JPH10133364A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive composition having high sensitivity and excellent preservable stability with age by incorporating a specific triaryl sulfonium sulfonate. SOLUTION: The triaryl sulfonium sulfonate obtained by the reaction of a triary sulfonium halogenide with a ammonium sulfonate and generating an acid by the irradiation with active ray or radiation is incorporated. As an ammonium cation of the ammonium sulfonate to be used, a tetraalkyl ammonium cation such as tetramethyl ammonium cation or tetraethyl ammonium cation, a trialkyl ammonium cation such as trimethyl ammonium cation or triethyl ammonium cation and a dialkyl ammonium cation such as dimethyl ammonium cation or diethyl ammonium cation are mentioned.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition containing a compound capable of generating an acid upon irradiation with actinic rays or radiation.
The present invention relates to a photosensitive composition having excellent aging stability.

[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, and US Pat.
No. 628, EP 249,139 and the like are generally used as chemically amplified resist compositions. Among them, the chemically amplified positive resist composition generates an acid in the exposed part by irradiation with radiation such as far ultraviolet light, and the reaction using the acid as a catalyst causes a developing solution between the irradiated part and the non-irradiated part of the active radiation. This is a pattern forming material that changes the solubility of the substrate to form a pattern on a substrate.

Examples of such a combination include a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (JP-A-48-90003), 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 (Japanese Patent Application Laid-Open No. 55-12959), a combination with an N-acyliminocarbonate compound (Japanese Patent Application Laid-Open No. 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),
Combination with a silyl ester compound (JP-A-60-102)
No. 47) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-12446).
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-63-250542, Polym.Eng.Sce., Vol. 23, 101
2 (1983); ACS.Sym. 242, 11 (1984); Semicond
uctor World 1987, November, p. 91; Macromolecules, 2
Vol. 1, p. 1475 (1988); SPIE, vol. 920, p. 42 (1988);
Combination systems with esters or carbonate compounds of primary or secondary carbons (eg t-butyl, 2-cyclohexenyl). These systems also have high sensitivity and have a deep-UV compared to the naphthoquinonediazide / novolak resin system.
Since the absorption in the region is small, it can be an effective system for shortening the wavelength of the light source.

The positive chemically amplified resist comprises an alkali-soluble resin, a compound that generates an acid upon exposure to radiation or the like (photoacid generator), and a compound that inhibits dissolution of the alkali-soluble resin having an acid-decomposable group. A three-component system,
A two-component system composed of a resin having a group (acid-decomposable group) which is decomposed by the reaction with an acid and becomes alkali-soluble (acid-decomposable group), or a resin having a group which is decomposed by the reaction with an acid and becomes alkali-soluble And a dissolution inhibiting compound and a photoacid generator.
They can be roughly classified into five-component systems. In these two-component, 2.5-component or three-component positive chemically amplified resists, an acid from a photoacid generator is interposed by exposure, and after heat treatment and development, a resist pattern is obtained.

[0006] Sulfonium salts, which are attracting attention for use as acid generators, are used, for example, as photoacid generators to form a positive image with the above-described structure, or are water-insoluble and alkali-soluble with a crosslinking agent. To form a negative image. Further, it is used as a compound that generates an acid by heat, and can form a negative image by combining a photothermal conversion material (such as a dye), a crosslinking agent and a water-insoluble and alkali-soluble resin.

The sulfonium salt is disclosed, for example, in JP-A-6-199770, by reacting a commercially available triphenylsulfonium chloride with sodium sulfonate in water, and subjecting the resultant to a salt exchange to obtain triphenylsulfonium sulfonate. It is described that the salt can be obtained by a method of filtering out a salt or dissolving and removing the salt in an organic solvent.

[0008]

However, when a sulfonium salt, which is an acid generator obtained by the above method, is used in a resist composition, the sensitivity becomes insufficient. Further, particles were generated when the resist composition was stored. That is, the storage stability over time was deteriorated. As described above, the triarylsulfonium sulfonate obtained by the conventional reaction of a triarylsulfonium halide salt with a sulfonate has problems in sensitivity and storage stability over time. Further improvement was desired. Accordingly, an object of the present invention is to provide a photosensitive composition having high sensitivity and good storage stability over time.

