JPH1090882A - Chemical amplification type positive resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure high sensitivity and high resolving power and to form a superior resist pattern by incorporating a specified soluble resin and a specified compd. generating sulfuric acid when irradiated with active light or radiation. SOLUTION: This positive resist compsn. contains an alkali-soluble resin having crosslinking bonds and groups which are decomposed by the action of an acid and increase solubility in an alkali developer and a compd. represented by formula I or II and generating sulfuric acid when irradiated with active light or radiation. In the formulae I, II, each of R1 -R5 , is H, alkyl, cycloalkyl, etc., and X-is an anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having one of branched or cyclic >=8C alkyl and alkoxy groups, two of straight chain, branched or cyclic 4-7C alkyl and alkoxy groups or three of straight chain or branched 1-3C alkyl and alkoxy groups.

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 chemically amplified positive resist composition used in a semiconductor manufacturing process such as, for example, a circuit board such as a liquid crystal and a thermal head, and further in a photofabrication process.

[0002]

2. Description of the Related Art Positive photoresist compositions include:
In general, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is used. For example, US Pat. No. 3,666,473, US Pat. No. 4,115,128 and US Pat. No. 4,173,470 as “Novolak-type phenolic resin / naphthoquinonediazide-substituted compound” and the most typical composition “Novolak resin comprising cresol-formaldehyde” / 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.

When a conventional alkali-soluble resin having an acid-decomposable group is used in a resist composition, there is still a problem in heat resistance. The problem of this heat resistance is that the protection rate by the acid-decomposable group in the alkali-soluble resin is made lower or the protection rate by the acid-decomposable group in the alkali-soluble resin is increased as much as possible. Can be solved. However, when a resin having a low protection rate by an acid-decomposable group in a resin is used, discrimination between an unexposed portion and an exposed portion is deteriorated, and the resolving power becomes insufficient. In addition, when a resin whose protection rate by the acid-decomposable group in the resin is as high as possible is used, there is a problem that the film shrinks by baking after exposure or the adhesion to the substrate is reduced.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art. More specifically, an object is to provide a high-sensitivity, high-resolution, excellent resist pattern, and An object of the present invention is to provide a positive photoresist composition having good heat resistance of the resist.

[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 form a resin having the following specific structure with a sulfonic acid in a positive-type chemical amplification system. It has been found that this can be achieved by using the specific compound generated. That is, the present invention has the following configuration. (1) An alkali-soluble resin having a group that decomposes by the action of a cross-linking bond and an acid to increase the solubility in an alkali developer, and a sulfonic acid that generates sulfonic acid upon irradiation with actinic rays or radiation. ) Or a compound represented by formula (II).

[0011]

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In the formula, R _{1 to} R ₅ may be the same or different, and each may be a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom or —S—R ₆
Represents a group. R ₆ represents an alkyl group or an aryl group. X
^- is a group selected from the group branched or cyclic having 8 or more alkyl groups and alkoxy groups of carbon atoms of at least 1
Or has at least two groups selected from the group consisting of linear, branched, or cyclic alkyl groups and alkoxy groups having 4 to 7 carbon atoms, or has a linear or branched carbon number. The anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least three groups selected from the group consisting of 1 to 3 alkyl groups and alkoxy groups is shown. (2) The cross-linking bond is formed by a reaction of a compound containing two or more phenolic hydroxyl groups in a molecule, a phenolic hydroxyl group of an alkali-soluble resin, and an alkyl vinyl ether compound. The chemically amplified positive resist composition according to 1). (3) The chemically amplified positive resist composition according to the above (1) or (2), comprising an organic basic compound.

(4) a group in which the alkali-soluble resin decomposes into low-dispersion poly (hydroxystyrene) obtained by anionic living polymerization by the action of a cross-linking bond and an acid to increase the solubility in an alkali developer. The chemically amplified positive resist composition according to any one of the above (1) to (3), wherein the resin is a resin into which is introduced. (5) The chemically amplified positive resist composition as described in any one of (1) to (4) above, which comprises at least one phenolic compound having a single molecular weight and a molecular weight of 3000 or less. (6) The above-mentioned (1) to (5), wherein the phenolic compound having a single molecular weight and a molecular weight of 3000 or less contains a low-molecular acid-decomposable dissolution-inhibiting compound in which an acid-decomposable group is introduced. The chemically amplified positive resist composition according to any one of the above.

As described above, by using a compound represented by the above general formula (I) or (II) and an alkali-soluble resin having an acid-decomposable group and a cross-linking bond as a photoacid generator, a chemically amplified type In the resist, the heat resistance and the resolving power were remarkably improved, and the sensitivity and profile were also improved.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. [I] Photoacid generator represented by general formula (I) or (II) In the general formula (I) or (II), the alkyl group of R _{1 to} R ₆ may have a substituent. Good, methyl group,
Examples thereof include those having 1 to 4 carbon atoms such as an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Examples of the cycloalkyl group include those having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group which may have a substituent.
Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aryl group include those having 6 to 14 carbon atoms which may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group and a naphthyl group.

The substituent is preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom or an iodine atom), an aryl group having 6 to 10 carbon atoms, or an alkenyl having 2 to 6 carbon atoms. Group, cyano group, hydroxy group,
Examples thereof include a carboxy group, an alkoxycarbonyl group, and a nitro group. General formula (I) or (I) used in the present invention
Sulfonium represented by I), iodonium compounds, the counter anion, X ^- as, branched or cyclic carbon number of 8 or more, or preferably at least 1 or more 10 or more alkyl or alkoxy groups, straight Chain,
It has at least two or more branched or cyclic C4-C7 alkyl or alkoxy groups, or has at least three linear or branched C1-C3 alkyl or alkoxy groups It has an anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid. This reduces the diffusivity of the acid (benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having the above group) generated after exposure, and improves the solvent solubility of the sulfonium or iodonium compound. In particular, from the viewpoint of reducing the diffusivity, a branched or cyclic alkyl group or alkoxy group is more preferable as the above group than a linear alkyl group or alkoxy group. When the number of the above groups is one, the difference in diffusivity between a straight chain and a branched or cyclic one becomes more remarkable.

