JPH11222460A - Transparent compound, transparent resin, photosensitive resin composition using the transparent resin and production of semiconductor apparatus using the photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound showing high transparency in a short wavelength range of ArF excimer laser, etc. by reacting a specific compound with a carboxylic acid in a strong acid. SOLUTION: A compound of formula I or II ((l) is 1 or 2; (m) is 0 or 2; (n) is 0, 1 or 2; R<1> to R<3> are each H or CH3 ; R<3> and R<4> are each a hydrocarbon) is reacted with a carboxylic acid (e.g. acrylic acid, methacrylic acid, maleic acid or the like) in a strong acid (e.g. sulfuric acid, benzenesulfonic acid, p- toluenesulfonic acid or the like) to give the objective compound. The compound of formula I or II is a compound containing a carbon-carbon bond bridged at the 1,3-positions or 1,4-positions of a cyclohexane ring, a cyclobutane ring or a cyclooctane ring and further a carbon-carbon bond of double bond and at least one of carbons forming the carbon-carbon bond of double bond is required to directly bond three carbon atoms. For example, pinene, camphene, carene, cedrene, cubebene, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent compound and a transparent resin having excellent transparency to short wavelength light such as an ArF excimer laser, and a short wavelength light such as an ArF excimer laser as an exposure energy source. The present invention relates to a photosensitive resin composition suitably used for lithography used. The present invention also relates to a method for manufacturing a semiconductor device capable of obtaining a highly integrated semiconductor device such as a super LSI by forming a fine pattern using the photosensitive resin composition as a resist.

[0002]

2. Description of the Related Art With the demand for higher integration of semiconductor devices, development of microfabrication technology is being promoted. In order to realize this technique, several techniques have been studied, and among them, shortening the wavelength of the light source used in the lithography technique is most promising. In the current lithography technology, i-line (wavelength 365 nm) and KrF excimer laser (wavelength 248 nm) are used.
Using an rF excimer laser (wavelength 193 nm) or a fifth harmonic (wavelength 218 nm) of a YAG laser, etc.
Are being considered.

Hitherto, as a resist for photolithography, a resist composed of a novolak resin and naphthoquinonediazide or a resist composed of tertiary butoxycarbonyloxystyrene and an acid generator has been used. All of them have a compound having a benzene skeleton, and since the compound having a benzene skeleton exhibits dry etching resistance, these compounds are used.

However, a compound having a benzene skeleton has a large absorption near the wavelength of the fifth harmonic of the short-wavelength ArF excimer laser or YAG laser.
A pattern having a good shape could not be formed.

As a method for solving this problem, Japanese Patent Laid-Open No.
JP-A-39665 and JP-A-8-12626 use an aliphatic compound having a cyclic structure, and JP-A-8-82925 discloses a photosensitive material containing a compound having a cyclic terpenoid skeleton. Described,
It is shown that the transmittance of light in the above wavelength range can be sufficiently increased.

[0006]

However, the above-mentioned compounds are hydrophobic, so that sufficient solubility cannot be obtained by conventional development using an aqueous alkali solution, and it is difficult to form a good fine pattern. Therefore, as disclosed in the above publication, this problem is solved by mixing an atomic group containing a water-soluble group by a method such as copolymerization, but this method expresses dry etching resistance. Since the atomic group content is reduced, etching resistance is reduced. Moreover, such compounds generally have strong hydrophobicity, which leads to a decrease in adhesion between the semiconductor substrate and the resin. From the above, there is a problem that it is impossible to achieve both the light transmittance and the dry etching resistance with the above-described conventional technology.

The present invention has been made to solve the above problems, and has as its object to obtain a transparent compound and a transparent resin having high transparency in a short wavelength region such as an ArF excimer laser. . Still another object of the present invention is to provide a photosensitive resin composition having high sensitivity to light having the above-mentioned wavelength and sufficient dry etching resistance, and a method for manufacturing a highly integrated semiconductor device capable of fine processing.

