JPH10140018A - Transparent resin, photosensitive resin composition using the same and production of semiconductor apparatus using the same composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin useful for a semiconductor apparatus, showing transparency in a short wavelength region of ArF excimer laser, comprising a specific first atomic group to a third atomic group. SOLUTION: This resin comprises a first atomic group of formula I [R1 is C=O or SO2 ; R2 is COOR3 , COR3 , NO2 , NO, etc., (R3 is 1-10C hydrocarbon or H)], a second atomic group in which one or two carbon-carbon bonds in a cyclohexane ring are double bonds and which contains one substituting group of -C=O, -SO2 or =O or a third atomic group in which one to four carbon- carbon bonds in a decalin ring are double bond and which contains one substituent group of -C=O, -SO2 or =O and preferably further a forth atomic group of formula II (R7 and R8 are each a 1-3C hydrocarbon and may form a ring structure; r9 is ethenyl, ethynyl or methyl).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transparent resin having excellent transparency to short-wavelength light such as ArF laser and to lithography using short-wavelength light such as ArF laser as an exposure energy source. The present invention relates to a photosensitive resin composition 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 an ArF excimer laser or a YAG laser having a short wavelength, so that a pattern having a good shape cannot be formed. Was.

As a method for solving this problem, Japanese Patent Laid-Open No.
JP-A-181687 describes a resist material containing a naphthalene compound. That is, the naphthalene compound exhibits dry etching resistance and, at the same time, the absorption near 200 nm, which is peculiar to the compound having a benzene skeleton, is shifted to the longer wavelength side.
The absorbance near the wavelength of the fifth harmonic of the AG laser can be reduced.

Further, JP-A-4-39665, JP-A-8-12626 and JP-A-8-82925 describe aliphatic compounds, which can sufficiently increase the transmittance of light in the above-mentioned wavelength region. It is shown that it can be higher.

[0007]

However, although the above-mentioned naphthalene compound has an etching resistance,
Since the transmittance of light in the above-mentioned wavelength region is not sufficient, deterioration of the shape of the formed pattern is inevitable. In addition, the above-mentioned aliphatic compounds are hydrophobic, and sufficient solubility cannot be obtained by conventional development using an aqueous alkali solution. Therefore, as disclosed in the above publication, this problem is solved by mixing an atomic group containing a group exhibiting water solubility by a method such as copolymerization. However, in this method, dry etching is exhibited. Since the atomic group content is reduced, etching resistance is reduced. 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.

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

[0009]

Means for Solving the Problems A first transparent resin according to the present invention comprises a first atomic group represented by the following general formula (1):

[0010]

Embedded image

One or two carbons in the cyclohexane ring
A carbon bond is a double bond, a second atomic group having one substituent of —C ＝ O, —SO ₂ or ＯO, or one to four carbon-carbon bonds in a decalin ring are double bonds; And a third atomic group having one substituent of —C ＝ O, —SO ₂ or ＯO.

The second transparent resin according to the present invention is one wherein the first transparent resin has a fourth atomic group which is decomposable by an acid.

In the third transparent resin according to the present invention, the fourth atomic group which is decomposable by an acid in the second transparent resin is represented by the following general formula (2):

[0014]

Embedded image

The atomic group represented by

The first photosensitive resin composition according to the present invention comprises:
A first atomic group represented by the following general formula (1),

[0017]

Embedded image

One or two carbons in the cyclohexane ring
A carbon bond is a double bond, a second atomic group having one substituent of —C ＝ O, —SO ₂ or ＯO, or one to four carbon-carbon bonds in a decalin ring are double bonds; A resin having a third atomic group having one substituent of —C ＝ O, —SO _2, or ＯO, and a fourth atomic group that is decomposable by an acid; And a compound to be generated.

The second photosensitive resin composition according to the present invention comprises:
In the first photosensitive resin composition, the fourth atomic group that is decomposable by an acid is represented by the following general formula (2)

[0020]

Embedded image

The atomic group represented by

In the method of manufacturing a semiconductor device according to the present invention, there is provided a step of providing a film of the first or second photosensitive resin composition on a semiconductor substrate; And a step of developing the exposed photosensitive resin composition film.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent resin of the present invention comprises
It has an atomic group, a second atomic group, or a third atomic group.