C8 or more, preferably C8 to C2
Examples of the zero alkyl group include a branched or cyclic octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group,
Examples include a tridecyl group, a tetradecyl group, and an octadecyl group. 8 or more carbon atoms, preferably 8 to 20 carbon atoms
Examples of the alkoxy group include a branched or cyclic octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, a tridecyloxy group,
Examples include a tetradecyloxy group and an octadecyloxy group. Examples of the alkyl group having 4 to 7 carbon atoms include a linear, branched, or cyclic butyl group, a pentyl group, a hexyl group, and a heptyl group. Examples of the alkoxy group having 4 to 7 carbon atoms include a linear, branched, or cyclic butoxy group, a pentyloxy group, a hexyloxy group, and a heptyloxy group. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group.

Further, X ^- in the aromatic sulfonic acid represented by, in addition to the above specific substituent, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), C6-10
It may contain as substituents aryl groups, cyano groups, sulfide groups, hydroxy groups, carboxy groups, nitro groups and the like.

The content of the compound of the present invention represented by the general formula (I) or (II) is 0.1 to 0.1 with respect to the solid content of the whole composition.
20% by weight is suitable, preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight. Hereinafter, specific examples of these compounds (I-1) to (I-59), (II-
Although 1) to (II-53) are shown, the present invention is not limited thereto.

[0020]

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[0021]

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[0022]

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[0023]

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[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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[0033]

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[0034]

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In the specific examples, n is a straight chain, s is a secondary, t is
Represents tertiary and i represents branching. The compound represented by the general formula (I) or (II) includes, for example, a corresponding Cl ⁻ salt (a compound in which X ⁻ is substituted with Cl ⁻ in the general formula (I) or (II)) and X ⁻ Y ⁺ The compound represented by the formula (X ⁻ has the same meaning as in formula (I) or (II), and Y ⁺ is H ⁺ , Na ⁺ ,
Shows cations such as K ⁺ , NH ₄ ⁺ , and N (CH ₃ ) ₄ ⁺ . ) Can be synthesized by salt exchange in an aqueous solution.

[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) or (II) which generates the above-mentioned sulfonic acid, it is decomposed by irradiation with other actinic rays or radiation. And a compound that generates an acid. The general formula (I) or (I)
The ratio of the photoacid generator that can be used in combination with the compound represented by I) is from 100/0 to 5/95, preferably 90 / molar, in a molar ratio.
10/20/80, more preferably 80 / 20-30 /
70. 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., phosphonium salts, JVCrivello et al., Macromorecules, 10 (6), 1307
(1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent No. 339,049, No. 410,201.
No., JP-A-2-150,848, iodonium salts described in 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
Nos. 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. Pat.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), and 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, JP-A-53-133022, etc.
TUNOOKA etal, Polymer Preprints Japan, 35 (8), G. Bern
er etal, J.Rad.Curing, 13 (4), WJMijs etal, Coating
Technol., 55 (697), 45 (1983), Akzo, H. Adachi et al, Po
lymer Preprints, Japan, 37 (3), European Patent No. 0199,672,
No. 84515, No. 199,672, No. 044,115, No. 0101,122
Nos., U.S. Pat.Nos. 618,564, 4,371,605, 4,431,
No. 774, JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No.
Compounds which generate sulfonic acid upon photolysis, such as iminosulfonates described in JP-A-3-140109, etc.
-166544 and the like.

A group which 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 are 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).

[0041]

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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.

[0043]

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[0044]

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[0045]

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

[0047]

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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, it is an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a substituted derivative thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom for the aryl group, and a substituent for the alkyl group. It is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, or an alkoxycarbonyl group.

[0049] Z ^- represents a counter anion, CF ₃ SO ₃ ^-
And the like, such as perfluoroalkanesulfonic acid anions and pentafluorobenzenesulfonic acid anions.

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.

[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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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).

[0062]

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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.

[0064]

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[0065]

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

[0067]

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In the formula, Y is an alkyl group, a cycloalkyl group, an aralkyl group which may be substituted,

[0069]

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Wherein R _{1 to} R ₁₂ may be the same or different and each may be a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonyl group. Represents an amino group, an aryl group, or an alkoxycarbonyl group). X represents an alkylene group which may be substituted, a cycloalkylene group which may be substituted, an arylene group which may be substituted, or an alkenylene group which may be substituted. Specific examples include the following compounds, but are not limited thereto.

[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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(5) An o-nitrobenzyl-type photoacid generator represented by the following general formula (PAG8).

[0080]

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

[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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Among the photoacid generators that can be used in combination, preferred are a sulfonylimide derivative represented by the general formula (PAG7) and an o-nitrobenzyl type photoacid generator represented by the general formula (PAG8). .

[III] Cross-linking and the action of an acid
Groups that increase solubility in alkaline developers (hereinafter referred to as
Below, also referred to as an acid-decomposable group)
Fat The alkali-soluble resin in the present invention is a main chain of the resin.
Or acid-decomposable on the side chain, or both main and side chains
It is a resin having a group. Of these, acid-decomposable groups are included in the side chain.
Is preferred. Preferred as an acid-decomposable group
A new group is -COOA⁰, -OB⁰Group
As a group containing these, -R⁰-COOA⁰Or -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
(R⁰, R⁰¹~ R⁰⁶, And Ar are the same as those described below.
Righteousness).

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. Among these, in combination with the photoacid generator according to the present invention, the resist pattern becomes thinner with the lapse of time from exposure to heat treatment with high sensitivity and high resolution, and the shape of the resist pattern surface becomes T-type ( In order to more effectively bring out the effect of the present invention of not exhibiting T-top) and suppressing profile degradation such as standing wave remaining or pattern collapse, a silyl ether group is used as the acid-decomposable group. An acid-decomposable group having relatively high acid-decomposability such as an acetal group and a tetrahydropyranyl ether group is more preferable. Particularly, an acetal group is preferable.

