JPH01217453A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To form a resist pattern with high accuracy by composing the title composition of a specified copolymer of a compd. contg. a norbornene skeleton and a specified maleic acid derivative, and a photosensitive agent. CONSTITUTION:The photosensitive composition is formed by mixing a compd. selected from the group comprising a naphthoquinone-1,2-diazide sulfonate, an azido compd., a diazomeldrumic acid compd. and an orthonitrobenzyl compd. as the photosensitive agent with the copolymer of bicyclo[2.2.1]hepto-2,5-diene, the compd. contg. the norbornene skeleton shown by formulas I and II and the maleic acid derivative shown by formula III. In the formula, R1-R3 are each hydrogen atom or 1-5C alkyl group, R4 and R5 are each hydrogen atom or 1-5C alkyl group, X is -O-, -NH- or -NR6- group, R6 is alkyl or aryl group. Thus, the fine photoresist pattern with the high accuracy can be formed.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a photosensitive composition, specifically a deep ultraviolet ray photosensitive composition made of a copolymer of a compound containing an alkali-soluble norbornene skeleton and a maleic acid derivative. and photoresist compositions suitable for excimer laser lithography.

The photosensitive composition of the present invention has deep ultraviolet rays (wavelengths of 250 to 300).
nm) and the wavelength associated with the excimer laser source (249,
In addition to providing high resolution, high contrast and sensitivity in the exposure range of 308r+n+), it is also suitable for exposure in mid-UV (wavelengths 300-3500I11) and near-UV (wavelengths 350-450r+n+).

These compositions can be used in various applications ranging from the formation of ordinary wiring patterns to the formation of IC
In addition to being used in the production of integrated circuits such as and LSI, it can also be used in the production of shadow masks, printed wiring boards, PS flat plates, and photographic whiteboards, and is widely used in fields such as the electronics industry, photography industry, and printing industry. be done.

[Prior Art] Conventionally, photoresist compositions made by mixing an alkali-soluble resin and a photosensitizer have been prepared using alkali-soluble resins such as novolak resin, polyvinylphenol,
Photosensitizers using, for example, quinonediazide compounds and bisazide compounds are generally well known; examples of the novolak resins include phenol formaldehyde novolac resins and cresol formaldehyde novolac resins; examples of quinonediazide compounds include naphthoquinone-(
Ester compounds of 0-quinonediazide sulfonic acid such as 1,2)-diazide sulfonic acid ester, and aromatic bisazide compounds such as 3,3-diazide diphenyl sulfone are used as bisazide compounds.

In these photoresist compositions, the photosensitizer contained in the composition is denatured by light irradiation, which changes polarity or undergoes a chemical reaction, resulting in a large solubility in an alkaline aqueous solution between exposed and unexposed areas. This method takes advantage of the difference that occurs and forms a positive or negative pattern by washing out areas with high alkali solubility through subsequent alkali development, and is widely used in the production of integrated circuits and lithographic printing plates. [Problems to be Solved by the Invention] However, as the demand for higher resolution resists increases, photoresist compositions made from the above-mentioned novolac resins or polyvinylphenol are becoming increasingly difficult to solve. Transparency is low in the relatively short wavelength range necessary for work to improve imageability, that is, deep ultraviolet and excimer laser wavelengths, and as a result, lithography using these wavelength ranges as a light source has low sensitivity or a rectangular resist pattern. There were problems such as inability to resolve.

Therefore, an object of the present invention is to provide a highly sensitive photosensitive composition with excellent transparency in the deep ultraviolet and excimer laser wavelength regions.

[Means for Solving the Problems] In view of the above circumstances, the present inventors have made extensive studies, and as a result, the present inventors have developed a method using a copolymer of a compound containing a norbornene skeleton and a maleic acid derivative as a material. The present invention was completed by discovering that a composition containing a combination of a combination and a photosensitizer becomes a photosensitive composition that achieves the above object.