The first atomic group represented by the general formula (1) is a compound having two substituents at the 1,3-positions of the benzene ring. Examples of the substituent include an alkoxycarbonyl group, a carboxyl group, an alkylcarbonyl group, It is an atomic group such as a nitro group, a nitroso group, a cyano group, a trihalomethyl group, a hydroxyl group, a dialkylsulfonium group or a trialkylamino group, or a halogen atom such as chlorine or bromine. These two substituents may be the same or different.
The first atomic group can reduce light absorption near a short wavelength such as an ArF excimer laser due to the effect of a substituent. Therefore, when the first atomic group represented by the general formula (1) is present in the molecule, the absorption of ArF excimer laser light can be suppressed.

In the second atomic group, one or two carbon-carbon bonds in the cyclohexane ring are double bonds, and -C =
It has one substituent of O, —SO ₂ or ＯO, and is specifically represented by the following formula. In the following formula, R ₁₀ is -C = O,-
SO ₂ or ＯO.

[0026]

Embedded image

This atomic group is used in the same manner as the second atomic group even if it is further substituted with a substituent such as a hydroxyl group, a carboxyl group or an alkyl group.

In the third atomic group, 1 to 4 carbon-carbon bonds in the decalin ring are double bonds, and —C ＝ O, —
It has one substituent of SO ₂ or ＯO, and is specifically represented by the following formula. In the following formula, R ₁₀ is —C ＝ O, —SO ₂
Or = O.

[0029]

Embedded image

Note that this atomic group is used in the same manner as the third atomic group even if it is further substituted with a substituent such as a hydroxyl group, a carboxyl group, or an alkyl group.

Since the second or third atomic group is different from an aromatic compound, the second or third atomic group has a small light absorption near the ArF excimer laser wavelength. Therefore, when the second atomic group or the third atomic group is present in the molecule, light absorption of ArF excimer laser light can be suppressed.

The transparent resin of the present invention can be obtained by bonding the first, second or third atomic group to a resin serving as a base. 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 transparent resin of the present invention comprises the first atomic group,
It has a second or third atomic group and a fourth atomic group that is decomposable by an acid. By having the above-mentioned fourth atomic group, it is suitably used for a photosensitive resin composition.

The fourth atomic group which is decomposable by an acid includes, for example, a tert-butyl group, a tert-amyl group,
1-ethoxyethyl group, 1-propyloxyethyl group,
1-tert-butoxyethyl group, tetrahydropyranyl group, 2-methyl-2-adamantyl group, 1-methyl-4
-Tetrahydropyra-3-noyl group, 1-methyl-4-
Examples include, but are not limited to, pentanoyl groups.

When the fourth atomic group is represented by the above general formula (2), the composition has an unsaturated bond, thereby improving the etching resistance of the composition. As the atomic group represented by the general formula (2), specifically, a double bond or a 3
It is a compound having an unsaturated bond of a heavy bond.

[0036]

Embedded image

That is, a 2-methyl-3-butenyl group, 2-
Examples include, but are not limited to, a methyl-3-butynyl group, a 1-ethynyl-1-cyclohexyl group, a 1-methyl-2-cyclohex-1-ynyl group, and the like.

The above transparent resin is suitably used for a photosensitive resin composition as described below. That is, the first
Since the atomic group has a benzene skeleton, etching resistance can be improved, and light absorption near a short wavelength such as an ArF excimer laser can be reduced by the effect of the substituent. Therefore, when the first atomic group represented by the general formula (1) is present in a molecule,
Etching resistance can be ensured while keeping the absorption of ArF excimer laser light low. The second or third atomic group can improve etching resistance by having at least one or more unsaturated bonds in a cyclohexane ring or a decalin ring. Further, since the second or third atomic group is different from an aromatic compound,
Light absorption around excimer laser wavelength is small. Therefore, when the second group or the third group is present in the molecule, Ar
The etching resistance can be ensured while the light absorption of the F excimer laser light is kept low. When the fourth atomic group is present in the molecule, the molecular structure is changed by the acid and the solubility in an alkali developing solution is changed.