A preferred group for the acetal group is —O—
C (R⁰⁴) (R⁰⁵) -OR⁰⁶It is represented by More preferred
Or the acid-decomposable group is -Ar-OC (R⁰⁴) (R⁰⁵) -O
-R ⁰⁶When the compound is bound by the structure shown by
You.

R ⁰⁴ and R ⁰⁵ may be the same or different, and each represents a hydrogen atom, an alkyl group, a cycloalkyl group,
R ⁰⁶ represents an alkenyl group or an aryl group, and R ⁰⁶ represents an alkyl group or an aryl group. However, R ⁰⁴ and R ⁰⁵ may combine to form a ring. -Ar- represents a divalent or higher valent aromatic group which may have a monocyclic or polycyclic substituent. Here, the alkyl group includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group,
Preferred are those having 1 to 4 carbon atoms such as -butyl group, and preferred cycloalkyl groups are those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl group Preferred are those having 2 to 4 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group, and aryl groups such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthracenyl group are preferred. Preferred are those having 6 to 14 carbon atoms.

Examples of the substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, and the above-mentioned alkyl groups, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group. Alkoxy groups such as groups, n-butoxy groups, isobutoxy groups, sec-butoxy groups, t-butoxy groups, alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups, aralkyl groups such as benzyl groups, phenethyl groups and cumyl groups, Aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzoyl groups, cyanyl groups, acyl groups such as valeryl groups, acyloxy groups such as butyryloxy groups, the above alkenyl groups, vinyloxy groups, propenyloxy groups, allyloxy groups, butenyloxy groups Alkenyloxy groups such as Serial aryl group, an aryloxy group such as phenoxy group, and an aryloxycarbonyl group such as benzoyloxy group.

As the acetal group,

[0095]

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A group represented by the following formula, particularly preferably,

[0097]

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[0098] The groups represented by

Next, as a base resin when these acid-decomposable groups are bonded as side chains, -OH or-
COOH, in particular, -R ⁰ -COOH or -AR-O
An alkali-soluble resin having an H group is preferable, for example,
An alkali-soluble resin not containing an acid-decomposable group described below (hereinafter simply referred to as an alkali-soluble resin), an alkali-soluble resin (preferably, polyhydroxystyrene, a novolak resin, a derivative thereof), and a p-hydroxystyrene unit are used. Contained alkali-soluble resin (preferably poly (p-hydroxystyrene, p / m-hydroxystyrene, p / o-hydroxystyrene, p-hydroxystyrene-styrene copolymer), 4-hydroxy-3
Preferred are alkyl-substituted hydroxy resins such as -methylstyrene resin and 4-hydroxy-3,5-dimethylstyrene resin, and alkylated or acetylated OH moieties of the above resins.

Further, when a part of the phenol nucleus (30 mol% or less of the total phenol nucleus) of the above resin is hydrogenated, the transparency of the resin is improved, and the sensitivity, the resolving power, and the profile of the rectangle are preferable. . As the alkali-soluble resin as the base resin, for example, a novolak resin,
Hydrogenated novolak resin, acetone-pyrogallol resin,
Polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-
Substituted maleimide copolymer, partially O-alkylated or O-acylated polyhydroxystyrene, styrene-maleic anhydride copolymer, carboxyl group-containing methacrylic resin and derivatives thereof, styrene-polyhydroxystyrene copolymer, Examples include, but are not limited to, hydrogenated polyhydroxystyrene.

Particularly preferred alkali-soluble resins as the base resin used in the present invention are novolak resins and p-type resins.
-An alkali-soluble resin containing a hydroxystyrene unit (preferably poly (p-hydroxystyrene, p
/ M-hydroxystyrene, p / o-hydroxystyrene, p-hydroxystyrene-styrene copolymer), 4
Alkyl-substituted hydroxy resins such as -hydroxy-3-methylstyrene resin, 4-hydroxy-3,5-dimethylstyrene resin, alkylated or acetylated OH moiety of the above resin, partially hydrogenated polyhydroxystyrene resin, polyhydroxy Styrene resin, partially hydrogenated novolak resin, and partially hydrogenated polyhydroxystyrene resin.

In the present invention, polyhydroxystyrene refers to a p-hydroxystyrene monomer, an m-hydroxystyrene monomer, an o-hydroxystyrene monomer or a hydroxystyrene monomer having an ortho-substituted alkyl group having 1 to 4 carbon atoms. It shows a polymer obtained by polymerizing at least one kind of monomer selected from the above.

The alkali dissolution rate of the alkali-soluble resin for the base resin was determined by measuring with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.) to be 1%.
Those at 70 ° / sec or more are preferred. Particularly preferably 33
0Å / sec or more (Å 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 248 nm film having a thickness of 1 μm
Is 20 to 80%.

From these viewpoints, more preferred alkali-soluble resins for the base resin are polyhydroxystyrene,
Hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, partially o-acylated polyhydroxystyrene, hydroxystyrene-styrene copolymer and hydrogenated novolak resin. A particularly preferred alkali-soluble resin for a base resin is a low-dispersion poly (hydroxystyrene) obtained by an anionic living polymerization method. In this case, the poly (hydroxystyrene) has a polydispersity of preferably from 1.0 to 4.0, more preferably from 1.0 to 3.5.

The resins having an acid-decomposable group of the present invention are described in European Patent No. 2,485,853, JP-A-2-25850, and JP-A-2-25850.
As disclosed in JP-A-223860 and JP-A-4-251259, an alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an alkali-soluble resin monomer having an acid-decomposable group bonded thereto is mixed with various monomers. It can be obtained by copolymerization. In the present invention, specific examples of the resin having an acid-decomposable group are shown below, but the present invention is not limited thereto.

[0106]

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[0107]

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[0108]

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[0109]

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Among the specific examples of the alkali-soluble resin containing an acid-decomposable group, (ii), (iv), (xiii), (x
v), (xxii), (xxv), (xxvi) are preferred.