[0008]

Means for Solving the Problems A first transparent compound according to the present invention comprises a compound represented by the following general formula (1) or (2):

[0009]

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It is obtained by reacting a carboxylic acid with a strong acid.

The first transparent resin according to the present invention is obtained by reacting the compound represented by the above general formula (1) or (2) with a carboxylic acid having a double bond in a strong acid. It contains a polymerizable compound.

The second transparent resin according to the present invention is the first transparent resin, wherein the compound represented by the general formula (1) or the general formula (2) is a compound selected from the group consisting of pinene, camphene, kalen, cedrene, and kebeben. belongs to.

[0013] A third transparent resin according to the present invention is the first or second transparent resin containing the first transparent compound.

The fourth transparent resin according to the present invention is the transparent resin according to any one of the first to third transparent resins, which is represented by the following general formula (3), (4), (5) or (6):

[0015]

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[0016]

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It contains an atomic group represented by the formula:

The fifth transparent resin according to the present invention is the fourth transparent resin according to the above formula (3), (4),
The atomic group represented by (5) or (6) is decomposed by an acid.

The first photosensitive resin composition according to the present invention comprises:
The transparent resin according to any one of the first to fifth aspects and a compound that generates an acid upon irradiation with light or radiation.

A first method for manufacturing a semiconductor device according to the present invention comprises the steps of providing a film of the first photosensitive resin composition on a semiconductor substrate, and pattern-exposing the photosensitive resin composition film with a short-wavelength laser. And a step of developing the exposed photosensitive resin composition film.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent compound of the present invention is an ester compound obtained by reacting a compound represented by the above general formula (1) or (2) with a carboxylic acid in a strong acid, It shows high transparency in a short wavelength region such as an ArF excimer laser.

The transparent resin of the present invention has the general formula (1)
Alternatively, it contains a polymerizable ester compound obtained by reacting a compound represented by the general formula (2) with a carboxylic acid having a double bond in a strong acid. The polymerizable ester compound obtained here exhibits high transparency in a short wavelength region such as an ArF excimer laser. Further, since the ester compound has an ester bond having a tertiary carbon, it can be decomposed by an acid and the solubility of the exposed portion in an aqueous alkaline solution can be increased, thereby improving the resolution of a pattern.

Further, when the above-mentioned ester compound is bound to or added to a resin serving as a base material, when used as a photosensitive resin composition described below, etching resistance can be improved. Examples of the resin serving as a base include, but are not limited to, polyacrylic acid, polymethacrylic acid, polyhydroxyethylacrylic acid, polyhydroxyethylmethacrylic acid, polymaleic acid, and polyitaconic acid.

The compound represented by the above general formula (1) or (2) relating to the transparent compound or the transparent resin of the present invention may be a 1,3- or 1-position of a cyclohexane ring, a cycloheptane ring or a cyclooctane ring. , A compound having a carbon-carbon bond bridged at the 4-position and further having a double-bonding carbon-carbon bond. However, at least one of the carbon atoms forming the double bond carbon-carbon bond needs to be directly bonded to three carbon atoms,
It may be substituted with an alkyl group, a hydroxyl group, a carboxyl group, a sulfoxyl group, or the like.

[0025]

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Pinene, camphene, karen,
Examples include, but are not limited to, Sedren, Kubeben, and the like. In addition, when the transparent resin of the present invention is used as a photosensitive resin composition as described below, when pinene, camphene, karen, cedrene, and kebeben are used, they are easily removed by decomposition with an acid because they have volatility, and high resolution is obtained. Obtainable.

Specific examples of the carboxylic acid which can be reacted with the compound represented by the above general formula (1) or (2) relating to the transparent compound or the transparent resin of the present invention include acrylic acid and methacrylic acid. Examples include, but are not limited to, acids, maleic acid, fumaric acid, itaconic acid, cyclohexane 1,2-dicarboxylic acid monomethacryloyloxyethyl ester, cyclohexane 1,2-dicarboxylic acid monoacryloyloxyethyl ester, and the like. It is necessary to use a carboxylic acid having a double bond as described above for the transparent resin of the present invention.

