitive compsn. contains a compd. which generates an acid by irradiating active light beams or radiation and an acid decomposable resin in which a polymer principal chain is crosslinked with acid decomposable groups represented by formula, wherein R1 and R2 are each a linear, branched or cyclic alkyl group, optionally substd. an aralkyl group or optionally substd. on aryl group, two or more of R1 and R2 may combine to form a monocycle or polycycle, X is a single bond, optionally substd. an arylene group, optionally substd. a linear, branched or cyclic alkylene group which may contains a heteroatom, optionally substd. a linear, branched or cyclic alkenylene group which may contain a heteroatom or the like and (n) is 2 or 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition, and more particularly to a photomask for manufacturing semiconductor circuit elements, integrated circuits, printed wiring boards, liquid crystal display panels and other microphotofabrication processes. The present invention relates to a chemically amplified positive resist composition.

[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 has been conventionally used. For example, “Novolak-type phenolic resin / naphthoquinonediazide-substituted compound” is disclosed in US Pat. No. 3,666,473.
No. 4,115,128 and U.S. Pat. No. 4,173,470, and the most typical composition is a combination of "novolak resin composed of cresol-formaldehyde / trihydroxybenzophenone-1,2-naphthoquinonediazide sulfonic acid ester" To Thompson "Introduction to Microlithography" (L.
F. Thompson "Introduction to Microlithography")
(ACS Publishing, No. 2, 19, pp. 112-121)
It is described in. In such a positive photoresist consisting essentially of a novolak resin and a quinonediazide compound, the novolak resin gives high resistance to plasma etching, the naphthoquinonediazide compound acts as a dissolution inhibitor, and the naphthoquinonediazide is exposed to light. When exposed to carboxylic acid, carboxylic acid is generated, the dissolution inhibiting ability is lost, and the alkali solubility of the novolak resin is increased.

[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 this problem is a chemically amplified resist composition described in US Pat. No. 4,491,628, European Patent 249,139 and the like. 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.

[0005] Examples of such a combination include a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (JP-A-48-90303) and a combination of an orthoester or an amide acetal compound (JP-A-48-90303). Showa 5
No. 1-120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-1334).
No. 29), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236), and a polymer having an orthoester group in the main chain. Combinations (JP-A-56-17345), combinations with tertiary alkyl ester compounds (JP-A-60-3625), combinations with silyl ester compounds (JP-A-60-10247),
And a combination with a silyl ether compound (JP-A-60-3
7549, 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 and JP-A-60-3625. JP-A-62-229242, JP-A-63-27829, JP-A-63-36240,
JP-A-63-250542, Polym.Eng.Sce., 23, 1
012 (1983); ACS. Sym. 242, 11 (1984); Semico
nductor World, 1987, November, p. 91; Macromolecule
s, vol. 21, 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) in combination with an ester or carbonate compound. These systems also have high sensitivity and have a smaller absorption in the Deep-UV region than the naphthoquinonediazide / novolak resin system, so that they can be effective systems for shortening the wavelength of the light source.

The positive chemically amplified resist has an alkali-soluble resin, a compound capable of generating an acid upon exposure to radiation (photoacid generator), and a group decomposed by an acid (referred to as an acid-decomposable group). It can be broadly classified into a three-component system composed of a dissolution inhibiting compound for a soluble resin, and a two-component system composed of a resin having a group which is decomposed by reacting with an acid to become 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.

The object of the present invention is to improve the above-mentioned drawbacks of the chemically amplified resist and to improve the practical performance. In any case, the basic requirement of the chemically amplified positive resist is that it is exposed to light. If the acid is present as a result of exposure, the dissolution inhibiting ability will be lost and the dissolution rate will be increased, and if this requirement is satisfied, the dissolution rate of both will, of course, be high. This increases the resolution, prevents dissolution loss (film loss) in unexposed portions, and increases the precision of the pattern shape. From this viewpoint, with respect to the resin having a group which is decomposed by the reaction with an acid to become alkali-soluble, a resin having a t-butoxy group as an acid labile group (DAConlon et al., Macromolecules, 22
Vol., P. 509 (1989)), resins having terahydropyranyl ether groups as acid labile groups (Hayashi et al., ACS Polymer Materi
al Science and Engineering, 61, 417 (1989)),
Resins containing trimethylsilyl ether groups as acid labile groups (Murata et al., J. Photopolymer Science and Technolog
y, Vol. 5, p. 79 (1992)), resins having carboxylic acid ester labile groups (Horibe et al., Proceedings, SPIE, 2483)
No., p. 61 (1995)), but at present, the difference in dissolution rate between exposed and unexposed areas is still not sufficient, and further improvement is expected. It is rare.