[0009]

Means for Solving the Problems The inventors of the present invention have made intensive studies while paying attention to the above-mentioned characteristics, and as a result, have found that the structure of a sulfonate to be reacted with a triarylsulfonium halide, specifically, a counter of a sulfonate anion. It has been found that the above object can be achieved by selecting a cation, and the present invention has been completed based on this finding. That is, it has been found that the object of the present invention is achieved by the following constitutions. (1) Photosensitivity comprising a triarylsulfonium sulfonate which is obtained by reacting a triarylsulfonium halide salt with an ammonium sulfonate and which generates an acid upon irradiation with actinic rays or radiation. Composition. (2) a resin having a group that is decomposed by the action of an acid to increase the solubility in an alkaline developer, and an actinic ray or radiation obtained by reacting a triarylsulfonium halogenide salt with an ammonium sulfonate salt A photosensitive composition comprising a triarylsulfonium sulfonate which generates an acid upon irradiation with light.

(3) A resin which is insoluble in water and soluble in an aqueous alkali solution, has a group which can be decomposed by an acid, and has a solubility in an alkali developing solution which is increased by the action of an acid.
And a triarylsulfonium sulfonate capable of generating an acid upon irradiation with actinic rays or radiation, which is obtained by reacting a triarylsulfonium halogenide salt with an ammonium sulfonate, and a low molecular weight acid-decomposable dissolution inhibiting compound of not more than 00. A photosensitive composition comprising: (4) The photosensitive composition as described in any one of (1) to (3) above, wherein the ammonium sulfonate is a tetramethylammonium sulfonate. (5) The above (1) to (1), wherein the ammonium sulfonate is a sulfonate NH ₄ salt.
The photosensitive composition according to any one of (3).

In the present invention, the reason why the object of the present invention has been attained by the above constitution is not clear, but it is considered that the object was achieved by selecting an ammonium salt as the counter cation of the sulfonate anion. This is unpredictable from conventional knowledge,
Although the details are unknown, a metal salt such as sodium as a counter cation of the conventional sulfonate anion is
It is considered that the metal salt mixed into the photosensitive composition had an adverse effect on the photosensitive composition, thereby deteriorating the sensitivity and the storage stability over time. Further, in the present invention, since a metal salt such as sodium is not used as the counter cation of the sulfonate anion, contamination by metal impurities does not occur from the viewpoint of manufacturing a resist material.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [I] Triarylsulfonium sulfonate which generates an acid upon irradiation with actinic rays or radiation obtained by reacting a triarylsulfonium halogenide salt with an ammonium sulfonate ammonium sulfonate used in the present invention Examples of the ammonium cation include a tetraalkylammonium cation, a tetraalkylammonium cation such as a tetraethylammonium cation, a trimethylammonium cation, a trialkylammonium cation such as a dimethylethylammonium cation, a dimethylammonium cation, a diethylammonium cation,
Examples thereof include dialkylammonium cations such as diisopropylammonium cation, pyrrolidinium cation, and piperidinium cation, monoalkylammonium cations such as methylammonium cation, ethylammonium cation, and butylammonium cation, and ammonium cations. Preferably, ammonium cation (NH ₄ ⁺ ), monomethyl ammonium cation, dimethyl ammonium cation,
Trimethylammonium cations and tetramethylammonium cations are more preferable, and ammonium cations (NH ₄ ⁺ ) and tetramethylammonium cations are more preferable.

The sulfonic acid of the ammonium sulfonic acid salt used in the present invention includes alkyl, aryl and aralkylsulfonic acids. The alkyl, aryl or aralkylsulfonic acid used in the present invention is not particularly limited, but the alkyl group in the case of the alkylsulfonic acid has 1 to 20 carbon atoms and may have a substituent, and may have a straight-chain or And branched alkyl groups. If the number of carbon atoms exceeds 20, undesirably, sensitivity decreases and development residue increases. As the substituent, a methoxy group, an alkoxy group having 1 to 4 carbon atoms such as an ethoxy group, a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom, an allyl group,
Examples thereof include an alkenyl group having 2 to 6 carbon atoms such as a vinyl group, a hydroxy group, an acyl group, and a carboxy group.

The aryl group in the case of arylsulfonic acid has 6 to 20 carbon atoms and may have a substituent, and examples thereof include a monocyclic or condensed aryl group. Further, a hetero ring containing a hetero atom in the aromatic ring of the aryl group may be used. If the number of carbon atoms exceeds 20, it is not preferable because sensitivity is reduced and development residue is increased. As the substituent, preferably a methoxy group, an alkoxy group having 1 to 4 carbon atoms such as an ethoxy group, a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom, an aryl group having 6 to 10 carbon atoms, an allyl group,
Examples thereof include an alkenyl group having 2 to 6 carbon atoms such as a vinyl group, a hydroxy group, an acyl group, and a carboxy group.