As the strong acid relating to the transparent compound or the transparent resin of the present invention, sulfuric acid, benzenesulfonic acid, p-
Examples include, but are not limited to, toluenesulfonic acid.

It is preferable that the transparent resin of the present invention further contains the above-mentioned transparent compound, because the dry etching resistance is further improved.

Further, when the transparent resin of the present invention contains the atomic group represented by the above general formula (3), (4), (5) or (6), the above general formula (3) (4),
The atomic group represented by (5) or (6) has a high hydrophilicity due to having a polar group in its molecular skeleton, and can secure sufficient adhesion to a semiconductor substrate or the like. When used as a photosensitive resin, peeling and falling of the pattern during development can be reduced. In addition, since the above atomic groups are different from aromatic compounds, ArF
Light absorption in a short wavelength region of an excimer laser or the like can be kept small.
The light absorption of the rF excimer laser light can be suppressed low. Further, when the atomic group represented by the above general formula (3), (4), (5) or (6) is decomposable by an acid, when used as a photosensitive resin composition as described below, Higher resolution of the pattern can be obtained.

That is, the transparent resin of the present invention is obtained, for example, by adding an atomic group represented by the general formula (3), (4), (5) or (6) to a resin containing the above-mentioned polymerizable ester compound. It can be obtained by bonding or adding a compound having the above atomic group. The compound may be an alkyl carboxylic acid having 3 to 15 carbon atoms, or 3 to 15 carbon atoms.
But not limited thereto.

The transparent resin of the present invention may be obtained by copolymerizing the polymerizable ester compound with another monomer. Other monomers such as acrylic acid,
Methacrylic acid, maleic acid, fumaric acid, itaconic acid, cyclohexane 1,2-dicarboxylic acid monomethacryloyloxyethyl ester, cyclohexane 1,2-dicarboxylic acid monoacryloyloxyethyl ester, ethylene glycol monomethacrylic acid ester, ethylene glycol mono Acrylic acid ester, vinyl alcohol, vinyl acetate, methyl methacrylate, methyl acrylate, tert-butyl methacrylate, tert-butyl acrylate, 1-ethoxyethyl-1-methacrylate,
1-ethoxyethyl-1-acrylate, 1-isopropoxyethyl-1-methacrylate, 1-
Isopropoxyethyl-1-acrylate, 1-
Examples include, but are not limited to, tert-butoxyethyl-1-methacrylate, 1-tert-butoxyethyl-1-acrylate, tetrahydropyranyl methacrylate, and tetrahydropyranyl acrylate. The content ratio of the ester compound to other monomers is 99% to 30% (mol%, the same applies hereinafter), preferably 95 to 50%, and the other monomer is 1%.
% To 70%, preferably 5 to 50%. When the content of the above compound is less than 30%, it becomes difficult to obtain sufficient etching resistance. 99% of the above compound
If it is larger, it is difficult to form a film.

Further, the transparent resin of the present invention is obtained by polymerizing the above-mentioned polymerizable ester compound and further bonding an atomic group decomposable with an acid to the resin, or as a compound having this atomic group. It may be added. Examples of the atomic group decomposable by an acid include a tert-butyl group, a tert-amyl group, a 1-ethoxyethyl group, a 1-propyloxyethyl group, a 1-tert-butoxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, Examples include, but are not limited to, 2-methyl-2 adamantyl group, 1-methyl-4 tetrahydropyran-3-noyl group, 1-methyl-4-pentanoyl group, and the like.

The transparent resin used in the photosensitive resin composition of the present invention can be obtained by adding a resin obtained by polymerizing the above polymerizable ester compound to the resin represented by the general formula (3), (4), (5) or (5). It can be obtained by bonding the atomic group represented by 6) or the atomic group decomposable by the acid to the resin, or adding a compound containing the atomic group.