[0009]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to increase the difference in the dissolution rate between a non-exposed portion and an exposed portion, thereby improving the resolution of a fine pattern and improving the unexposed portion. It is an object of the present invention to provide a photosensitive composition which has little film loss and does not decrease sensitivity.

[0010]

Means for Solving the Problems As a result of intensive studies of the means for solving the above problems, the present inventors have found that a resin having a specific partial structure that can be decomposed by an acid is used as a component of the photosensitive composition. The present inventors have found that high resolution is imparted to the photosensitive composition and the above-mentioned problems can be solved, and the present invention has been accomplished. That is, the present invention has the following configuration.

1. (A) a compound which generates an acid upon irradiation with actinic rays or radiation, and (B) an acid-decomposable resin having a polymer main chain crosslinked with an acid-decomposable group represented by the following formula [I]. A positive photosensitive composition characterized by the following. Formula [I]

[0012]

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In the formula, R ₁ and R ₂ may be the same or different and represent a linear, branched, or cyclic alkyl group, an optionally substituted aralkyl group, or an optionally substituted aryl group.
Two or more of R ₁ and R ₂ may combine to form a monocyclic or polycyclic ring. X is a single bond, an arylene group which may be substituted, a linear, branched or cyclic alkylene group which may be substituted and may contain a hetero atom, and which may be substituted and contains a hetero atom. A linear, branched, or cyclic alkenylene group, an alkynylene group, an aralkylene group which may be substituted, or a divalent or trivalent organic group which may contain two or more of these; n represents 2 or 3. 2. 2. The photosensitive composition according to the above item 1, wherein the acid-decomposable resin is a resin containing a structural unit represented by the following formula [II]. Formula (II)

[0014]

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In the formula, m is 0 or 1, and R ₁ , R ₂ ,
R ₃ and R ₄ have the same meanings as R ₁ and R ₂ in the formula [I], and X has the same meaning as X in the formula [I].

3. 3. The photosensitive composition as described in 1 or 2 above, wherein the acid-decomposable resin is a resin containing a structural unit represented by each structural formula of the following formula [III]. Formula [III]

[0017]

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In the formula, m represents 0 or 1, A represents a hydrogen atom, an acyl group, an acyloxy group, a linear or branched, cyclic alkyl group, which may be substituted or contain a hetero atom, an alkoxy group, Shows an acid-decomposable group. Two or more acid-decomposable groups may be contained. R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as R ₁ and R ₂ in the formula [I], and X has the same meaning as X in the formula [I].

4. The above (1) to (3), comprising a low-molecular 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 alkali developer is increased by the action of an acid. The photosensitive composition as described in the above.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each component compound used in the photosensitive composition of the present invention will be described in detail.

[I] The acid-decomposable resin of the present invention in which the polymer main chain is cross-linked by the acid-decomposable group represented by the formula [I] First, the acid-decomposable cross-linkable group which is a feature of the resin of the present invention will be described. I do. In the formula (I), examples of the alkyl group for R ₁ and R ₂ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a cyclopentyl group, and a hexyl group. And straight-chain, branched or cyclic ones having 1 to 8 carbon atoms such as cyclohexyl group, octyl group and the like. Examples of the aralkyl group which may be substituted include those having 7 to 9 carbon atoms such as a benzyl group and a phenethyl group. Examples of the aryl group which may be substituted include a phenyl group, an anthracenyl group and a naphthyl group. R ₁
And preferred substituents for the aralkyl group, aryl group, X arylene group, and aralkylene group for R ₂ include an alkyl group, an alkoxy group, an acyl group, a holomyl group, a nitro group,
Examples include an acylamino group, a sulfonylamino group, a halogen group, an aryl group, and an alkoxycarbonyl group.

As the alkylene group for X, an ethylene group,
Examples thereof include linear, branched or cyclic ones having 1 to 10 carbon atoms such as 1,4-butylene group and 1,4-cyclohexylene group. Examples of the linear, branched, or cyclic alkenylene group which may be substituted and contain a hetero atom include an ethenylene group, a 1,4-butenylene group, a cyclohexenylene group and the like, and an alkynylene group includes ethynylene Groups, propynylene group and the like, and preferred substituents of the alkylene group, alkenylene group, and alkynylene group include an alkyl group, an alkoxy group, an acyl group, a folimil group, a nitro group, an acylamino group, a sulfonylamino group, and a halogen atom. , Aryl groups and alkoxycarbonyl groups. Examples of the case where X is an optionally substituted arylene group are a phenylene group and a naphthylene group. As the aralkylene group which may be substituted,
Examples include a phenylmethylene group and a 2,2-phenethylene group.