In the present invention, the cross-linking contained in the resin may have any structure, but is preferably a cross-linking containing at least a structure decomposed by the action of an acid. Examples of such an acid-decomposable structure include an acetal bond represented by —CO—C— and a silyl ether bond represented by —O—Si—O—. Particularly preferred is an acetal bond. In the present invention, the resin protected by an acetal group as an acid-decomposable group can be introduced with a cross-linking bond by the following method. However, the method is not limited to this method as long as the same result is obtained. When protecting existing polyhydroxystyrene with an acid-decomposable group, by adding a compound containing two or more phenolic hydroxyl groups to a small amount of the molecule, the polyhydroxystyrene chain can be in the same molecular chain, or Crosslinking between different molecular chains can be achieved via compounds containing two or more phenolic hydroxyl groups in the molecule. This improves the heat resistance of the resist. In the present invention, the cross-linking is carried out in a molecule.
A compound formed by the reaction of a compound containing two or more phenolic hydroxyl groups, a phenolic hydroxyl group of an alkali-soluble resin and an alkyl vinyl ether compound is preferred.

The compound containing two or more phenolic hydroxyl groups in the molecule to be added for crosslinking is not particularly limited, but an aromatic compound is not limited to an actinic ray or a radiation in the ultraviolet region which is the exposure wavelength. High absorption is not preferred. Specific examples of such compounds include 1,4-dihydroxycyclohexane, 2,2-bis (4′-hydroxycyclohexyl) propane, tri (4′-hydroxycyclohexyl) ethane, and pentaerythritol. Although possible, the content of the present invention is not limited to these. The amount of the compound containing two or more phenolic hydroxyl groups in the molecule to be added for crosslinking may vary depending on the alkali-soluble group (phenolic hydroxyl group or carboxyl group, etc.) of the unprotected resin before protecting the acid-decomposable group. ) On average 0.01% to 10%
Is preferably, more preferably 0.05 to 5%, particularly preferably 0.1 to 3%. The following general formula (X) is preferable as the alkyl vinyl ether compound.

General formula (X)

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In the formula (X), R _{11 to} R ₁₃ may be the same or different and represent a hydrogen atom, an alkyl group, an allyl group, an aralkyl group or a cycloalkyl group. R ₁₄ is an alkyl group,
Represents an allyl group, an aralkyl group, or a cycloalkyl group. R
₁₁ and R ₁₃ , or R ₁₁ and R ₁₂ are a 5- to 10-membered ring of carbon atoms,
Alternatively -O -, - S -, - SO 2 -, - N (R 15) -
May form a ring containing a hetero atom of R ₁₅ represents an alkyl group, an allyl group, or an aralkyl group. R ₁₂ and R ₁₄ may form a ring containing a 5- to 8-membered ring containing an oxygen atom and a carbon atom.

In the formula (1), the alkyl group represented by R _{11 to} R ₁₅ has 1 to 1 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.
Preferably, the aryl group is a vinyl group, and as the aralkyl group, an aralkyl group having 7 to 10 carbon atoms such as a benzyl group, a phenethyl group, and a cumyl group is preferable. , A cyclopropyl group, a cyclobutyl group, a cyclohexyl group and an adamantyl group are preferred.

Examples of the 5- to 10-membered ring of carbon atoms formed by R ₁₁ and R ₁₃ or R ₁₁ and R ₁₂ include a cyclohexyl group, a cyclopentyl group and a cyclobutyl group. R ₁₁
And R ₁₃ , or R ₁₁ and R ₁₂ form —O—, —S—,
_{-SO 2 -, - N (R} 15) - The ring containing a hetero atom,

[0117]

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These heterocycles may further have a substituent. However, in the above structure,
The position bonded to the general formula (X) is a carbon atom portion of each structure. The ring containing 5-8 membered ring containing an oxygen atom and the carbon atom to which R ₁₂ and R ₁₄ form, tetrahydropyranyl group, tetrahydrofuranyl group, and the like. The amount of the alkyl vinyl ether compound to be added is appropriately determined according to the desired acid-decomposable group protection rate.

The content of the acid-decomposable group in the resin is represented by B / (B) based on the number of acid-decomposable groups in the resin (B) and the number of alkali-soluble groups not protected by the acid-decomposable group (S). B + S)
It is represented by The content is preferably 0.03 to 0.55,
It is more preferably 0.08 to 0.45, and further preferably 0.12 to 0.42. If the content is larger than the above range, it is not preferable because it causes film shrinkage due to heat treatment (PEB) after exposure, poor adhesion to a substrate, and scum. On the other hand, if the content is smaller than the above range,
This may hinder image formation, such as a reduction in resolution. However,
The other proportion of the copolymerized monomer is appropriately added to adjust the glass transition point and the like of the resin.

The weight average molecular weight (Mw) of the resin having a crosslinking bond and an acid-decomposable group is preferably in the range of 2,000 to 200,000. If it is less than 2,000, the film is greatly reduced due to the development of the unexposed portion, and if it exceeds 200,000, the dissolution rate of the resin itself in alkali becomes slow and the sensitivity is lowered. More preferably, 5,000 to 1
50,000, more preferably 8,000.
-100,000, particularly preferably 10,
000-80,000. In addition, the degree of dispersion (M
(w / Mn) is preferably from 1.0 to 4.5, more preferably from 1.0 to 3.5, and particularly preferably from 1.0 to 3.0. If the degree of dispersion exceeds 4.5, it is not preferable because resolution and heat resistance are reduced. The smaller the degree of dispersion, the better the heat resistance and image forming properties (pattern profile, defocus latitude, etc.). Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.