The aralkyl group in the case of the aralkyl sulfonic acid includes an aralkyl group having 7 to 20 carbon atoms and optionally having a substituent. When the number of carbon atoms exceeds 20, it is not preferable because the sensitivity is lowered and the development residue is increased. As the substituent, preferably a methoxy group, an alkoxy group having 1 to 4 carbon atoms such as an ethoxy group, a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom, an aryl group having 6 to 10 carbon atoms, an allyl group,
Examples thereof include an alkenyl group having 2 to 6 carbon atoms such as a vinyl group, a hydroxy group, an acyl group, and a carboxy group.

The triarylsulfonium cation in the triarylsulfonium halide used in the present invention includes a compound represented by the following general formula (1).

[0017]

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In the formula (1), A ₁ , A ₂ and A ₃ each represent an arylene group such as a phenylene group and a naphthylene group;
R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, a thioaryl group, a thioalkyl group, an alkenyl group, or an acyl group. a, b, and c each represent an integer of 1-3. Specific examples of these triarylsulfonium cations are shown below, but the present invention is not limited thereto.

[0019]

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The halogen anion in the triarylsulfonium halide used in the present invention includes anions such as chlorine, bromine and iodine.

In the present invention, a procedure for producing a triarylsulfonium sulfonate will be described below. However, the content of the present invention is not limited to these. (1) Synthesis of the above-mentioned alkyl, aryl or aralkylsulfonic acid from the above-mentioned hydroxide salt of ammonium cation or a method such as hydrolysis reaction of the above-mentioned sulfonyl chloride under basic conditions, or the like, or commercially available. The ammonium salt of is used. (2) a commercially available triphenylsulfonium halogenide,
Or reacting an aqueous solution of a triarylsulfonium halogenide synthesized by the method described in J. Am. Chem. Soc. 1990, 112, 6004 with the ammonium salt of sulfonic acid obtained in the above (1) in an aqueous solution system. (3) After the reaction, the obtained precipitate is collected by filtration and washed with water to obtain a solid of triarylsulfonium sulfonate, or dissolved in an organic solvent, and the solution is washed with water and concentrated to give triarylsulfonium sulfonate. A solid of the acid salt is obtained or dissolved in an organic solvent, and this solution is washed with water, and then replaced with a solvent having a high boiling point capable of dissolving the solid content of the photosensitive composition, particularly the resist composition, to obtain a triarylsulfonium sulfonic acid. Obtained as a solution of the salt coating solvent.

The base used in the basic hydrolysis reaction in the above (1) may be a hydroxide salt of the above ammonium cation.

In the above (3), as the organic solvent used at the time of taking out, any solvent can be used as long as it can dissolve the triarylsulfonium salt, is hardly soluble in water, and can be concentrated. But not limited thereto, such as ester solvents, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ether solvents such as dimethoxyethane. Since these solvents require concentration, the boiling point is 5
The temperature is preferably from 0 ° C to 120 ° C. When the boiling point is lower than 50 ° C., the volatility is increased, and the handling property is poor, which is not preferable. On the other hand, when the boiling point exceeds 120 ° C., concentration becomes difficult, which is not preferable in operation.

The high-boiling solvent used at the time of resist coating for replacing the condensable organic solvent may be 2-
Examples include heptanone, γ-butrolactone, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl lactate, ethyl pyruvate, propyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate. The boiling point of these solvents is preferably from 140 ° C to 200 ° C. If the boiling point is lower than 140 ° C., the difference in boiling point between the solvent and the low boiling point solvent to be replaced is small, which is not preferable in terms of the replacement operation. If the temperature exceeds 200 ° C., the amount of the coating solvent remaining during the formation of the resist is increased, and the heat resistance is deteriorated, which is not preferable.

In the above reaction, the preferable range of the charged molar ratio (triarylsulfonium halogenide salt / triarylsulfonium halogenide salt + ammonium sulfonate) is 0.5 to 2.0, more preferably 0.5 to 2.0. 0.6-1.5, particularly preferably 0.75-
1.2.

As the triarylsulfonium sulfonate which generates an acid upon irradiation with actinic rays or radiation, any photosensitive composition using a photoacid generator can be used. For example, a negative or positive photoresist composition can be used.
In the case of a negative photoresist composition, examples include the above-mentioned photoacid generator of the present invention, a crosslinking agent for crosslinking a resin by the action of an acid, an alkali-soluble resin, and a composition containing other additives that can be added. In the case of a positive photoresist composition, the above-mentioned two-component, 2.5-component or three-component chemically amplified photoresist composition containing the photoacid generator of the present invention can be mentioned. The content of the triarylsulfonium sulfonate that generates an acid upon irradiation with actinic rays or radiation is appropriately set depending on the type of the photosensitive composition. Is suitably 0.1 to 20% by weight, preferably 0.5 to 10% by weight, and more preferably 1 to 7% by weight.