The photosensitive resin composition of the present invention contains the above transparent resin and a compound capable of generating an acid upon irradiation with light or radiation.

Compounds that generate an acid upon irradiation with light or radiation according to the photosensitive resin composition of the present invention include:
Triphenylsulfonium hexafluoroantimonate, triphenylsulfonium triflate, triphenylsulfonium nanofrate, triphenylsulfonium tosylate, triphenylsulfonium methanesulfonate, triphenylsulfoniumethanesulfonate, triphenylsulfoniumpropanesulfonate,
Triphenylsulfonium butanesulfonate, dimethylphenylsulfonium hexafluoroantimonate,
Dimethylphenylsulfonium triflate, dimethylphenylsulfonium nanoflate, dimethylphenylsulfonium tosylate, dimethylphenylsulfonium methanesulfonate, dimethylphenylsulfonium ethanesulfonate, dimethylphenylsulfonium propanesulfonate, dimethylphenylsulfonium butanesulfonate, 4-tertbutylfunyldiphenylhexyl Fluoroantimonate, 4-tert-butylfunyldiphenyl triflate, 4-tert-butylfunyldiphenyl nanoflate, 4-tertbutylfunyldiphenyltosylate, 4-tertbutylfunyldiphenylmethanesulfonate, 4-tertbutylfunyldiphenyl Ethanesulfonate, 4-tertbutylphenyldiphenyl Bread sulfonate, 4-tert-butyl-off sulfonyl diphenyl butane sulfonate, tris (4
-Methylphenyl) sulfonium hexafluoroantimonate, tris (4-methylphenyl) sulfonium triflate, tris (4-methylphenyl) sulfonium nanofrate, tris (4-methylphenyl) sulfonium tosylate, tris (4-methylphenyl) Sulfonium methanesulfonate, tris (4-methylphenyl) sulfoniumethanesulfonate, tris (4-
Methylphenyl) sulfoniumpropanesulfonate,
Tris (4-methylphenyl) sulfonium butanesulfonate, tris (4-methoxyphenyl) sulfonium tohexafluoroantimonate, tris (4-methoxyphenyl) sulfonium triflate, tris (4-
(Methoxyphenyl) sulfonium nanofreate, tris (4-methoxyphenyl) sulfonium tosylate, tris (4-methoxyphenyl) sulfonium methanesulfonate, tris (4-methoxyphenyl) sulfoniumethaneethanesulfonate, tris (4-methoxyphenyl) sulfoniumpropanesulfonate , Tris (4-
Methoxyphenyl) sulfonium butanesulfonate,
Diphenyliodonium hexafluoroantimonate,
Diphenyliodonium triflate, diphenyliodonium nanofreite, diphenyliodonium tosylate, diphenyliodonium methanesulfonate, diphenyliodonniuetansulfonate, diphenyliodonium propane sulfonate, diphenyliodonium butane sulfonate, 4-methoxyphenylphenyliodonium hexafluoroantimonate, 4-methoxyphenylphenyliodonium triflate, 4-methoxyphenylphenyliodonium nanofrate, 4-methoxyphenylphenyliodonium tosylate, 4-
Methoxyphenylphenyliodonium methanesulfonate, 4-methoxyphenylphenyliodoniuuetanesulfonate, 4-methoxyphenylphenyliodonium propanesulfonate, 4-methoxyphenylphenyliodoniubutanesulfonate, 4,4'-ditert
Butyldiphenyliodonium hexafluoroantimonate, 4,4'-ditertbutyldiphenyliodonium triflate, 4,4'-ditertbutyldiphenyliodonium nanofrate, 4,4'-ditert
Butyldiphenyliodonium tosylate, 4, 4'-
Ditertbutyldiphenyliodonium methanesulfonate, 4,4'-ditertbutyldiphenyliodoniumethanesulfonate, 4,4'-ditertbutyldiphenyliodoniumpropanesulfonate, 4,