In the present invention, the dissolution rate of the resin having a cross-linking bond and an acid-decomposable group varies depending on the amount of the cross-linking bond and the content of the acid-decomposable group. By increasing the amount of cross-linking or the amount of acid-decomposable groups, the dissolution rate in an aqueous alkali solution decreases, and by decreasing the amount of cross-linking or the amount of acid-decomposable groups, the dissolution rate in an aqueous alkali solution increases. I do. It is effective to simply increase the amount of the acid-decomposable group to improve the resist performance, which is greatly affected by the dissolution contrast between the unexposed portion and the exposed portion, such as the resolution. However, if the amount of the acid-decomposable group introduced is too large, the profile may be deformed by baking after exposure, resulting in deformation of the profile or poor adhesion to the substrate. Further, in order to enlarge the latitude such as the exposure latitude and the process latitude, it is effective to control the dissolution rate of the resin to be used within a certain range. For this reason, the resin used in the present invention has an alkali dissolution rate which is independently controlled by the amount of the cross-linking bond and the amount of the acid-decomposable group by separately performing the reaction of introducing the acid-decomposable group and the cross-linking into the alkali-soluble resin. Since it can be changed, it was found that it was suitable as a resist resin.

As a result of intensive studies, the present inventors have found that it is preferable to satisfy the following two points as a guide for effectively exerting the effects of the present invention. 1. 10 mol% or more of acid-decomposable groups have been introduced into sites where they can be introduced.
2. The alkali dissolution rate in a 0.331 normality tetramethylammonium hydroxide aqueous solution (23 ° C.) is 1 nm / sec or less. The alkali dissolution rate is more preferably 0.1 nm / sec or more and 1 nm / sec or less,
Particularly preferably, it is not less than 0.2 nm / sec and not more than 0.8 nm / sec.

The resins having a crosslinkable bond and an acid-decomposable group in the present invention may be used as a mixture of two or more kinds.
That is, a resin which is easily decomposable with respect to an acid such as an acetal group and a resin which is hardly decomposable with respect to an acid such as a tertiary alkyl ester group may be used in combination. The amount of the resin used in the present invention is 40 to 98% by weight, preferably 5 to 98% by weight, based on the total solid content (excluding the solvent) of the photosensitive composition.
0 to 95% by weight. Further, in order to adjust the alkali solubility, an alkali-soluble resin having no acid-decomposable group may be mixed.

It is preferable to mix an acid-decomposable low-molecular-weight dissolution-inhibiting compound described later together with the above-mentioned acid generator, a resin having a crosslinking bond and an acid-decomposable group. In this case, the content of the dissolution inhibiting compound is from 3 to 45% by weight, preferably from 5 to 45% by weight, based on the total weight of the photosensitive composition (excluding the solvent).
It is 30% by weight, more preferably 10 to 20% by weight.

[IV] Alkali-Soluble Resin Used in the Present Invention In the present invention, it is preferable to use a resin that is insoluble in water and soluble in an aqueous alkali solution (hereinafter, also referred to as an alkali-soluble resin). As the alkali-soluble resin used in the present invention, for example, a novolak resin, a 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 relative to hydroxyl group of polyhydroxystyrene (for example, 5 to 30 mol% of O-methylated product, O- (1
-Methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product, O- (t-
Butoxycarbonyl) methylated product) 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 derivatives thereof, 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 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 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
Based on the total solid content (excluding solvent) of the photosensitive composition,
80% by weight or less, more preferably 60% by weight
It is as follows. If the amount is more than 80% by weight, the film slippage becomes remarkable, and it is not preferable because it hinders image formation.

[V] Low-molecular acid-decomposable dissolution inhibiting compound used in the present invention In the present invention, it is preferable to use a low-molecular acid-decomposable dissolution-inhibiting compound. In the present invention, the low-molecular acid-decomposable dissolution inhibiting compound has a constant molecular weight of 3000 or less, has a structure in which an acid-decomposable group is introduced into a phenol compound having a single structure, and is alkali-soluble by the action of an acid. It is a compound which becomes. 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.
Individual. 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 you are more than a certain distance away,
The dissolution inhibiting property with respect to the alkali-soluble resin is significantly 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 bonding atoms, and in the compound (3), the bonding atom is 12 bonding atoms.

[0130]

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The acid-decomposable dissolution-inhibiting compound of the present invention may have a plurality of acid-decomposable groups on one benzene ring, but it is preferable that one compound be present 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 in single molecular weight, preferably 500
~ 3,000, more preferably 1,000 ~ 2,500
It is.

In a preferred embodiment of the present invention,
A group which can be decomposed by⁰, -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, and 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 decomposable 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 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 a part or all of the phenolic OH group of the polyhydroxy compound described in the specification such as No. 95 is bonded and protected with the above-mentioned group, -R ⁰ -COO-A ⁰ or B ⁰ group, 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 [XVI]
The compound represented by these is mentioned.

[0138]

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[0139]

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[0140]

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[0141]

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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

[0144]

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[0145] 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 ~ R ¹⁰⁷ , R ¹⁰⁹ , R ^{111
~R 118, R 121 ~R 123,} R 128 ~R 129, R 131 ~
R ¹³⁴ , R ^{138 to} R ¹⁴¹ and R ¹⁴³ may be the same or different and represent 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, a nitro group, a carboxyl group, a cyano group, or -N ( ^R155 ) ( ^R156 ) ( ^R155 , ^R156 : H, an alkyl group, or an aryl group) ^R110 : a single bond, an alkylene group, or

[0146]

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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

[0149]

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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 haloalkyl group; E: single bond or oxymethylene group , A to z, a1 to y1: at plural times, 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, z1, a
2, at least one of 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.

[0151]

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[0152]

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[0153]

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[0154]

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Specific examples of preferred compound skeletons are shown below.

[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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

[0176]

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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 3 to 50% by weight, based on the total weight of the photosensitive composition (excluding the solvent), when combined with the acid generating compound and the alkali-soluble resin. Preferably it is in the range of 5 to 40% by weight, more preferably 10 to 35% by weight.

[VI] Organic Basic Compound 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).

[0180]

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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 imidazole, 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 Alternatively, unsubstituted piperazine, substituted or unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is. As particularly preferred compounds, guanidine, 1,1-dimethylguanidine, 1,1,3,
3, -tetramethylguanidine, 2-aminopyridine,
3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-
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, imidazole, 2,4,5
-Triphenylimidazole, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1
-P-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine,
-Pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine and the like, but are not limited thereto.