Examples of the above substituents include alkyl, alkoxy, methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl and t-butyl.
-Butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, adamantyl group, octyl group,
Examples thereof include straight-chain, branched and cyclic ones having 1 to 8 carbon atoms such as methoxy, ethoxy, propoxy, t-butoxy, i-butoxy and t-octyloxy groups. 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 1 to 8 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Further, one or both of R ₁ and R ₂ may form an alicyclic or condensed alicyclic group such as an adamantyl group and a cyclohexyl group together with X.

The resin of the present invention preferably has a partial structure represented by the formula [II]. Formula [II] and Formula [III]
In formula (I), the specific contents of each group represented by R ₁ , R ₂ , R ₃ , R ₄ and X are those represented by R ₁ , R ₂ and X
Is the same as that described in the description. A in the formula [III] represents a hydrogen atom, an acyl group such as an acetyl group, a propionyl group or a benzoyl group, an acyloxy group such as a propionyloxy group or a benzoyloxy group, or a hetero atom which may be substituted. A linear, branched, or cyclic alkyl group, an alkoxy group, or an acid-decomposable group, and may contain two or more acid-decomposable groups. Examples of straight-chain, branched, cyclic alkyl groups and alkoxy groups which may be substituted or contain a hetero atom include a methyl group, an ethyl group,
Propyl, isopropyl, n-butyl, i-butyl, t-butyl, pentyl, cyclopentyl,
Hexyl, cyclohexyl, adamantyl, octyl, methoxy, ethoxy, propoxy, t-
Examples thereof include linear, branched and cyclic ones having 1 to 8 carbon atoms such as a butoxy group, an i-butoxy group and a t-octyloxy group. When A is an acid-decomposable group, its specific content is described later in "[III] Other resins having an acid-decomposable group which can be used in combination with the resin having an acid-decomposable cross-linking group of the present invention".
And the same as the acid-decomposable group described in the section.

The resin forming the main chain in the resin of the present invention is a resin containing an alkali-soluble group. As the alkali-soluble group, a hydroxyl group, a phenolic hydroxyl group, an amide group, a sulfonamide group, an imide group, a sulfonimide group,
Examples include, but are not limited to, N-hydroxyimide groups, N-hydroxyamide groups, hydroxycarbonyl groups, hydroxysulfonyl groups, and the like. Two or more of these alkali-soluble groups may be contained. The resin forming the main chain preferably has all or a part of the alkali-soluble group protected by an acid-decomposable group. As a result, the acid-decomposable group is deprotected at the same time as the cleavage of the crosslinked site by the acid generated in the exposed portion, and the difference between the dissolution rates of the exposed portion and the unexposed portion in the developer can be further increased.

The ratio of the acid-decomposable group to the alkali-soluble group of the resin forming the main chain (the resin before being crosslinked) is preferably 1 to 80%, more preferably 5 to 60%.
Preferred acid-decomposable groups are acetal groups, ketal groups,
Tertiary alkyloxycarbonyl group, tertiary alkyl ether group, tertiary aralkyloxycarbonyl group, tertiary alkyl ester group, tertiary aralkyl ester group, silyl ether group, benzyl ether derivative, tetrahydrofuranyl ether group, tetrahydropyranyl ether group, Examples include, but are not limited to, enol ether groups and enol ester groups. The preferred molecular weight of the resin forming the main chain (resin before being crosslinked) is from 1,000 to 100,000, more preferably from 3,000 to 50,000 in weight average molecular weight. The preferred molecular weight of the resin (crosslinked resin) of the present invention is 5000 in terms of weight average molecular weight.
To 300,000, more preferably 10,000 to
200,000. The preferable introduction rate of the acid-decomposable crosslinking group in the resin of the present invention is 0.1 to 30% on average, more preferably 0.5 to 20%, based on the number of monomer units of the resin forming the main chain. , More preferably 1 to 10
%. Further, the resin of the present invention may contain structural units other than those described above.
0% or less, preferably 10% or less. Hereinafter, specific examples of the resin having an acid-decomposable crosslinkable group used in the present invention are shown, but the content of the present invention is not limited thereto. Further, in the following specific examples of the resin, the ratio of each repeating structural unit can be freely changed by the above composition ratio.