4'-ditertbutyldiphenyliodonium butanesulfonate, 4,4'-dimethyldiphenyliodonium hexafluoroantimonate, 4,4'-dimethyldiphenyliodonium triflate, 4,4'-dimethyldiphenyliodonium nanofrate, 4,4 ' ―
Dimethyldiphenyliodonium tosylate, 4, 4 '
-Dimethyldiphenyliodonium methanesulfonate, 4,4'-dimethyldiphenyliodoniumethanesulfonate, 4,4'-dimethyldiphenyliodoniumpropanesulfonate, 4,4'-dimethyldiphenyliodoniumbutanesulfonate, 3,3'-dinitrodiphenyliodonium hexafluoro Antimonate, 3,3'-dinitrodiphenyliodonium triflate, 3,3'-dinitrodiphenyliodonium tosylate, 3,3'-dinitrodiphenyliodonium tosylate, 3,3'-dinitrodiphenyliodonium methanesulfonate, 3,3 '-Dinitrodiphenyliodonium ethanesulfonate, 3,3'-dinitrodiphenyliodoniumpropanesulfonate, 3,
3'-dinitrodiphenyliodonium butanesulfonate, naphthylcarbonylmethyltetrahydrothiophenylhexafluoroantimonate, naphthylcarbonylmethyltetrahydrothiophenyltriflate, naphthylcarbonylmethyltetrahydrothiophenyl nanoflate, naphthylcarbonylmethyltetrahydrothiophenyltosylate, naphthylcarbonylmethyl Tetrahydrothiophenylmethanesulfonate, naphthylcarbonylmethyltetrahydrothiophenylethanesulfonate, naphthylcarbonylmethyltetrahydrothiophenylpropanesulfonate, naphthylcarbonylmethyltetrahydrothiophenylbutanesulfonate, dimethylhydroxynaphthylhexafluoroantimonate, dimethylhydroxynaphthy Rutrifreite, dimethylhydroxynaphthyl nanofrate, dimethylhydroxynaphthyltosylate, dimethylhydroxynaphthylmethanesulfonate, dimethylhydroxynaphthylethanesulfonate, dimethylhydroxynaphthylpropanesulfonate, dimethylhydroxynaphthylbutanesulfonate,
Hydroxysuccinimide trifluoromethanesulfonate, hydroxysuccinimide nanofluorobutanesulfonate, hydroxysuccinimide trimethanesulfonate, hydroxysuccinimide triethanesulfonate, hydroxysuccinimide Tripropanesulfonic acid ester, hydroxysuccinimide tributanesulfonic acid ester,
Hydroxysuccinimide toluenesulfonic acid ester, hydroxycyclohexanedicarboxylic acid imide trifluoromethanesulfonic acid ester, hydroxycyclohexanedicarboxylic acid imide nanofluorobutanesulfonic acid ester, hydroxycyclohexanedicarboxylic acid imide trimethanesulfonic acid ester, hydroxycyclohexane Triethanesulfonic acid ester of dicarboxylic acid imide, tripropanesulfonic acid ester of hydroxycyclohexanedicarboxylic acid imide, tributanesulfonic acid ester of hydroxycyclohexanedicarboxylic acid imide, toluenesulfonic acid ester of hydroxycyclohexanedicarboxylic acid imide, hydroxynorbornene dicarboxylic acid imide Trifluoromethanesulfonic acid ester, hydr Nanofluorobutanesulfonic acid ester of xinorbornene dicarboxylic acid imide, trimethanesulfonic acid ester of hydroxynorbornene dicarboxylic acid imide, triethanesulfonic acid ester of hydroxynorbornene dicarboxylic acid imide, tripropanesulfonic acid ester of hydroxynorbornene dicarboxylic acid imide, hydroxy Examples include tributanesulfonic acid ester of norbornene dicarboxylic acid imide and toluenesulfonic acid ester of hydroxynorbornene dicarboxylic acid imide.