That is, the present invention provides bicyclo[2,2,1]hept-2,5-diene, a compound containing a norbornene skeleton represented by the following general formula (I) and - formula (II), and the following - formula (I [)]. The present invention relates to a composition in which a compound selected from naphthoquinone-1,2-diazide sulfonic acid ester, an azide compound, a diazomeldrum acid compound, and an ortho-nitrobenzyl compound is added as a photosensitizer to a copolymer with a maleic acid derivative as shown. It is something.

(R,, R2, R, in the formula -Hs represents an alkyl group having 1 to 5 carbon atoms, and may be the same or different from each other) 1'(5 (R,, R in the formula , represents -H or an alkyl group having 1 to 5 carbon atoms, and may be the same or different from each other) (X in the formula represents 10-, -NH-, or -NR6-, and R6 is The photosensitive composition of the present invention will be described in detail below.

The copolymer constituting the photosensitive composition of the present invention can be obtained by copolymerizing a compound containing a norbornene skeleton and a maleic acid derivative. Compounds containing such a norbornene skeleton include bicyclo[2,2,1]hept-2,
5-Diene, a compound represented by formula (I) and formula (n). Here, (I> and (II) in the formula R1~
In R9, hydrogen is a group selected from alkyl groups having 1 to 5 carbon atoms, and specific examples of such compounds include the following.

The maleic acid derivative, which is also used as a raw material for copolymer synthesis, is a compound represented by the formula (I), (I [> where X is 10-, -NH- is -NR, - Here, R6 is an alkyl group or an aryl group,
As such compounds, the compounds specifically shown in the following are desirable.

Next, a copolymer of a compound containing a norbornene skeleton and a maleic acid derivative used in the photosensitive composition of the present invention will be explained by giving specific examples.

In the photosensitive composition of the present invention, bicyclo[2,2,1]
A copolymer using hepto-2,5-diene as a raw material is, for example, a copolymer having a structural unit represented by: bicyclo[2,2,1]hept-2,5-diene and a maleic acid derivative. It can be obtained by radical copolymerization of

- The copolymer using the formula (I) as a raw material is, for example, a copolymer having a structural unit represented by (3) and (4).
The copolymer represented by (5) can be obtained by a radical copolymer of 5-vinylbicyclo[2,2,2-heptot-2-ene and a maleic acid derivative. It can be obtained by thermal copolymerization of vinylbicyclo[2,2,heptoheptyl-2-ene and a maleic acid derivative.

When the general formula (II) is used as a raw material, the copolymer is, for example, a copolymer having a structural unit represented by:

The copolymers represented by (6) and (7) are obtained by radical copolymerization of 5-methylenebicyclo[2,2,1]hept-2-ene and a maleic acid derivative, and (
The copolymer shown in 8) is 5-ethylidene bicyclo[2
, 2, 1] by radical copolymerization of hept-2-ene and a maleic acid derivative. All of these copolymers are alkali soluble.

Furthermore, for example, copolymers of a compound containing a norbornene skeleton and a maleic acid derivative as shown in (1), +2) and (5) can have any copolymerization composition,
In the formula, the ratio of n and (n+m) is preferably 0.1≦□≦0.9 m + n. The copolymer smell is n and (n
+m) If the ratio [n/(n+m)] exceeds 0.9, the alkali solubility will decrease, and if it becomes smaller than 0 or 1, the coating film will become weak, or the photoresist will have different irradiated and non-irradiated areas. It is not suitable because it becomes difficult to distinguish between the alkali solubility of the two.

The copolymer used in the present invention has a weight average molecular weight (M w ) of 1,00 as determined by gel permeation chromatography (GPC method) using monodisperse polystyrene as a standard.
It is preferably in the range of 0 to 100,000, more preferably in the range of 2,000 to so, ooo. Outside the above range, sensitivity, resolution, heat resistance, film performance, adhesion to the substrate, etc. will be adversely affected.