[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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[0033]

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In the above specific examples, Me is a methyl group, E
t represents an ethyl group, Ph represents a phenyl group, t-Bu represents a t-butyl group, and i-Bu represents an i-butyl group. Represents The compounds represented by the formula [II] used in the present invention may be used alone or in combination of two or more.

The description of the resin having an acid-decomposable group as a cross-linking group according to the present invention is completed above, and then the resin is added to another component of the present invention, a photoacid generator and the photosensitive composition of the present invention. Other possible components will be described sequentially.

[II] A compound capable of generating an acid by the action of actinic rays or radiation In the present invention, the compound capable of generating an acid by the action of actinic rays or radiation used in combination with the above resin having a group capable of decomposing by an acid ( Hereinafter referred to as photoacid generator)
Is described.

The photoacid generator applied to the present invention includes:
Photo-initiators for photo-cationic polymerization, photo-initiators for photo-radical polymerization, photo-decolorants for dyes, photo-discolorants, or compounds that generate an acid by known light used in micro resists and the like, and mixtures 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. Patent No.
Nos. 4,069,055 and 4,069,056, and phosphonium salts described in JVCrivello et al., Macromorecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 10
No. 4,143, U.S. Pat.Nos. 339,049, 410,201, JP-A-2-150,848, iodonium salts described in JP-A-2-296,514, etc., JVCrivello et al., Polymer J. 17, 73 (1985),
JVCrivello et al. J. Org.Chem., 43, 3055 (1978), WRW
att etal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1
984), JVCrivello etal, Polymer Bull., 14,279 (198
5), JVCrivello etal, Macromorecules, 14 (5), 1141 (19
81), JVCrivello etal, J. PolymerSci., Polymer Che
m.Ed., 17,2877 (1979), European Patent Nos. 370,693, 3,90
No. 2,114, No. 233,567, No. 297,443, No. 297,442, U.S. Pat.Nos. 4,933,377, 161,811, No. 410,201, No. 3
No. 39,049, No. 4,760,013, No. 4,734,444, No. 2,833,82
No. 7, Dokoku Patent Nos. 2,904,626, 3,604,580, 3,60
No. 4,581, etc., sulfonium salt, JVCrivello eta
l, Macromorecules, 10 (6), 1307 (1977), JVCrivello et
al, J. PolymerSci., Polymer Chem. Ed., 17,1047 (1979)
Selenonium salts, CSwen et al, Teh, Proc.Co
Onium salts such as arsonium salts described in nf.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.
No., JP-B-46-4605, JP-A-48-36281, JP-A-55-3
No. 2070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401
No., JP-A-63-70243, organic halogen compounds described in JP-A-63-298339, K. Meier et al., J. Rad.Curing, 13
(4), 26 (1986), TPGill et al., Inorg.Chem., 19, 3007
(1980), D. Astruc, Acc. Chem. Res., 19 (12), 377 (1896),
Organometallic / organic halides described in JP-A-2-14145, S. Hayase et al., J. Polymer Sci., 25, 753 (1987), ER
eichmanis etal, J.Pholymer Sci., Polymer Chem.Ed., 2
3,1 (1985), QQ Zhu et al., J. Photochem., 36, 85, 39, 317 (1
987), B. Amit etal, Tetrahedron Lett., (24) 2205 (197
3), DHR Barton et al., J. Chem Soc., 3571 (1965), PM
Collins et al., J. Chem.SoC., Perkin I, 1695 (1975), M. Rud
instein etal, Tetrahedron Lett., (17), 1445 (1975), J.
W. Walker et al. J. Am. Chem. Soc., 110, 7170 (1988), SCBu
sman et al, J. Imaging Technol., 11 (4), 191 (1985), HMH
oulihan etal, Macormolecules, 21, 2001 (1988), PMColl
ins etal, J. Chem. Soc., Chem. Commun., 532 (1972), S. Haya
se etal, Macromolecules, 18, 1799 (1985), E. Reichmanis
etal, J.Electrochem.Soc., Solid State Sci.Technol., 1
30 (6), FMHoulihan et al., Macromolcules, 21, 2001 (198
8), European Patent Nos. 0290,750, 046,083, 156,535
No. 271,851, No. 0,388,343, U.S. Pat.No. 3,901,7
No. 10, 4,181,531, JP-A-60-198538, JP-A-53-1
Photoacid generator having an o-nitrobenzyl-type protecting group described in No. 33022, M. Tunooka et al., Polymer Preprints Ja
pan, 35 (8), G. Berner et al., J. Rad. Curing, 13 (4), WJMij
s etal, Coating Technol., 55 (697), 45 (1983), Akzo, H.Ad
achi etal, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 199,672, 044,115
Nos. 0101,122; U.S. Pat.Nos. 618,564; 4,371,605
No. 4,431,774, JP-A-64-18143, JP-A 2-2457
No. 56, iminosulfone described in Japanese Patent Application No. 3-140109, etc.
And disulfone compounds described in JP-A-61-166544 and the like.