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 to 10 parts by weight, preferably 0.00 parts by weight, per 100 parts by weight of the photosensitive resin composition (excluding the solvent).
1 to 5 parts by weight. If the amount exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

[VII] Molecular weight having a single molecular weight of 30
00 or less phenolic compound The phenolic compound is preferably 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 3,000 or less, more preferably 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 based on the resin, more preferably 5 to 50% by weight.
３０30% by weight. With an addition amount exceeding 50% by weight,
It is not preferable because a new defect that development residue is deteriorated and a pattern is deformed during development is generated.

Such phenol compounds having a molecular weight of 3000 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, 1,3,3,5-tetrakis (hydroxyphenyl) pentane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1 , 3-tris (hydroxyphenyl) butane, para [α, α,
α ', α'-tetrakis (4-hydroxyphenyl)]
-Xylene and the like.

In the present invention, the phenol compound is preferably a compound represented by the following formula (A) or (B).

[0189]

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In the formulas (A) and (B), A is a hydrogen atom or a hydroxyl group, E and G are groups represented by the following,

[0191]

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R _{1 to} R ₄ each represent a hydrogen atom, -XR ₁₃
Or a halogen atom, R _{5 to} R ₆ : hydrogen atom, methyl group, ethyl group, haloalkyl group having 1 to 2 carbon atoms, R ₇ : hydrogen atom, methyl group, ethyl group, haloalkyl having 1 to 2 carbon atoms Groups, a to f and k to n: each an integer of 0 or 1 to 3; g to j: 0, 1 or 2, each; an integer of 1 to 3; D is a single bond, a carbonyl group, a sulfide group, or a sulfonyl A group, —C (R ₅ ) (R ₆ ) — or a group represented by the following:

[0193]

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R _{8 to} R ₁₂ : a hydrogen atom, —OH,
-CN, -COOH, -X-R ₁₃ or halogen atom, R _13: 1-8C alkyl group having a carbon, X: a single bond, -O -, - S -, - CO -, - OCO-, a Represent.

In the compounds represented by the general formulas (A) and (B) of the present invention, examples of the alkyl group represented by R ₁₃ include a methyl group, an ethyl group, a hydroxyethyl group, a propyl group, a hydroxypropyl group, Examples thereof include an alkyl group having 1 to 8 carbon atoms such as an n-butyl group, an isobutyl group, a hexyl group, and a 2-ethylhexyl group. Among them, an alkyl group having 1 to 4 carbon atoms is particularly preferable. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom, and a chlorine atom and a bromine atom are particularly preferable. R ₅
Examples of the haloalkyl group having 1 to 2 carbon atoms of to R ₇ include a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, a chloroethyl group, a dichloroethyl group, and a trichloroethyl group. Examples thereof include an ethyl group, a bromoethyl group, and a tribromoethyl group, and particularly, R _{5 to} R ₇ are preferably a hydrogen atom and a methyl group. X is a single bond, -O-, -S
-, -CO-, -OCO-, in which a single bond,-
O- and -OCO- are preferred.

The compound represented by the general formula (A) or (B) has an aromatic hydroxyl group in which the total number of carbon atoms in the molecule is 27 to 60 and the total number of aromatic hydroxyl groups is 2 to 10. Low molecular weight compounds are preferred. Among these compounds, compounds that increase the alkali dissolution rate of the alkali-soluble resin when added to the alkali-soluble resin are particularly desirable. When the compound has more than 60 carbon atoms, the effect is reduced. If the diameter is smaller than 27, new disadvantages such as a decrease in heat resistance occur. In order to exert the effect sufficiently, it is necessary to have at least two hydroxyl groups in the molecule, but if this number exceeds 10, the effect is reduced. In the present invention, the compound represented by the general formula (A) or (B)
Specific examples of the useful low molecular weight compound having an aromatic hydroxyl group represented by the following are shown below, but are not limited thereto.

[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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[0202]

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[0203]

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[0204]

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[0205]

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[0206]

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[0207]

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[0208]

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[0209]

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[0210]

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[0211]

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[0212]

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[0213]

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[0214]

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[0215]

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[0216]

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The preferable addition amount of the compounds represented by formulas (A) and (B) is 2 to 50% by weight, more preferably 3 to 30% by weight, and further preferably 3 to 30% by weight based on the resin.
１５15% by weight. With an addition amount exceeding 50% by weight,
A new disadvantage occurs in that the pattern is deformed during development. The compounds represented by the above general formulas (A) and (B)
Two or more kinds may be used as a mixture.

The general formula (A) or the general formula (B) of the present invention
The low molecular weight compound having an aromatic hydroxyl group represented by the following formula is disclosed in, for example, JP-A-2-28531, U.S. Pat. No. 4,916,621.
0, it can be easily synthesized by those skilled in the art with reference to the method described in European Patent No. 219294 and the like.

[VIII] Other components used in the present invention The photosensitive composition of the present invention may further contain, if necessary, a dye, a pigment, a plasticizer, a surfactant, a photosensitizer and the like. Can be.

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 the above-mentioned components, and coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate,
Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

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, 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 above-mentioned 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.

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

[0226]

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 of Polymer 1] (no crosslinking) 21.0 g (0.175 mol) of poly (p-hydroxystyrene) (VP-8000 manufactured by Nippon Soda) and 7.0 g
(0.07 mol) of t-butyl vinyl ether in 100
was dissolved in tetrahydrofuran (THF), and 5 mg of p-toluenesulfonic acid was added thereto.
Stirred for hours. The reaction solution was poured into 3 liters of water, and the precipitated powder was collected by filtration and dried to obtain Polymer 1. The protection rate was determined by TGA measurement (protection rate 32%)

[Synthesis Example of Polymer 2] (with crosslinking) 21.0 g (0.175 mol) of poly (p-hydroxystyrene) (VP-8000 manufactured by Nippon Soda) and 7.0 g
(0.07 mol; 40 mol% based on poly (p-hydroxystyrene)) and 0.86 g (0.0035 mol; 2.0 mol based on poly (p-hydroxystyrene)) %) Of 2,2-bis (4
(Hydroxycyclohexyl) propane was dissolved in 100 ml of THF, 5 mg of p-toluenesulfonic acid was added thereto, and the mixture was stirred at room temperature for 24 hours. The reaction solution was poured into 3 liters of water, and the precipitated powder was collected by filtration, dried,
Polymer 2 was obtained. The protection rate was determined by TGA measurement (protection rate 31%)

[Synthesis Examples of Polymers 3 to 8] The type and amount of vinyl ether and the amount of 2,2-bis (4-hydroxycyclohexyl) propane are shown in Table 1 below with respect to poly (p-hydroxystyrene). The polymers 3 to 8 were synthesized in the same manner as in the synthesis example of the polymer 2 except for the above.