Furthermore, by using naphthoquinone diazide sulfonic acid esters or benzoquinone diazide sulfonic acid esters as the photosensitizer used in the photosensitive composition of the present invention, the photosensitive composition of the present invention can be used as a positive-working photosensitive composition. be able to. Such naphthoquinonediazide sulfonic acid esters and benzoquinonediazide sulfonic acid esters include, for example, naphthoquinonediazide sulfonic acid chloride, benzoquinonediazide sulfonic acid chloride, and a functional group that can be condensed with an acid chloride such as a hydroxyl group or an amino group. It is obtained by reaction with a compound having Examples of the above-mentioned compounds having a hydroxyl group or an amino group include phenol 1. ρ-methoxyphenol, hydroquinone, resorcinol, 2,4-dihydroxybenzophenone, aniline, 4,4-isopropylidenediphenol, 3,4-dihydroxybenzophenone, 2゜2-dihydroxybenzophenone, 2,3
, 4.4-tetra-droxybenzophenone, 2,3.
4-trihydroxybenzophenone, resorcinol,
Examples include, but are not limited to, monoacetate and diphenylamine. These photosensitizers can be used alone or in combination of two or more.

In addition to the above-mentioned photosensitizers, diazomeldrum acid compounds or ortho-nitrobenzyl compounds may also be used as preferable photosensitizers for positive photosensitive compositions.

Furthermore, among the copolymers used in the present invention, formula (2
) etc., the photosensitive composition of the present invention can be used as a negative photosensitive composition by using an azide compound as a photosensitizer. Such a suitable azide compound is preferably an aromatic azide compound containing at least one aromatic azide compound per molecule, and specifically, 4-azidobenzalacetophenone, 4-azidobenzalacetone, 2,6- Bis(4-azidobenzal)cyclohexanone, 4,4-diazidodiphenylmethane, 3,3-diazidodiphenyl sulfone, 4,4-diazidodiphenyl ether, 4,4-diazidodiphenyl sulfide, 4,4'-diazidobenzophenone ,3
-(4-azidostyryl)-5,5-dimethyl-2-cyclohexen-1-one, 3-[41p-azidophenyl)-1,3-butadienyl]-5,5-dimethyl-2
-cyclohexen-1-one, 1-azidopyrene, 4,
4-Diazidochalcone, 1,3-bis(4-azidobenzal)-2-propanone, 4,4-diazidostilbene, 2,6-bis(4°-azidocinnamylidene)cyclohexanone, 2.6-bis Examples include (4°-azidocinnamylidene)-4-hydroxycyclohexanone, but are not limited thereto.

In addition, these photosensitizers can be used alone or in combination.
8! The above can be used together.

The blending ratio of the copolymers (1) to (8) and the photosensitizer is such that the photosensitizer is used in an amount of 5 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the copolymer. Especially 1
It is preferable to use 0 parts by weight or more and 50 parts by weight or less. If it deviates from the above range, it will adversely affect the sensitivity of the resist, the solubility difference between exposed and unexposed areas, pattern accuracy, and film properties.

The photosensitive composition according to the present invention is organic solvent soluble;
When used in the production of integrated circuits, etc., it is usually put into practical use in the form of a solution (resist solution).

In this case, the composition is generally 1 to 50% by weight in an organic solvent.
Preferably, it is dissolved and adjusted at a ratio of 5 to 30% by weight. In this case, the solvent used is to uniformly dissolve each constituent component of the photosensitive composition of the present invention, and after applying it to the surface of a substrate such as silicon or aluminum, the organic solvent is evaporated to form a uniform and smooth coating film. It is preferable to obtain the following. Specifically, ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl cellosolve, ethyl cellosolve, butyl cellosolve,
Examples include, but are not limited to, cellosolve solvents such as methyl cellosolve acetate and ethyl cellosolve acetate, ether solvents such as tetrahydrofuran and diethylene glycol dimethyl ether, and ester solvents such as ethylene glycol monoethyl ester and ethylene glycol monomethyl acetate. The organic solvents may be used alone or in combination of two or more.