The content ratio of the transparent resin according to the photosensitive resin composition of the present invention to the compound capable of generating an acid upon irradiation with light or radiation is 90.0 to 99.9% by weight, preferably 95% by weight. 0.0 to 99.5% by weight of a compound capable of generating an acid upon irradiation with light or radiation.
0% by weight, preferably in the range of 0.5 to 5.0% by weight is suitable. When the amount of the transparent resin exceeds 99.9% by weight, patterning tends to be difficult. When the amount of the transparent resin is less than 90.0% by weight, it becomes difficult to obtain uniform compatibility. Is more likely to occur. Compounds which generate an acid upon irradiation with light or radiation are 0.1%.
When the amount is less than 1% by weight, a good pattern cannot be formed, and when the amount exceeds 10% by weight, it becomes difficult to obtain uniform compatibility. Become.

According to the method of manufacturing a semiconductor device of the present invention, a film of the photosensitive resin composition is provided on a semiconductor substrate, and the film of the photosensitive resin composition is pattern-exposed to a short-wavelength laser such as ArF. Is a method of developing a film of the photosensitive resin composition of (1), and the photosensitive resin composition can secure dry etching resistance while suppressing light absorption of ArF excimer laser light or the like, thereby enabling fine processing. .

The photosensitive resin composition of the present invention is applied onto a substrate such as a silicon wafer, prebaked, and irradiated with light such as ArF excimer laser.
Heating at about 70 ° C. is performed for 30 seconds to 10 minutes, and then development is performed to form a pattern. An alkaline aqueous solution can be used as a resist developer. As the alkaline aqueous solution, for example, an aqueous solution of ammonia, triethylamine, dimethylaminomethanol, monoethanolamine, triethanolamine, tetraalkylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, choline, or a mixture of these aqueous solutions is used. Can be.

As a solvent used for applying the photosensitive resin composition of the present invention to a substrate, any solvent can be used as long as it can rapidly dissolve the components to be mixed and does not react with them. Cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl butyrate, 2 -Heptanone, diglyme, cyclohexanone, cyclopentanone, γ-butyrolactone, isoamyl acetate, chlorobenzene, dichlorobenzene and the like are common. Preferably, a solvent having a boiling point in the range of 100 to 220 ° C. is suitable. If the boiling point is lower than this, unevenness tends to occur when applied, and if the boiling point is higher than this, drying of the solvent is not easy.

[0041]

[Embodiment 1] A mixture of 150 g of β-pinene and 40 g of methacrylic acid was cooled with ice, 10 ml of concentrated sulfuric acid was slowly added thereto, and stirring was continued for 24 hours. A solution obtained by adding 300 ml of ether thereto was washed with an aqueous sodium hydrogen carbonate solution and water in that order. After the solvent was distilled off, 40 g of the desired polymerizable ester compound was obtained by distillation under reduced pressure. 10.7 g of the above ester compound, methacrylic acid 1.
1 g and 0.2 g of azobisisobutyronitrile were dissolved in 60 ml of dioxane, polymerized at 70 ° C. for 4 hours after deaeration in vacuo. The reaction solution was poured into 1000 ml of hexane to recover a polymer. The polymer was dissolved in 50 ml of tetrahydrofuran, filtered, and then put again in 1000 ml of hexane to form a polymer, thereby obtaining 6.5 g of a transparent resin according to the example of the present invention.