[Synthesis Examples of Polymers 9 to 10] Polymer 2
In the synthesis examples of the above, 2,2-bis (4-hydroxycyclohexyl) propane was changed to 1,4-dihydroxycyclohexane or tri (4-hydroxycyclohexyl) ethane, and the others were the same as in the synthesis example of the polymer 2 except that the polymer 9 or 10 was synthesized. Table 1 below shows the charge ratio, protection rate, and alkali dissolution rate of the synthesized polymer.

[0230]

[Table 1]

Here, the method of measuring the alkali dissolution rate was such that 0.85 g of each polymer was dissolved in 4.15 g of methoxypropyl-
The polymer was dissolved in 2-acetate and filtered through a 0.2 μm filter to prepare a polymer solution. This polymer solution is applied on a silicon wafer using a spin coater,
The polymer was dried on a vacuum adsorption type hot plate at 00 ° C. for 90 seconds to obtain a polymer film having a thickness of 1.0. The alkali dissolution rate of this polymer film in a 0.331 normal tetramethylammonium hydroxide (TMAH) aqueous solution (23 ° C.) was measured using a dissolution rate monitor (DRM, manufactured by Orbital Science).

The abbreviations used in Table 1 represent the following contents. TBVE: t-butyl vinyl ether EVE: ethyl vinyl ether BHCP: 2,2-bis (4-hydroxycyclohexyl) propane DHCH: 1,4-dihydroxycyclohexane THCE: tri (4-hydroxycyclohexyl) ethane

Hereinafter, a synthesis example of the photoacid generator used in the present invention will be described. [Synthesis Example 1] 45 of triphenylsulfonium Cl salt
19.9 g (0.030 mol) of a 1% aqueous solution was dissolved in 200 ml of ion-exchanged water. Hard type (branch type)
Dodecylbenzenesulfonic acid Na salt 10.5 g (0.0
(30 mol) in 400 ml of ion-exchanged water was added with stirring at room temperature. The precipitated viscous solid was separated by decanting, and washed with 1 L of ion-exchanged water. The obtained viscous solid was dissolved in 100 ml of acetone, and 500 m
and stirred for 1 hour to recrystallize. Deposit the precipitate under vacuum, 5
As a result of drying at 0 ° C., 15.5 g of a glassy solid was obtained. According to NMR measurement, this solid was converted to the compound (I) of the present invention.
-3).

[Synthesis Example 2] Instead of 10.5 g (0.030 mol) of sodium dodecylbenzenesulfonate of Synthesis Example 1, 9.3 g (0.030 mol) of branched octyloxybenzenesulfonic acid Na salt was used. And others are Synthesis Example 1.
13.2 g of a glassy solid was obtained in the same manner as described above. NMR
By measurement, it was confirmed that this solid was the compound (I-10) of the present invention.

Synthesis Example 3 In place of 10.5 g (0.030 mol) of sodium dodecylbenzenesulfonate of Synthesis Example 1, 25.7 g (0.030 mol) of a 40% aqueous solution of sodium dibutylnaphthalenesulfonic acid was used. The other conditions were the same as in Synthesis Example 1 to obtain 14.8 g of a glassy solid. N
According to MR measurement, this solid was identified as Compound (I-3) of the present invention.
4) was confirmed.

[Synthesis Example 4] Diphenyliodonium C
9.5 g (0.030 mol) of salt 1 in deionized water 200
Dissolved in ml. To this solution was added a solution of 10.5 g (0.030 mol) of hard (branched) sodium dodecylbenzenesulfonic acid salt in 400 ml of ion-exchanged water while stirring at room temperature. The precipitated viscous solid was separated by decanting, and washed with 1 L of ion-exchanged water. The obtained viscous solid was dissolved in 100 ml of acetone, and charged into 500 ml of ion-exchanged water with stirring to cause recrystallization. The precipitate was dried at 50 ° C. under vacuum to obtain 14.5 g of a glassy solid. NM
By R measurement, this solid was converted to the compound (II-3) of the present invention.
Was confirmed.

[Synthesis Example 5] Instead of 10.5 g (0.030 mol) of sodium dodecylbenzenesulfonate of Synthesis Example 4, branched-type sodium octyloxynaphthalenesulfonate was used.
Using 12.3 g (0.030 mol) of the salt, 16.2 g of a glassy solid was obtained in the same manner as in Synthesis Example 4 except for the above. NM
By R measurement, this solid was converted to the compound (II-3) of the present invention.
1) was confirmed.

[Synthesis Example 6] 12.9 g of 4,4'-bis (t-butylphenyl) iodonium Cl salt (0.03
0 mol) was dissolved in 400 ml of ion-exchanged water. To this solution, a solution of 12.7 g (0.030 mol) of 9,10-n-dibutoxy-2-anthracenesulfonic acid Na salt in 400 ml of ion-exchanged water was added with stirring at room temperature. The precipitated viscous solid was separated by decanting, and 1 L of ion-exchanged water was used.
And washed with water. The obtained solid was dissolved in acetone (100 ml) and poured into ion-exchanged water (500 ml) with stirring to cause recrystallization. The precipitate was dried at 50 ° C. under vacuum to obtain 21.7 g of powder. By NMR measurement, it was confirmed that this solid was the compound (II-41) of the present invention. Hereinafter, the sulfonium and iodonium compounds of the present invention were synthesized in the same manner.