In addition to the above-mentioned components, the photosensitive composition of the present invention may optionally contain plasticizers, sensitizers, dyes, other resins, various inhibitors such as thermal reaction inhibitors, adhesion improvers, etc. With the photosensitive composition of the present invention, a relief pattern can be formed by conventional photoresist techniques by adjusting the resist solution as described above. The method for forming this relief pattern will be explained below.

First, a resist solution prepared as described above is applied to a substrate. This coating on the substrate can be carried out using a spinner, for example.Next, it is coated at a temperature of 60 to 120°C, preferably 80°C.
Dry at 0-100°C for 20-60 minutes. After drying, this coated film is irradiated with deep ultraviolet rays and excimer laser through a positive photomask chart, but intermediate ultraviolet rays or near ultraviolet rays may also be used.

Next, a relief pattern is obtained by washing out the exposed area with 9H. As the developer, a weak alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, metasilicate sorter, tetramethylammonium hydroxide, etc. having a concentration of 5% by weight or less can be used. The relief pattern thus formed has good resolution and contrast.

Furthermore, a substrate can be etched using the photosensitive composition of the present invention and the pattern formed as described above as a mask.

[Effects of the Invention] As explained above, the photosensitive composition of the present invention has high transparency in the exposure region of deep ultraviolet rays and wavelengths associated with excimer laser sources.

As a result, sensitivity, resolution, heat resistance, and contrast can be significantly improved even in lithography using the above-mentioned light beam as a light source, which is necessary for work to improve the resolution of resists.Moreover, since it can be developed with an alkaline aqueous solution, there is no risk of swelling. It is possible to form a fine photoresist pattern with high accuracy and no bleed.

Therefore, these compositions can be used as resists for the production of integrated circuits such as ICs and LSIs, where the demands for sensitivity and resolution will become increasingly common in the future, as well as for the formation of ordinary wiring patterns, printed wiring boards, and PS. It can be used in the production of flat plates and photoplates, and can be used in a wide range of fields such as the electronics industry, photography industry, and printing industry.

(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Synthesis Example 1 Bicyclo[2,
23 g of hepto-2,5-diene and 500 ml of dehydrated xylene as a solvent were added, and the mixture was thoroughly stirred at 50° C. under a nitrogen stream until the system became homogeneous. Next, 949 q of maleic anhydride was added to this mixture, and 0.242 q of dibenzoyl peroxide was added, and the reaction was carried out at 90°C for 3 hours under a nitrogen stream.Thereafter, N-phenyl-2-naphthylamine in xylene was added to this mixture. The solution was added and the system was cooled to room temperature.The precipitated polymer was filtered and purified by precipitation with methyl alcohol dissolved in tetrahydrofuran.

Thereafter, it was dried at 70° C. for 24 hours to obtain the desired bicyclo[2,2,1]hept-2,5-diene-maleic anhydride copolymer DH-123.8 g. This polymer
The weight average molecular weight (MW) determined by gel permeation chromatography (GPC method) using monodisperse polystyrene as a standard was 5,500. Further, the ratio of weight average molecular weight to number average molecular weight (Nv/Hn) was 1.87.

Furthermore, 1) I-11HR measurement revealed that the copolymerization ratio was about 5:5. Further, the extinction coefficient (absorbance at a film thickness of 1 crQ) of this compound was 1840.

Synthesis Example 2 Bicyclo[2
,2,1]hept-2,5-diene 23 (l) and dehydrated xylene 5001 as a solvent were added and heated at 50° under a nitrogen stream.
The system was thoroughly stirred at C until the system became homogeneous.Next, maleimide 48.5! was added to this mixture. II, added 0.242 g of dibenzoyl peroxide, and heated under nitrogen stream for 9 hours.
The reaction was carried out at 0''C for 3 hours. A xylene solution of tophenyl-2-naphthylamine was then added to the mixture.
The system was cooled to room temperature. After filtering the precipitated polymer, it was purified by dissolving in tetrahydrofuran and precipitation with methyl alcohol.