The transparent resin used in the photosensitive resin composition of the present invention can be obtained by bonding a first, second or third atomic group and an atomic group decomposable by an acid to a resin serving as a base. Obtainable. Examples of the resin serving as a matrix include polyacrylic acid, polymethacrylic acid, polyhydroxyethylacrylic acid, polyhydroxyethylmethacrylic acid, polymaleic acid, and polyitaconic acid. Examples of the compound include, but are not limited to, alkyl carboxylic acids having 3 to 15 carbon atoms and alkyl dicarboxylic acids having 3 to 15 carbon atoms.

The photosensitive resin composition of the present invention contains the above transparent resin and a compound capable of generating an acid by light.

Compounds that generate an acid upon irradiation with light include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium triflate,
Triphenylsulfonium tosylate, triphenylsulfonium methanesulfonate, 4-tertbutylphenyldiphenylhexafluoroantimonate, 4-te
rt butyl phenyl diphenyl triflate, 4-ter
t-butyl phenyl diphenyl tosylate, 4-tert-butyl phenyl diphenyl methanesulfonate, tris (4
-Methylphenyl) sulfonium hexafluoroantimonate, tris (4-methylphenyl) sulfonium triflate, tris (4-methylphenyl) sulfonium tosylate, tris (4-methylphenyl) sulfonium methanesulfonate, tris (4-methoxyphenyl) Sulfonium tohexafluoroantimonate, tris (4-methoxyphenyl) sulfonium triflate, tris (4-methoxyphenyl) sulfonium tosylate, tris (4-methoxyphenyl) sulfonium methanesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium triflate Freight, diphenyliodonium tosylate, diphenyliodonium methanesulfonate, 4,4'-ditert
Butyldiphenyliodonium hexafluoroantimonate, 4,4′-ditertbutyldiphenyliodonium triflate, 4,4′-ditertbutyldiphenyliodonium tosylate, 4,4′-ditertbutyldiphenyliodonium methanesulfonate, 4,
4'-dimethyldiphenyliodonium hexafluoroantimonate, 4,4'-dimethyldiphenyliodonium triflate, 4,4'-dimethyldiphenyliodonium tosylate, 4,4'-dimethyldiphenyliodonium methanesulfonate, 3,3'-dinitro Diphenyliodonium hexafluoroantimonate,
3,3'-dinitrodiphenyliodonium triflate, 3,3'-dinitrodiphenyliodonium tosylate, 3,3'-dinitrodiphenyliodonium methanesulfonate, naphthylcarbonylmethyltetrahydrothiophenylhexafluoroantimonate, naphthylcarbonylmethyltetrahydrothiophenyl Triflate, naphthylcarbonylmethyltetrahydrothiophenyltosylate, naphthylcarbonylmethyltetrahydrothiophenylmethanesulfonate, dimethylhydroxynaphthylhexafluoroantimonate, dimethylhydroxynaphthyltriflate, dimethylhydroxynaphthyltosylate, dimethylhydroxynaphthylmethanesulfonate, hydroxysuccinic acid Trifluoromethanesulfonic acid ester of imide Hydroxysuccinimide trimethanesulfonic acid ester, hydroxysuccinimide toluenesulfonic acid ester, hydroxycyclohexanedicarboxylic acid imide trifluoromethanesulfonic acid ester, hydroxycyclohexanedicarboxylic acid imide trimethanesulfonic acid ester, hydroxycyclohexanedicarboxylic acid Toluenesulfonic acid ester of imide, trifluoromethanesulfonic acid ester of hydroxynorbornenedicarboxylic acid imide, trimethanesulfonic acid ester of hydroxynorbornenedicarboxylic acid imide, toluenesulfonic acid ester of hydroxynorbornenedicarboxylic acid imide and the like can be mentioned.