[Synthesis Example 1 of Dissolution Inhibitor Compound] α,
α ′, α ″ -tris (4-hydroxyphenyl) -1,
20 g of 3,5-triisopropylbenzene was dissolved in 400 ml of tetrahydrofuran. Under a nitrogen atmosphere
14 g of potassium tert-butoxide was added, and after stirring at room temperature for 10 minutes, 29.2 g of di-tert-butyl dicarbonate 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 2 of Dissolution Inhibitor Compound] α,
α, α ', α', α ", α" -hexakis (4-hydroxyphenyl) -1,3,5-triethylbenzene 14.3 g
(0.020 mol) of N, N-dimethylacetamide 1
In a 20 ml solution, 21.2 g (0.15 mol) of potassium carbonate and 27.1 g (0.14 mol) of t-butyl bromoacetate were added.
Mol) was added and the mixture was stirred at 120 ° C for 7 hours. Thereafter, the reaction mixture was poured into 1.5 l of water and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 2/8 (volume ratio)), and as a result, a pale yellow powder was obtained. 24 g were obtained. N
According to MR, this is a compound example (62: R is all -CH ₂
—COO—C ₄ H ₉ ^t group).

[Synthesis Example 3 of Dissolution Inhibitor Compound] α,
α ', α "-tris (4-hydroxyphenyl) -1,
48.1 g of 3,5-triisopropylbenzene (0.1
0 mol) in 300 ml of dimethylacetamide,
To this, 22.1 g (0.16 mol) of potassium carbonate and 42.9 g (0.22 mol) of t-butyl bromoacetate were added. Then, it stirred at 120 degreeC for 5 hours. The reaction mixture was poured into 2 l of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate. The ethyl acetate extract is concentrated and subjected to column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 1/5 (volume ratio))
)), The compound example (31: 2 R
It is _{-CH 2 -COO-C 4 H 9} t group, one R to give a hydrogen atom) 10 g.

Examples 1 to 15 and Comparative Examples 1 to 3 Resists were prepared using the compounds of the present invention shown in the above Synthesis Examples. The formulations at that time are shown in Tables 2 and 3 below.

[0243]

[Table 2]

[0244]

[Table 3]

The structures of the compounds used in Tables 2 and 3 are shown below.

[0246]

Embedded image

[Preparation and Evaluation of Photosensitive Composition] Each material shown in Tables 2 and 3 was dissolved in 48 g of methoxypropyl-2-acetate, and filtered with a 0.2 μm filter to prepare a resist solution. This resist solution was applied on a silicon wafer using a spin coater,
℃, dried on a vacuum adsorption type hot plate for 60 seconds,
A polymer film having a thickness of 0.83 μm was obtained. A KrF excimer laser stepper (NSR150
5EX; NA = 0.42; manufactured by Nikon). Immediately after the exposure, heating was performed for 60 seconds on a vacuum adsorption type hot plate at 100 ° C., and immediately 2.38% tetramethylammonium hydroxide (TMA)
H) Dipped in an aqueous solution for 60 seconds, rinsed with pure 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 4 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 for reproducing a 0.35 μm mask pattern. [Resolving power] The resolving power indicates a limit resolving power at an exposure amount for reproducing a mask pattern of 0.35 μm. [Heat resistance] 130 ° C.
Was adsorbed on a vacuum adsorption type hot plate for 2 minutes, and then cooled on a cooling plate for 1 minute. 10μ on this substrate
The cross-sectional profile of the m pattern was observed with a scanning electron microscope, and the loosening of the resist pattern was observed. ○ indicates that the slack was smaller (more rectangular) than that of Comparative Example 1, △ indicates the equivalent, and × indicates the larger (dome type).

[0249]

[Table 4]

From the results shown in Table 4, it can be seen that the resist of the present invention is a positive resist composition having a good profile, high sensitivity and high resolution, and having better heat resistance than Comparative Examples 1 to 3. .

[0251]

Industrial Applicability The chemically amplified positive resist composition of the present invention has a good profile, high sensitivity, high resolution and good heat resistance.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshiaki Aoi 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd. (72) Kazuya Uenishi 4000, Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Photo Film Co., Ltd.

Claims (6)

[Claims] 1. An alkali-soluble resin having a group that decomposes by the action of a cross-linking bond and an acid to increase the solubility in an alkali developer, and a sulfonic acid that generates sulfonic acid upon irradiation with actinic rays or radiation. (I) or (I
A chemically amplified positive resist composition comprising the compound represented by I). Embedded image In the formula, R _{1 to} R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom, or a —S—R ₆ group. R
₆ represents an alkyl group or an aryl group. X ^- has at least one group selected from the group consisting of a branched or cyclic alkyl group and an alkoxy group having 8 or more carbon atoms,
It has at least two groups selected from the group consisting of linear, branched or cyclic alkyl groups and alkoxy groups having 4 to 7 carbon atoms, or linear or branched carbon groups having 1 to 7 carbon atoms.
It represents an anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least three groups selected from the group consisting of three alkyl groups and alkoxy groups. 2. The method according to claim 1, wherein the cross-linking is formed by a reaction of a compound containing two or more phenolic hydroxyl groups in a molecule, a phenolic hydroxyl group of an alkali-soluble resin, and an alkyl vinyl ether compound. The chemically amplified positive resist composition according to claim 1. 3. The chemically amplified positive resist composition according to claim 1, wherein the composition comprises an organic basic compound. 4. A group in which the alkali-soluble resin is decomposed into a low-dispersion poly (hydroxystyrene) obtained by anionic living polymerization by the action of a crosslinking bond and an acid to increase the solubility in an alkali developer. The chemically amplified positive resist composition according to any one of claims 1 to 3, wherein the resin is a resin into which is introduced. 5. The chemically amplified positive resist composition according to claim 1, comprising one or more phenolic compounds having a single molecular weight and a molecular weight of 3000 or less. 6. The phenolic compound having a single molecular weight and a molecular weight of 3000 or less, which contains a low-molecular acid-decomposable dissolution inhibiting compound having a group decomposable by an acid introduced therein. 6. The chemically amplified positive resist composition according to claim 1.