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 etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Rap
id Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Che
m., 152, 153, 163 (1972), JVCrivello etal, J. Polyme
rSci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
No. 3,849,137, German Patent No. 3914407, JP-A-63-26653
No., JP-A-55-164824, JP-A-62-69263, JP-A-63-69
No. 146038, JP-A-63-163452, JP-A-62-153853,
The compounds described in JP-A-63-146029 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 which can be used together and decompose upon irradiation with actinic rays or radiation to generate an acid, those which are particularly effectively used are described below. The photoacid generator used in the present invention is described below. It is not limited to. (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).

[0042]

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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.

[0044]

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[0045]

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[0046]

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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).

[0048]

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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 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. .

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.

[0054]

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[0055]

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[0056]

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[0057]

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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).

[0060]

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Where Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
It represents 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.

[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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In the photosensitive composition of the present invention, the content of the above-mentioned photoacid generator is 0.1 to the total solid of the photosensitive composition.
1-20% by weight is suitable, preferably 0.5-10%.
% By weight, more preferably 0.8 to 7% by weight
It is. [III] Other resins having an acid-decomposable group which can be used in combination with the resin having an acid-decomposable cross-linking group of the present invention. In the present invention, the above-mentioned resin is used as a component of the photosensitive composition for forming a chemically amplified resist. In addition to the resin having an acid-decomposable crosslinking group of the invention, a resin having another acid-decomposable group may be used in combination. The resin that can be used in combination is a conventionally known arbitrary resin having a group decomposable with an acid in the main chain or side chain, or in both the main chain and the side chain. Among them, a resin having a group which can be decomposed by an acid in a side chain is more preferable. A preferred group that can be decomposed by an acid is-
COOA ^0, a -O-B ⁰ group, further examples of the group containing these, include groups represented by -R ⁰ -COOA ^0, or -A _r -O-B ^0. Here, A ⁰ is -C (R ⁰¹ ) (R
^{02) (R 03), -} Si (R 01) ( indicating the R ⁰²⁾ (R ^{0 3)} or ^{-C (R 04) (R 05} ) -O-R 06 group. B ⁰ is
A ⁰ or -CO-OA ⁰ represents a group (R ⁰ , R ^{01 to} R ⁰⁶ ,
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, an enol ether group, an enol ester group, a tertiary alkyl ether group, or a tertiary alkyl ester. And tertiary alkyl carbonate groups. 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. Particularly preferred is an acetal group.

Next, as a base resin when the groups decomposable by these acids are bonded as side chains, -OH or -COOH, preferably -R ⁰ -COOH or -A _r -OH group is added to the side chains. It is an alkali-soluble resin having. For example, an alkali-soluble resin described below can be used.

The alkali dissolution rate of these alkali-soluble resins was measured using a 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.) and measured at 170 ° C.
A / sec or more is preferable. Particularly preferably 330A
Per second or more (where 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, a 1 μm film thickness of 24
The transmittance at 8 nm is 20 to 90%. From these viewpoints, 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- An acylated product, a styrene-hydroxystyrene copolymer, an α-methylstyrene-hydroxystyrene copolymer, and a hydrogenated novolak resin.

In the present invention, a resin having an acid-decomposable group which can be used in combination with a resin having an acid-decomposable cross-linking group is disclosed in European Patent 2
No. 54853, JP-A-2-25850 and 3-223
No. 860, 4-251259, etc., an alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an alkali-soluble resin monomer to which an acid-decomposable group is bonded is used. It can be obtained by copolymerization with various monomers.