The content of the transparent resin used in the present invention and the compound capable of generating an acid upon irradiation with light is from 90.0 to 99.9% (% by weight, the same applies hereinafter), preferably 95.0%.
The suitable range is 0 to 99.5%, and the range of 0.1 to 10.0% (wt%, the same applies hereinafter), preferably 0.5 to 5.0%, of the compound which generates an acid upon irradiation with light. 9 resin
If it exceeds 9.9%, patterning tends to be difficult to perform, and if it is less than 90.0%, it becomes difficult to obtain uniform compatibility, so that defects in the pattern to be formed tend to occur. If the amount of the compound that generates an acid upon irradiation with light is less than 0.1%, a good pattern cannot be formed, and if it exceeds 10%, it becomes difficult to obtain uniform compatibility. A defect of a pattern to be formed easily occurs.

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. This is a method of developing the photosensitive resin composition film later. Since the etching resistance can be secured while the light absorption of the ArF excimer laser light is kept low, fine processing can be performed.

The photosensitive resin composition of the present invention is applied on a substrate such as a silicon wafer, prebaked, and
After irradiation with short wavelength light such as an excimer laser, heating at about 80 to 170 ° 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 the solvent used in the present invention, any solvent can be used as long as it can rapidly dissolve the components to be mixed and does not react with them. Examples thereof include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and the like.
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,
Commonly used are cyclopentanone, γ-butyrolactone, isoamyl acetate, chlorobenzene, dichlorobenzene and the like. 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.

[0046]

【Example】

Embodiment 1 FIG. 17 parts by weight of an esterified product of m-nitrobenzoic acid and 2-hydroxyethyl methacrylate, a copolymer of methacrylic acid and tert-butyl methacrylate (molar composition ratio 20:30:50), and 1 part by weight of triphenylsulfonium triflate It was dissolved in 82 parts by weight of cyclohexanone and filtered through a 0.2 μm membrane filter to prepare a pattern forming material solution. 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 irradiating this film with an ArF excimer laser of 10 mJ / cm ^2, the film was heated on a hot plate at 100 ° C. for 90 seconds. Thereafter, development was carried out with a 0.079% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds. As a result, a 0.18 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, it was found that the etching rate of the film of the photosensitive resin composition was 1.2 times that of the novolak resin, and the etching resistance was almost the same. Was.

Comparative Example 1 M- of the resin used in Example 1
Using an esterified product of p-nitrobenzoic acid and 2-hydroxyethyl methacrylate instead of an esterified product of nitrobenzoic acid and 2-hydroxyethyl methacrylate, or an ester of o-nitrobenzoic acid and 2-hydroxyethyl methacrylate The patterning was performed in the same manner as in Example 1 except that the compound was used. In each case, the resolution was limited to 0.7 μm.

Embodiments 2 to 5 As shown in Table 1, in the same manner as in Example 1 except that a photosensitive resin composition containing a resin having an atomic group represented by the general formula (1) and a compound which generates an acid upon irradiation with light was used. Then, a resist film was prepared and a pattern was formed.

[0049]

[Table 1]

As a result, as shown in Table 1, in each case, a good pattern was obtained by ArF excimer laser exposure, and good etching resistance was exhibited. In addition, the etching rate was shown as 1 in the case of novolak resin.

Embodiments 6 to 8 As shown in Table 2, adjustment was performed in the same manner as in Example 1 except that a photosensitive resin composition containing a resin having a second or third atomic group and a compound that generates an acid upon irradiation with light was used. Thus, a resist film was formed and a pattern was formed.

[0052]

[Table 2]

As a result, as shown in Table 2, in each case, a good pattern was obtained by ArF excimer laser exposure, and good etching resistance was exhibited. In addition, the etching rate was shown as 1 in the case of novolak resin.

Embodiments 9 to 12 As shown in Table 3, the first
A resist film was prepared in the same manner as in Example 1 except that a photosensitive resin composition containing a resin having an atomic group or a second atomic group and a compound generating an acid upon irradiation with light was used. Pattern formation was performed.