In the present invention, the content of the ammonium salt in the photosensitive composition containing a triarylsulfonium sulfonate is preferably 0.1 to 1000 ppm. As a result, the sensitivity is further improved, and the precipitation of particles and the like can be further prevented when the photosensitive composition is stored over time, and the storage stability of the composition over time is further improved. Although the cause of the improvement in sensitivity is not clear, it is considered that the ammonium salt assists the penetration of the developer into the photosensitive layer during development. When the content of the ammonium salt is less than 0.1 ppm, the permeability of the developer tends to be insufficient, and when it exceeds 1000 ppm, precipitation of particles and the like tends to occur when stored over time. The content of the ammonium salt is more preferably 0.3 to 100 ppm, and still more preferably 0.5 to 100 ppm.
-10 ppm. The content of the ammonium salt in the photosensitive composition is determined by ion chromatography (for example,
It can be measured using Tosoh Corporation IC-8010).

[II] In the present invention, in addition to the above triarylsulfonium sulfonates which generate an acid upon irradiation with actinic rays or radiation, other photoacid generators may be used within the range where the above effects of the present invention can be obtained. Agents may be used in combination. The amount of the photoacid generator that can be used in combination in the photosensitive composition is preferably equal to or less than the weight of the photoacid generator according to the present invention. When the used amount exceeds the equivalent amount, an insufficient result is obtained in the point of the sensitivity improvement which is an effect of the present invention. 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, US Pat. No. 3,905,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070,
JP-A-60-239736, JP-A-61-169835, JP-A-61-16
No. 9837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243, Organic halogen compounds described in JP-A-63-298339, K. Meier et al., J. Rad .Curing, 13 (4), 26 (198
6), TPGill et al., Inorg.Chem., 19,3007 (1980), DA
struc, Acc.Chem.Res., 19 (12), 377 (1896), JP-A-2-614
Organometallics / organic halides described in No. 45, S. Hayase
etal, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et.
al, J.Pholymer Sci., Polymer Chem. Ed., 23, 1 (1985), Q.
Q. Zhu et al., J. Photochem., 36, 85, 39, 317 (1987), B. Amit
etal, Tetrahedron Lett., (24) 2205 (1973), DHRBart
on etal, J. Chem Soc., 3571 (1965), PMCollins etal,
J. Chem.SoC., Perkin I, 1695 (1975), M. Rudinstein et al.
Tetrahedron Lett., (17), 1445 (1975), JWWalker etal
J. Am. Chem. Soc., 110, 7170 (1988), SCBusman et al., JI
maging Technol., 11 (4), 191 (1985), HM Houlihan et al.
Macormolecules, 21, 2001 (1988), PMCollins et al, J. Ch.
em.Soc., Chem.Commun., 532 (1972), S.Hayase et al, Macro
molecules, 18, 1799 (1985), E. Reichmanis et al, J. Electr
ochem.Soc., Solid State Sci.Technol., 130 (6), FMHou
lihan et al, Macromolcules, 21, 2001 (1988), European Patent No. 0
290,750, 046,083, 156,535, 271,851,
No. 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531
JP-A-60-198538, JP-A-53-133022, etc., a photoacid generator having an o-nitrobenzyl-type protecting group, M.
TUNOOKA etal, Polymer Preprints Japan, 35 (8), G. Berne
r etal, J.Rad.Curing, 13 (4), WJMijs etal, Coating Te
chnol., 55 (697), 45 (1983), Akzo, H. Adachi et al, Polyme
r Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84
No. 515, No. 199,672, No. 044,115, No. 0101,122, U.S. Pat.No. 618,564, No. 4,371,605, No. 4,431,774,
JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No. 3-14010
Compounds which generate sulfonic acid upon photodecomposition, such as iminosulfonate described in JP-A No. 9-16654.
Disulfone compounds described in No. 4, etc. can be exemplified.

A group that generates an acid by the light;
Alternatively, a compound having a compound introduced into a main chain or a side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Rap
id Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Che
m., 152, 153, 163 (1972), JVCrivello etal, J. Polyme
rSci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
No. 3,849,137, Dokoku Patent No. 3914407, JP-A-63-26653
No., JP-A-55-164824, JP-A-62-69263, JP-A-63-69
No. 146038, JP-A-63-163452, JP-A-62-153853,
The compounds described in JP-A-63-146029 can be used.

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

Among the compounds which can be used together and which 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).

[0033]

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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.