Specific examples of the resin having an acid-decomposable group which can be used in combination with the resin having an acid-decomposable cross-linking group used in the present invention 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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In the above specific examples, Me is a methyl group, E
t represents an ethyl group, nBu represents an n-butyl group, iso-Bu represents an isobutyl group, and tBu represents a t-butyl group. The content of acid-decomposable groups is represented by the number of groups decomposable by acids (B) and the number of alkali-soluble groups not protected by acid-decomposable groups (S) in the resin. B + S). The content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.10 to 0.
0.50. PEB when B / (B + S)> 0.7
(Heat treatment after exposure) causes undesired film shrinkage, poor adhesion to the substrate and scum. On the other hand, B / (B + S)
A value of <0.01 is not preferable because standing waves may be remarkably left on the pattern side wall.

The weight average molecular weight (Mw) of the resin having an acid-decomposable group is preferably in the range of 2,000 to 300,000. If it is less than 2,000, the film thickness is greatly reduced due to the development of the unexposed portion, and if it exceeds 300,000, the dissolution rate of the resin itself in alkali becomes slow and the sensitivity is lowered. Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.

Further, two or more resins having an acid-decomposable group which may be used in combination with the resin having an acid-decomposable cross-linking group may be used in combination. The amount of the resin having an acid-decomposable cross-linking group obtained by combining the resin having an acid-decomposable cross-linking group of the present invention and the resin that may be used in combination with the resin is based on the total weight of the photosensitive composition (excluding the solvent). 40-99% by weight, preferably 6
0 to 98% by weight, of which the amount of the resin having an acid-decomposable crosslinking group is at least the same as the amount of the resin which may be used in combination, preferably 70 to 100%, more preferably 8 to 100%.
0 to 100%.

Further, in order to adjust the alkali solubility,
In the photosensitive composition, together with the photoacid generator and the acid-decomposable group-containing resin, an alkali-soluble resin having no acid-decomposable group described below may be mixed, or acid-decomposable low-molecular dissolution inhibition Compounds may be mixed.

[IV] Alkali-Soluble Resin Used in the Present Invention In the present invention, a resin that is insoluble in water and soluble in an aqueous alkali solution (hereinafter, also referred to as an alkali-soluble resin) may be used. As the alkali-soluble resin used in the present invention,
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 with respect to hydroxyl group of polyhydroxystyrene (for example, 5 to 30 mol% of O-methylated product, O- (1-methoxy) ethylated product, O- (1- Ethoxy) ethylated,
O-2-tetrahydropyranylated product, O- (t-butoxycarbonyl) methylated product, etc.) or O-acylated product (for example, 5 to 30 mol% o-acetylated product, O-
(T-butoxy) carbonyl compound, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing methacrylic resin and its derivatives, polyvinyl alcohol Derivatives can be mentioned, but are not limited thereto. 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 an O-acylated product, a styrene-hydroxystyrene copolymer, or an 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.

As the predetermined monomer, phenol, 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 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 compounds, such as 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 novolak resin thus obtained preferably has a weight average molecular weight 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. The amount of alkali-soluble resin used is
It is 20% by weight or less based on the total weight of the photosensitive composition (excluding the solvent).

[V] Low-molecular acid-decomposable dissolution inhibiting compound used in the present invention In the present invention, a low-molecular acid-decomposable dissolution-inhibiting compound may be used. 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. 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,
Further, even in the case of having two acid-decomposable groups, when the acid-decomposable groups are separated from each other by a certain distance or more, the dissolution inhibiting property with respect to an alkali-soluble resin is remarkably improved. In addition, the distance between the acid-decomposable groups in the present invention is represented by the number of via bond atoms excluding the acid-decomposable groups. For example, in the case of the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bond atoms each, and in the compound (3), the bond atom is 12 bond atoms.
Individual.

[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, an acid-decomposable group, ie, —COO-A ⁰ , —O—B ⁰
The group containing a group, -R ⁰ -COO-A ^0, or -Ar
Include groups represented by -O-B ^0. Where A ⁰ is −
C ( ^R01 ) ( ^R02 ) ( ^R03 ), -Si ( ^R01 ) ( ^R02 )
Shows the (R ^{0 3)} or ^{-C (R 04) (R 05} ) -O-R 06 group. B ⁰ represents A ⁰ or a —CO—OA ⁰ group.
R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ may be the same or different and each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group;
⁰⁶ represents an alkyl group or an aryl group. Where R ⁰¹
At least two of to R ⁰³ is a group other than a hydrogen atom,
Further, two groups out of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ may combine to form a ring. R ⁰ represents a divalent or higher valent aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- is a divalent or higher valent which may have a monocyclic or polycyclic substituent. Shows an aromatic group.

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 acid-decomposable group 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 ester group. And tertiary alkyl carbonate groups. More preferably, a tertiary alkyl ester group,
They are 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
And a compound represented by [XVI].