[0055]

[Table 3]

As a result, as shown in Table 3, in each case, a good pattern was obtained by ArF excimer laser exposure, and good etching resistance was exhibited. In addition, the etching rate was shown as 1 in the case of novolak 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.

[0058]

According to the first transparent resin of the present invention, the first atomic group represented by the above general formula (1) and one or two carbon-carbon bonds in the cyclohexane ring are double bonds. ,
—C ＝ O, —SO _2, or a second atomic group having one substituent of ＝ O, or 1 to 4 carbon atoms in a decalin ring—
The carbon bond is a double bond, and has a third atomic group having one substituent of —C ＝ O, —SO ₂ or ＯO, and is transparent to short-wavelength light such as ArF. This has the effect of having

According to the second transparent resin of the present invention, the first transparent resin has a fourth atomic group which is decomposable by an acid, and is used in a photosensitive resin composition. There is.

According to the third transparent resin of the present invention, the fourth atomic group which is decomposable by acid in the second transparent resin is an atomic group represented by the following general formula (2), There is an effect that resistance is improved.

According to the first photosensitive resin composition of the present invention, the first atomic group represented by the above general formula (1) and one or two carbon-carbon bonds in the cyclohexane ring are double bonds. , -C = O, -SO ₂ or a second atomic group having one substituent of -O, or 1 to 4 carbon-carbon bonds in the decalin ring are double bonds, -C = O, ―SO ₂
Or a resin having a third atomic group having one substituent of ＯO and a fourth atomic group that is decomposable by an acid, and a compound that generates an acid by irradiation with light;
There is an effect that the transmittance of short wavelength light such as rF is excellent and the etching resistance is excellent.

According to the second photosensitive resin composition of the present invention, in the first photosensitive resin composition, the fourth atomic group which is decomposable by an acid is represented by the general formula (2). In addition, there is an effect that the transmittance of light having a short wavelength such as ArF is excellent and the etching resistance is also excellent.

The method of manufacturing a semiconductor device according to the present invention comprises the steps of providing a film of the first or second photosensitive resin composition on a semiconductor substrate, and pattern-exposing the photosensitive resin composition film with a short-wavelength laser. By performing the step of performing 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.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Ikuhiro Yoshida 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Mitsui Electric Co., Ltd. (72) Inventor Hiroshi Adachi 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Electric Corporation

Claims (6)

[Claims] 1. A first atomic group represented by the following general formula (1): When one or two carbon-carbon bonds in the cyclohexane ring are 2
A heavy bond, one of —C ＝ O, —SO ₂ or ＯO
The second atom group having a substituent or 1 to 4 carbon-carbon bonds in the decalin ring is 2
A heavy bond, one of —C ＝ O, —SO ₂ or ＯO
A transparent resin comprising a third atomic group having a substituent. 2. The transparent resin according to claim 1, further comprising a fourth atomic group decomposable by an acid. 3. The fourth atomic group decomposable by an acid is represented by the following general formula (2): The transparent resin according to claim 2, wherein the transparent resin is an atomic group represented by the formula: 4. A first atomic group represented by the following general formula (1): When one or two carbon-carbon bonds in the cyclohexane ring are 2
A heavy bond, one of —C ＝ O, —SO ₂ or ＯO
The second atom group having a substituent or 1 to 4 carbon-carbon bonds in the decalin ring is 2
A heavy bond, one of —C ＝ O, —SO ₂ or ＯO
A photosensitive resin composition comprising a resin having a third atomic group having a substituent and a fourth atomic group that is decomposable by an acid, and a compound that generates an acid when irradiated with light. 5. The fourth atomic group decomposable by an acid is represented by the following general formula (2): The photosensitive resin composition according to claim 4, wherein the photosensitive resin composition is an atomic group represented by the formula: 6. The semiconductor device according to claim 4, wherein the semiconductor substrate is formed on a semiconductor substrate.
The step of providing a film of the photosensitive resin composition according to the above, the step of pattern exposure of the photosensitive resin composition film with a short-wavelength laser and the step of developing the exposed photosensitive resin composition film Production method.