[0035]

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[0036]

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[0037]

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

[0039]

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

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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Hereinafter, the present invention will be described in detail using a positive photoresist composition as a preferred embodiment of the present invention as an example. [III] A resin having a group that is decomposed by the action of an acid and increases the solubility in an alkali developer Decomposed by an acid used in the chemically amplified resist in the present invention to increase the solubility in an alkali developer As the resin having a group, the main chain or side chain of the resin,
Alternatively, it is a resin having an acid-decomposable group in both the main chain and the side chain. Among them, a resin having a group which can be decomposed by an acid in a side chain is more preferable. Preferred groups that can be decomposed by an acid are —COOA ⁰ and —O—B ⁰ groups, and further containing these groups include —R ⁰ —COOA ⁰ and —A _r
Include groups represented by -O-B ^0. Where A ⁰ is −
C ( ^R01 ) ( ^R02 ) ( ^R03 ), -Si ( ^R01 ) ( ^R02 )
Shows the (R ^{0 3)} or ^{-C (R 04) (R 05} ) -O-R 06 group. B ⁰ represents A ⁰ or a —CO—O—A ⁰ group (R ⁰ , R ^{01 to} R ⁰⁶ , and Ar have the same meanings as described below).

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

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

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

The resin having an acid-decomposable group used in the present invention is disclosed in EP 254853, JP-A-2-25.
No. 850, No. 3-223860, No. 4-251259
As disclosed in US Pat. No. 6,086,098, 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 copolymerized with various monomers. Can be obtained.

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

[0052]

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[0053]

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[0054]

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[0055]

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The content of the group decomposable with an acid is determined by the number of groups decomposable by an acid (B) and the number of alkali-soluble groups not protected by an acid decomposable group (S) in the resin. B /
It is represented by (B + S). The content is preferably 0.01 to
0.6, more preferably 0.05 to 0.50, and still more preferably 0.1 to 0.45. B / (B + S)> 0.
No. 6 is not preferred because it causes film shrinkage after PEB, poor adhesion to the substrate and scum.

The weight average molecular weight (Mw) of the resin having an acid-decomposable group is preferably in the range of 2,000 to 200,000. If the molecular weight is less than 2,000, the film loss is large due to the development of the unexposed portion. If the molecular weight exceeds 200,000, the dissolution rate of the alkali-soluble resin itself in alkali becomes slow and the sensitivity is lowered. More preferably, 5,
The range is from 000 to 150,000, more preferably from 8,000 to 100,000. Further, the dispersity (Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 2.0, and particularly preferably 1.0 to 2.0.
1.6, and 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, two or more kinds of resins having a group decomposable with an acid may be used in combination. The amount of these resins used in the present invention is 40 to 99% by weight, preferably 50 to 95% by weight, based on the total weight of the photosensitive composition (excluding the solvent). Further, in order to adjust the alkali solubility, an alkali-soluble resin having no acid-decomposable group may be mixed.

Similarly, an acid-decomposable low-molecular-weight dissolution inhibiting compound may be mixed. In this case, the content of the dissolution inhibiting compound is 3 to 45% by weight, preferably 5 to 30% by weight, more preferably 10 to 20% by weight based on the total weight of the photosensitive composition (excluding the solvent). .

[IV] Alkali-soluble resin used in the present invention In the present invention, it is preferable to use a resin which 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, and polyvinyl alcohol derivatives can be mentioned, but are not limited thereto. Not something. Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene,
-Polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partially O-alkylated or O-acylated product of polyhydroxystyrene,
Styrene-hydroxystyrene copolymer and α-methylstyrene-hydroxystyrene copolymer. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

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

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

The weight-average molecular weight of the novolak resin thus obtained is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred are 2,000-20,
000. In addition, the weight average molecular weight of the polyhydroxystyrene other than the novolak resin, its derivative, and the copolymer is 2,000 or more, preferably 5,000.
~ 200,000, more preferably 10,000-1000
00. Further, from the viewpoint of improving the heat resistance of the resist film, 25,000 or more is preferable. here,
The weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography. In the present invention, these alkali-soluble resins may be used as a mixture of two or more kinds. The amount of alkali-soluble resin used is
On the basis of the total weight of the photosensitive composition (excluding the solvent), in a mixed system with a resin having a group capable of decomposing by the action of an acid and increasing the solubility in an alkali developing solution, the total solid content is 80%. % By weight or less, more preferably 60% by weight
Or less, more preferably 40% by weight or less. 8
When the amount is more than 0% by weight, film thinning becomes remarkable, and it is not preferable because image formation is hindered. In a system in which a resin having a group that is decomposed by the action of an acid and increases the solubility in an alkaline developer is not mixed, 40
It is preferably from 90 to 90% by weight, more preferably from 50 to 85% by weight, and still more preferably from 60 to 80% by weight.
If the added amount of the resin is less than 40% by weight, the sensitivity is unfavorably lowered, and if it is more than 90% by weight, the film thinning becomes remarkable and the image formation is hindered.