[0092]

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[0093]

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[0094]

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[0095]

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Here, R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ and R ¹³⁰ may be the same or different, and represent a hydrogen atom, —R ⁰ —COO—C (R ⁰¹ ) (R
⁰²⁾ (R ⁰³⁾ or ^{-CO-O-C (R 01} ) (R 0 2) (R
⁰³ ) provided that the definitions of R ⁰ , R ⁰¹ , R ⁰² and R ⁰³ are the same as described above.

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

[0098]

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[0099] 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 ) ( ^R156 ) ( ^R155 , ^R156 : H, alkyl group, or aryl group) ^R110 : single bond, alkylene group, or

[0100]

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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 haloalkyl group, provided that the lower alkyl group means 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

[0103]

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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 may be hydrogen, hydroxyl, halogen, nitro, cyano, carbonyl, alkyl, alkoxy, alkoxycarbonyl, aralkyl, aralkyloxy 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 symbols do not have to 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 haloalkyl group; E: single bond or oxymethylene group , A to z, a1 to y1: when plural, the groups in () may be the same or different; a to q, s, t, v, g1 to i1, k1 m1, o1, q1, s1, u1: 0 or an integer of 1 to 5, r, u, w, x, y, z, a1~f1, p1, r1, t1, v1~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.

[0105]

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[0106]

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[0107]

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[0108]

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Specific examples of preferred compound skeletons are shown below.

[0110]

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

[0130]

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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 the present invention, the amount of the dissolution inhibiting compound to be added is 50% by weight or less of the total solid content of the photosensitive composition when combined with a resin containing an acid-decomposable group, a photoacid generator and an alkali-soluble resin. And preferably 40% by weight
Or less, more preferably in the range of 35% by weight or less.

[VI] Other Components Used in the Photosensitive Composition of the Present Invention The positive photosensitive composition of the present invention may further contain a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, if necessary. It may contain a sensitizer, an organic basic compound, and a compound having two or more phenolic OH groups for promoting solubility in a developer.

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 a phenol compound having a molecular weight of 1,000 or less can be prepared by those skilled in the art by referring to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. It can be easily synthesized 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).

[0139]

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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 are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001-10 parts by weight, preferably 0.01-5 parts by weight, per 100 parts by weight of the photosensitive 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.

[0142] Suitable dyes include oily 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 far 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 onto a substrate (eg, silicon / silicon dioxide coating) used for the production of precision integrated circuit devices by an appropriate 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.

As the developer for the photosensitive composition of the present invention,
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.

[0148]

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 Resin Example-1) Polyhydroxystyrene (VP-8000 manufactured by Nippon Soda)
20 g were dissolved in 100 ml of THF. To this, 6.7 g of isobutyl vinyl ether and 5.4 mg of p-toluenesulfonic acid were added and reacted at room temperature for 16 hours. To this solution, 3.4 g of triethylamine and 3.2 g of the crosslinking agent (1) were added, and reacted at room temperature for 70 hours. When the reaction solution was poured into 500 ml of water, a viscous substance precipitated. This viscous material was dissolved in acetone / toluene, and hexane was added to the solution. After removing the supernatant, hexane was added, and the obtained solid was filtered.
After drying, Resin Example 1 was obtained. (Protection rate 35%, weight average molecular weight 26000)

[0149]

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Synthesis Example 2 (Synthesis of Resin Example-2) Polyhydroxystyrene (VP-5000 manufactured by Nippon Soda)
28 g was dissolved in 200 ml of pyridine.
25 g of t-butyl were added. After reacting this solution at 50 ° C. for 2 hours, 4.2 g of the crosslinking agent (2) was added thereto and reacted at room temperature for 60 hours. The reaction solution was concentrated hydrochloric acid 120 ml / water 2
The powder precipitated by pouring into L was filtered, washed with water, and dried to obtain Resin Example 2. (Protection rate 30%, weight average molecular weight 380
00)

[0151]

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Synthesis Example 3 (Synthesis of Comparative Resin 1) Polyhydroxystyrene (VP-8000 manufactured by Nippon Soda)
20 g were dissolved in 100 ml of THF. To this, 6.7 g of isobutyl vinyl ether and 5.4 mg of p-toluenesulfonic acid were added and reacted at room temperature for 16 hours. When the reaction solution was poured into 1 g of triethylamine / 500 ml of water, powder was precipitated. The powder was filtered, washed with water, and dried to obtain Comparative Resin 1. (Protection rate 35%, weight average molecular weight 11,000)