Embodiment 2 FIG. Polymer 4 obtained in Example 1
g and triphenylsulfonium triflate 0.08 g
Was dissolved in 22 g of diethylene glycol dimethyl ether, and the photosensitive resin composition of Example 1 was dissolved in 22 g of diethylene glycol dimethyl ether.
The solution was filtered through a 2 μm membrane filter to prepare a pattern forming material solution. This solution was applied to a silicon wafer having enhanced adhesion with hexamethyldisilazane,
A μm-thick pattern forming material film was obtained. 10mJ for this film
/ Cm ² of ArF excimer laser,
Heating was performed on a hot plate at 90 ° C. for 90 seconds. At this time, the transparent resin portion relating to the photosensitive resin composition of the present invention is decomposed by the acid generated by ArF excimer laser irradiation as shown in the following formula, and becomes soluble in an alkaline aqueous solution.

[0043]

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Thereafter, development was carried out with a 0.079% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds. As a result, a 0.16 μm line and space pattern was resolved with good shape. Table 1 compares the etching rate by CF ₄ gas plasma with the etching rate of a polyhydroxystyrene resin conventionally used as a base resin of a photosensitive resin composition as 1. From Table 1, it was found that the etching rate of the film of the photosensitive resin composition of the example of the present invention had the same etching resistance as that of the polyhydroxystyrene resin.

[0045]

[Table 1]

Embodiments 3 to 14 As shown in Tables 1 to 4, an ester compound obtained by reacting a compound represented by the general formula (1) or (2) with a carboxylic acid having a polymerizable double bond in a strong acid is used. A transparent resin contained in a part of the polymer and a compound which generates an acid upon irradiation with light or radiation are obtained in the same manner as in Example 2 to obtain a photosensitive resin composition of Example of the present invention, and a resist film And a pattern was formed in the same manner as in Example 2.

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

As a result, as shown in Tables 1 to 4, in each case, a good pattern was obtained by ArF excimer laser exposure, and it was shown that the film had the same dry etching resistance as polyhydroxystyrene resin.

In the above embodiment, the short wavelength light is A
An example using an rF excimer laser has been described.
The same effect can be obtained with light having a wavelength around 200 nm, such as the fifth harmonic of the G laser.

Embodiment 15 FIG. Pinene methacrylate and α-
44 parts by weight of a copolymer with methylene-γ-butyrolactone (molar composition ratio 50:50) and 1 part by weight of triphenylsulfonium triflate were dissolved in 365 parts by weight of cyclohexanone, and the solution was filtered through a 0.2 μm membrane filter. A pattern forming material solution was prepared. This solution was applied onto a silicon wafer having enhanced adhesion with hexamethyldisilazane to obtain a 0.5 μm thick pattern forming material film. After the film was irradiated with 8 mJ / cm ² of ArF excimer laser light, it was heated on a hot plate at 110 ° C. for 90 seconds. Thereafter, development was performed for 60 seconds with a 0.119% by weight aqueous solution of tetramethylammonium hydroxide. As a result, a 0.14 μm line and space pattern was resolved with good shape. Further, as a result of comparing the etching rate by CF ₄ gas plasma with that of the novolak resin, the etching rate of the film of the photosensitive resin composition was 1.09 times that of the novolak resin, and the dry etching resistance was improved with respect to PMMA resin and the like. It can be seen that the adhesion is improved and the resolution is improved.

Comparative Example 1 In Example 15, α-
When patterning was performed in the same manner as in Example 1 using methacrylic acid instead of methylene-γ-butyrolactone, the pattern of 0.18 μm or less was peeled off.

Embodiments 16 to 39. As shown in Tables 5 to 12, an ester compound obtained by reacting the compound represented by the above general formula (1) or (2) with a carboxylic acid having a double bond in a strong acid and the above general formula ( 3),
Example 15 was a resin containing the atomic group represented by (4), (5) or (6), and a compound (triphenylsulfonium triflate) which generates an acid upon irradiation with light.
A photosensitive resin composition was obtained in the same manner as described above, a resist film was formed, and a pattern was formed. Further, the dry etching resistance was examined in the same manner as in Example 15.