[V] Low-molecular acid-decomposable dissolution inhibiting compound used in the present invention In the present invention, a low-molecular acid-decomposable dissolution-inhibiting compound may be used. The acid-decomposable dissolution inhibiting compound used in the present invention has at least two acid-decomposable groups in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, the acid-decomposable group Is a compound having at least 8 bonding atoms excluding. In the present invention, the acid-decomposable dissolution-inhibiting compound preferably has at least two groups capable of being decomposed by an acid in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, the acid-decomposable group A compound having at least 10, preferably at least 11, and more preferably at least 12 bonding atoms excluding the above, or a position where the distance between the acid-decomposable groups is the longest, having at least three acid-decomposable groups Is a compound having at least 9, preferably at least 10, and more preferably at least 11 bonding atoms excluding an acid-decomposable group. The preferred upper limit of the number of the bonding atoms is 50, more preferably 30. In the present invention, when the acid-decomposable dissolution inhibiting compound has three or more, preferably four or more acid-decomposable groups,
Further, even in the case of having two acid-decomposable groups, when the acid-decomposable groups are separated from each other by a certain distance or more, the dissolution inhibiting property with respect to an alkali-soluble resin is 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 bond atoms each, and
Individual.

[0065]

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

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

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.

Preferably, a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group,
And a tertiary alkyl ester group and a tertiary alkyl carbonate group. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group and a tetrahydropyranyl ether group.

The acid-decomposable dissolution-inhibiting compound is preferably a compound described in JP-A-1-289946 and JP-A-1-2899.
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 [XV]
The compound represented by I] is mentioned.

[0073]

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[0074]

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[0075]

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[0076]

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

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

[0079]

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[0080] Here, G = 2 to 6, provided that at least one alkyl group of R ^0.99, R ¹⁵¹ when the ^{G = 2, R 150, R} 151: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH,
-CN, halogen atom, -R ¹⁵² -COOR ^{15 3} or ^{-R 154 -OH, R 152, R} 154: an alkylene group, R ^153: a hydrogen atom, an alkyl group, an aryl group or an aralkyl group,, R ^99, R ¹⁰³ To R ¹⁰⁷ , R ¹⁰⁹ , R ^{111 to} R ¹¹⁸ , R
^{121 to} R ¹²³ , R ^{128 to} R ¹²⁹ , R ^{131 to} R ¹³⁴ , R
^{138 to} R ¹⁴¹ and R ¹⁴³ may be the same or different and include a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a halogen atom, nitro Group, carboxyl group, cyano group, or -N ( ^R155 ) ( ^R156 ) ( ^R155 , ^R156 : H, alkyl group, or aryl group) ^R110 : single bond, alkylene group, or

[0081]

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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 in the present application refers to 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

[0084]

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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 the general formula [V]
In the case of (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 + l
1), (i1 + m1), (o1 + q1), (s1 + u1) ≦ 5.

[0086]

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[0087]

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[0088]

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[0089]

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Specific examples of preferred compound skeletons are shown below.

[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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

[0111]

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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 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] 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 an organic basic compound. And phenolic O that promotes solubility in developing solutions
A compound having two or more H groups can be contained.

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

The preferable addition amount of the phenol compound is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the alkali-soluble resin. An addition amount exceeding 50% by weight is not preferable because new development defects such as development residue deterioration and pattern deformation during development occur.

Such a phenol compound having a molecular weight of 1,000 or less can be prepared by those skilled in the art by referring to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. It can be easily synthesized at Specific examples of the phenol compound are shown below, but the compounds that can be used in the present invention are not limited to these.

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

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

[0120]

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Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol,
Substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted Or, unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group,
An aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, and a cyano group. As particularly preferred compounds, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-
Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino -4-methylpyridine, 2-amino-5
-Methylpyridine, 2-amino-6-methylpyridine,
3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 -Tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p- Tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline,
Examples include, but are not limited to, N-aminomorpholine and N- (2-aminoethyl) morpholine.

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

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

Further, the photosensitive composition of the present invention is sensitized by adding a spectral sensitizer as described below and sensitizing the photoacid generator to be used in a longer wavelength region than far ultraviolet where the photoacid generator does not have 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 components and applied 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 manufacture of precision integrated circuit devices by an appropriate application method such as a spinner or a coater, and then passed through a predetermined mask. By exposing, baking and developing, a good resist pattern can be obtained.