[0153]

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Synthesis Example 4 (Synthesis of Comparative Resin 2) Polyhydroxystyrene (VP-5000, manufactured by Nippon Soda)
28 g was dissolved in 200 ml of pyridine.
25 g of t-butyl were added. This solution was reacted at 50 ° C. for 2 hours. The reaction solution was poured into concentrated hydrochloric acid (120 ml) / water (2 L), and the precipitated powder was filtered, washed with water and dried to obtain Comparative Resin 2. (Protection rate 30%, weight average molecular weight 1,1000)

[0155]

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Examples 1 to 4 and Comparative Examples 1 to 4 Resists were prepared using the compounds shown in the above synthesis examples.
The prescription at that time is shown in Table 1 below.

[0157]

[Table 1]

Among the compounds used in Table 1, abbreviations other than those exemplified as specific examples are shown in the notes of Table 1. The compound used as the dissolution inhibitor is exemplified as specific example (18), in which the acid-decomposable group represented by R is a t-butyloxycaubonylmethyl group. [Preparation and evaluation of photosensitive composition]
-Dimethylaminopyridine was added and dissolved in 9.5 g of propylene glycol monomethyl ether acetate,
The solution was filtered through a 0.2 μm filter to prepare a resist solution. This resist solution was applied on a silicon wafer using a spin coater, and dried on a vacuum adsorption type hot plate at 90 ° C. for 120 seconds to form a film having a thickness of 0.83 μm.
m was obtained. 248 nm
KrF excimer laser stepper (NA = 0.42)
Exposure was performed using. Immediately after the exposure, each was heated for 60 seconds on a vacuum adsorption hot plate at 90 ° 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, resolution, and line width change of the pattern on the silicon wafer thus obtained were evaluated and compared as described below. The results are also shown in Table 1.

[Sensitivity] Sensitivity was defined as an exposure amount for reproducing 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. [Film loss] The measurement and evaluation methods are described in the remarks in Table 1. From the results shown in Table 1, the positive photosensitive composition of the present invention shows no change in line width even after aging after PEB with respect to Comparative Examples 1 and 2, has high sensitivity and high resolution, and has an unexposed portion of the resist film. Has a small dissolution loss (film loss), indicating that it is an excellent photosensitive composition.

[0160]

According to the positive photosensitive composition of the present invention containing a resin in which the polymer main chain is crosslinked by an acid-decomposable group having a specific structure containing a tertiary carbon group, the resolution of a fine pattern is high, and unexposed. Thus, a resist with little dissolution loss (film loss) of the resist film in the portion and with no decrease in sensitivity can be obtained.

Claims (4)

[Claims] 1. An acid-decomposable compound in which (A) a compound which generates an acid upon irradiation with actinic rays or radiation, and (B) a polymer main chain is crosslinked with an acid-decomposable group represented by the following formula [I]: A positive photosensitive composition comprising a resin. Formula [I] In the formula, R ₁ and R ₂ may be the same or different, and represent a linear, branched, or cyclic alkyl group, an optionally substituted aralkyl group, or an optionally substituted aryl group. Two or more of R ₁ and R ₂ may combine to form a monocyclic or polycyclic ring. X is a single bond, an arylene group which may be substituted,
A straight-chain, branched, or cyclic alkylene group which may be substituted and may contain a hetero atom, a linear, branched or cyclic alkenylene group or an alkynylene group which may be substituted and contain a hetero atom And an aralkylene group which may be substituted or a divalent or trivalent organic group which may contain two or more of these. n represents 2 or 3. 2. The photosensitive composition according to claim 1, wherein the acid-decomposable resin is a resin containing a structural unit represented by the following formula [II]. Embedded image Wherein m is 0 or 1, and R ₁ , R ₂ , R ₃ and R
₄ has the same meaning as R ₁ and R ₂ in formula [I], and X
Has the same meaning as X in formula [I]. 3. The photosensitive composition according to claim 1, wherein the acid-decomposable resin is a resin containing all the structural units represented by the following formula [III]. Embedded image In the formula, m is 0 or 1, A is a hydrogen atom, an acyl group, an acyloxy group, a linear, branched, or cyclic alkyl group which may be substituted and may contain a hetero atom, an alkoxy group,
Shows an acid-decomposable group. Two or more acid-decomposable groups may be contained. R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as R ₁ and R ₂ in formula [I], and X is X in formula [I].
Is synonymous with 4. 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 photosensitive composition according to claim 1.