[0055]

[Table 5]

[0056]

[Table 6]

[0057]

[Table 7]

[0058]

[Table 8]

[0059]

[Table 9]

[0060]

[Table 10]

[0061]

[Table 11]

[0062]

[Table 12]

As a result, as shown in Tables 5 to 12, good patterns were obtained by ArF excimer laser exposure in all cases. In addition, as in Example 15, it is shown that the adhesion is improved and the resolution is improved.

[0064]

According to the first transparent compound of the present invention,
It is obtained by reacting the compound represented by the general formula (1) or (2) with a carboxylic acid in a strong acid, and has an effect of having transparency to short-wavelength light such as ArF. There is.

According to the first transparent resin of the present invention, the compound represented by the general formula (1) or (2) is
It contains a polymerizable compound obtained by reacting a carboxylic acid having a double bond with a strong acid, has transparency to short-wavelength light such as ArF, and can be used as a photosensitive resin. There is an effect that can be.

According to the second transparent resin of the present invention, in the first transparent resin, the compound represented by the general formula (1) or the general formula (2) is selected from the group consisting of pinene, camphene, kalen, cedrene and It is of Kubeben, and has an effect of improving resolution when used as a photosensitive resin.

According to the third transparent resin of the present invention, the first or second transparent resin contains the first transparent compound, and when used as a photosensitive resin, the resolution is improved. There is an effect of doing.

According to the fourth transparent resin of the present invention, in any one of the first to third transparent resins, the compound represented by the above general formula (3), (4), (5) or (6) It contains the atomic group shown, and when used as a photosensitive resin, it has the effect of improving resolution.

According to the fifth transparent resin of the present invention, in the above four transparent resins, the above general formulas (3), (4),
The atomic group represented by (5) or (6) is decomposed by an acid, and when used as a photosensitive resin, there is an effect that the resolution is improved.

According to the first photosensitive resin composition of the present invention, the first photosensitive resin composition contains any of the first to fifth transparent resins and a compound which generates an acid upon irradiation with light or radiation. , ArF, etc., have an effect of being excellent in transparency to short-wavelength light, high resolution and excellent etching resistance.

According to the first method for manufacturing a semiconductor device of the present invention, a step of providing a film of the first photosensitive resin composition on a semiconductor substrate, and applying a short-wavelength laser to the photosensitive resin composition film By performing the step of exposing and the step of developing the exposed photosensitive resin composition film, there is an effect that a highly integrated semiconductor device capable of forming a fine pattern can be obtained.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 35/02 C08L 35/02 C09D 133/04 C09D 133/04 135/02 135/02 G03F 7/004 503 G03F 7/004 503 7/038 505 7/038 505 7/039 501 7/039 501 H01L 21/027 H01L 21/30 502R

Claims (8)

[Claims] 1. A compound represented by the following general formula (1) or (2): A transparent compound obtained by reacting a carboxylic acid with a strong acid. 2. A transparent resin containing a polymerizable compound obtained by reacting a compound represented by the above general formula (1) or (2) with a carboxylic acid having a double bond in a strong acid. . 3. The transparent resin according to claim 2, wherein the compound represented by the general formula (1) or the general formula (2) is pinene, camphene, karen, cedrene, or kebeben. 4. The transparent resin according to claim 2, which contains the transparent compound according to claim 1. 5. The following general formula (3), (4), (5) or (6): Embedded image 3. An atomic group represented by the formula:
The transparent resin according to claim 4. 6. The transparent resin according to claim 5, wherein the atomic group represented by the general formula (3), (4), (5) or (6) is decomposed by an acid. 7. A photosensitive resin composition comprising the transparent resin according to claim 2 and a compound capable of generating an acid upon irradiation with light or radiation. 8. A step of providing a film of the photosensitive resin composition according to claim 7 on a semiconductor substrate, a step of patternwise exposing the photosensitive resin composition film to a short-wavelength laser, and a step of exposing the photosensitive resin composition to light. A method for manufacturing a semiconductor device, comprising a step of developing a material film.