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

[0129]

EXAMPLES The present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.
"%" Used in the following examples is "% by weight" unless otherwise specified. Synthesis Example (1) Synthesis of sulfonium salt A 4 equipped with a stirrer, a reflux condenser, a thermometer, and a dropping device
In a one-necked flask, 303 g of triisopropylbenzenesulfonyl chloride and 500 mL of isopropyl alcohol
Was added and stirred to obtain a homogeneous solution, 150 g of tetramethylammonium hydroxide and 300 mL of distilled water were added, and the mixture was heated and stirred under reflux for 5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure. When the powder was deposited, the residue was filtered to obtain 64 g of tetramethylammonium triisopropylbenzenesulfonate.

A tetramethylammonium triisopropylbenzenesulfonate 64 obtained above was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping device.
g and 1 L of distilled water were added and stirred to dissolve, and then 126 g of a commercially available 45% aqueous solution of triphenylsulfonium chloride was added.
Was added dropwise over 1 hour while stirring, and the mixture was stirred for 30 minutes after the completion of the dropwise addition.
Thereafter, 1.5 L of ethyl acetate was added thereto, and the mixture was stirred. After allowing to stand for 1 hour, the oil layer was separated and taken out. Again, add 1 L of ethyl acetate to the aqueous layer
After stirring for 30 minutes, the mixture was allowed to stand for 1 hour, and the oil layer was separated and taken out. The obtained ethyl acetate solution was washed three times with 1 L of distilled water, concentrated, and dried by heating under reduced pressure at 50 ° C. to obtain 88 g of triphenylsulfonium triisopropylbenzenesulfonate as a target substance.

Synthesis Example (2) Synthesis of Sulfonium Salt B After synthesizing tetramethylammonium triisopropylbenzenesulfonate by the same operation as in Synthesis Example (1), a stirrer, a reflux condenser, a thermometer, and a dropping device were used. 64 g of the obtained tetramethylammonium triisopropylbenzenesulfonate and 1 L of distilled water were added to a four-necked flask equipped with, stirred and dissolved, and 126 g of a 45% aqueous solution of commercially available triphenylsulfonium chloride was dissolved in 500 mL of distilled water. The diluted aqueous solution was added dropwise over 1 hour, and the mixture was stirred for 30 minutes after completion of the dropwise addition. Thereafter, 1.5 L of ethyl acetate was added thereto, and the mixture was stirred. After allowing to stand for 1 hour, the oil layer was separated and taken out. Again, 1 L of ethyl acetate was added to the aqueous layer, and the mixture was stirred for 30 minutes. After standing for 1 hour, the oil layer was separated and taken out.

The obtained ethyl acetate solution was diluted with 1 L of distilled water for 3 hours.
Washed twice. 600 g of propylene glycol monomethyl ether acetate was added to the obtained ethyl acetate solution,
Ethyl acetate was distilled off under reduced pressure at 50 ° C./15 mmHg, and again propylene glycol monomethyl ether acetate 20 was removed.
0 g was added, and the mixture was distilled off under reduced pressure at 60 ° C./15 mmHg. After removing the ethyl acetate, the concentration was adjusted with propylene glycol monomethyl ether acetate to obtain 900 g of a 10% solution of the target triphenylsulfonium triisopropylbenzenesulfonate in propylene glycol monomethyl ether acetate. The residual ethyl acetate was confirmed by gas chromatography.

Synthesis Example (3) Synthesis of Sulfonium Salt C An NH ₄ ⁺ salt of dodecylbenzene sulfonic acid (hard type) was synthesized by mixing commercially available dodecyl benzene sulfonic acid (hard type) with aqueous ammonia. In the same apparatus as in Synthesis Example (1), 126 g of a 45% aqueous solution of triphenylsulfonium chloride and 700 g of a 10% aqueous solution of dodecylbenzenesulfonic acid (hard type) in NH ₄ ⁺ were used.
Was added and stirred to deposit a viscous substance. To this, propylene glycol monomethyl ether acetate was added, and
After stirring for 0 minutes, the aqueous layer was removed, and the obtained propylene glycol monomethyl ether acetate layer was washed twice with water. The remaining water was distilled off under reduced pressure, propylene glycol monomethyl ether acetate was added, and propylene glycol monomethyl ether acetate 10 was added. As a% solution, 880 g of triphenylsulfonium dodecylbenzenesulfonate as a target substance was obtained.

Synthesis Example (4) Synthesis of Sulfonium Salt D [Comparative] Except that sodium hydroxide was used in place of tetramethylammonium hydroxide in Synthesis Example (1), an ethyl acetate solution was prepared in exactly the same manner. The resultant was washed with 1 L of distilled water three times, concentrated, and dried by heating under reduced pressure at 50 ° C. to synthesize triphenylsulfonium triisopropylbenzenesulfonate as a target substance.

Synthesis Example (5) Resin E Synthesis Poly (p-hydroxystyrene) (weight average molecular weight 11
000, molecular weight distribution 1.10, use after drying under reduced pressure
48.1 g and 0.47 g of 1,4-dihydroxycyclohexane were dissolved in 250 ml of dehydrated tetrahydrofuran and kept at room temperature. 13. Add t-butyl vinyl ether to this solution.
0 g and p-toluenesulfonic acid monohydrate 0.19 g
Was added, the atmosphere was replaced with nitrogen, and the mixture was sealed and stirred at room temperature for 20 hours. Thereafter, the reaction solution was neutralized with triethylamine, and poured into a solution of 3 liters of ion-exchanged water / 3 g of triethylamine with stirring. The precipitated resin was separated by filtration, washed with water, and dried at 70 ° C. under reduced pressure. 56g of white resin
And 27% of the OH groups of the starting resin were found to be t-
It was confirmed that it was butoxy-1-ethylated (t-butylacetalized). GPC measurement revealed that the weight average molecular weight was 33,000, the molecular weight distribution was 1.75, and the protection rate was 32%.

[Preparation and Evaluation of Resist Solution] 3 g of triphenylsulfonium triisopropylbenzenesulfonate, triphenylsulfonium triisopropylbenzenesulfonate or triphenylsulfonium dodecylbenzenesulfonate obtained in each of the above synthesis examples. 30 g of a 10% solution of a salt in propylene glycol monomethyl ether acetate and 50 g of the resin E synthesized in the above synthesis example were dissolved in propylene glycol monomethyl ether acetate, and filtered through a 0.2 μm filter to prepare a resist solution having a solid content of 15%. Here, the concentration of the ammonium salt in the resist solution containing the sulfonium salts A to D is 1.0 ppm (A),
0.8 ppm (B) and 0.5 ppm (C), and Comparative Example (D) was not detected.

This resist solution was applied on a silicon wafer using a spin coater, dried on a vacuum suction type hot plate at 110 ° C. for 90 seconds, and the applied film thickness was 0.8
A 3 μm resist film was obtained. 248n on this resist film
mKrF excimer laser stepper (NA = 0.4
Exposure was performed using 2). Immediately after the exposure, heating was performed on a vacuum adsorption type hot plate at 100 ° C. for 60 seconds, immediately immersed in a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds, rinsed with distilled water for 30 seconds, and dried. The sensitivity of the pattern on the silicon wafer thus obtained was evaluated as follows. [Evaluation of Sensitivity] Sensitivity was defined as an exposure amount for reproducing a mask pattern of 0.35 μm. [Evaluation over time test] The resist solution prepared by the above method
At 3 ° C., and the particles in the liquid of 0.30 μm or more in the third month were subjected to an automatic particle counter KL manufactured by Rion Co., Ltd.
It measured using -20. The case where the number of particles in 1 mL was 10 or less was evaluated as ○, and the case where the number of particles exceeded 10 was evaluated as ×.

[0138]

[Table 1]

As shown by the above results, the resist containing the triarylsulfonium sulfonate of the present invention has higher sensitivity and hardly any generation of particles due to storage over time as compared with the resist containing the comparative example. You can see that.

[0140]

According to the present invention, it is possible to provide a photosensitive composition capable of increasing sensitivity and suppressing generation and increase of particles with time.

Claims (5)

[Claims] Claims: 1. A triarylsulfonium sulfonate which is obtained by reacting a triarylsulfonium halide salt with an ammonium sulfonate and which generates an acid upon irradiation with actinic rays or radiation. Photosensitive composition. 2. An actinic ray obtained by the reaction of a resin having a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer and a triarylsulfonium halide salt and an ammonium sulfonate. Alternatively, a photosensitive composition containing a triarylsulfonium sulfonate that generates an acid upon irradiation with radiation. 3. A low molecular acid having a molecular weight of 3,000 or less, which is a resin which is insoluble in water and soluble in an aqueous alkali solution, has a group which can be decomposed by an acid, and has an increased solubility in an alkali developer due to the action of an acid. It contains a decomposable dissolution inhibiting compound and a triarylsulfonium sulfonate which is obtained by reacting a triarylsulfonium halide salt with an ammonium sulfonate and which generates an acid upon irradiation with actinic rays or radiation. Photosensitive composition. 4. The photosensitive composition according to claim 1, wherein the ammonium sulfonate is tetramethylammonium sulfonate. 5. The sulfonic acid ammonium salt is a sulfonic acid NH ₄ salt.
4. The photosensitive composition according to any one of 3.