Thereafter, it was dried at 70°C for 24 hours to obtain 5 g of the desired cyclo[2,2,1]hept-2,5-diene-maleimide copolymer DH-222. The weight average molecular weight of this polymer was determined by gel permeation chromatography (GPC method) using monodisperse polystyrene as a standard.
hv) was 5200. Moreover, the ratio of weight average molecular weight to number average molecular weight (Hw/Hn) was 1.97. In addition, the copolymerization ratio was approximately 5:5 according to NHR measurement, and the extinction coefficient of this compound (absorbance at a film thickness of 1 cn+)
was 2240.

Synthesis Example 3 29.6 g of 5-vinylbicyclo[2,2,1]hebdo-2-ene was placed in a 10,001-volume separable flask equipped with a thermometer, stirrer, condenser, and condenser gas inlet tube.
and maleic anhydride 1124. ．． 5g dehydrated xylene 40
0111, added 24 (l) of dibenzoyl peroxide as a radical initiator, and heated under a nitrogen stream for 9 hours.
After the reaction was completed at 0° C. for 1 hour, the polymer was precipitated with methyl alcohol, and purified by precipitation with tetrahydrofuran and methyl alcohol. Thereafter, it was dried at 60° C. for 24 hours to obtain 6 g of the desired 5-vinylbicyclo[2,2, heptose-2-ene-maleic anhydride copolymer VN-122. The weight average molecular weight of this polymer was determined to be 6,100 by gel permeation chromatography (GPC method) using monodisperse polystyrene as a standard. Further, the ratio of weight average molecular weight to number average molecular weight (Hw/Mn) was 1.59.

Further, the extinction coefficient (absorbance when the film thickness is 1 cn+) of this compound was 2020.

Synthesis Example 4 Remove the thermometer, stirrer, cooling tube, and gas introduction tube and make a 1-inch (
In a separable flask with a capacity of 10,100 O, 29.6 g of 5-vinylbicyclo[2,2,2,2,2-heptot-2-ene and 24.29 g of maleimide were added to 4001'I1 of dehydrated xylene.
1, add dibenzoyl peroxide o, 24 CI as a radical initiator, and heat at 90°C under a nitrogen stream.
After the reaction was completed for 1 hour, the polymer was precipitated with methyl alcohol, and the polymer was purified by dissolving in tetrahydrofuran and precipitating with methyl alcohol. Thereafter, it was dried at 60°C for 24 hours to obtain the desired 5-vinylbicyclo[2,2,1]hept-2-ene-maleimide copolymer VN-222°69. The weight average molecular weight (MW) of this polymer was determined to be 5,800 by gel permeation chromatography (GPC method) using monodisperse polystyrene as a standard. Further, the ratio of weight average molecular weight to number average molecular weight (Hw/Hn) was 1.65. In addition, the extinction coefficient of this compound (absorbance at a film thickness of 1C11)
was 2340.

Synthesis Example 5 5-
vinylcyclo[2,2,1]hegto-2-ene46.
8 g and maleic anhydride 39. : IJ was charged, and the mixture was stirred at 90°C for 4.5' hours while blowing dry air into the mixture at a rate of 20111/min. During this time, methyl isobutyl getone 1011 was added three times in total every 1.5 hours to adjust the viscosity of the solution. After continuing the reaction for another 2 hours, the solvent and volatile components were distilled off under reduced pressure.
The produced solid substance was purified by dissolving in tetrahydrofuran and precipitation with methyl alcohol. After that, it is dried at 70°C for 24 hours to obtain the desired 5-vinylbicyclo[2,2,
1] Hept-2-ene-maleic anhydride copolymer VN-
380.3g was obtained. Gel permeation chromatography (GP) using monodisperse polystyrene as a standard for this polymer
The weight average molecular weight (lh) determined by method C) is 560
It was 0. Also, the ratio of weight average molecular weight to number average molecular weight (
+tv/Hn) was 2.19. Also l1l-N
According to HR measurement, the copolymerization ratio was about 5.5. In addition, the extinction coefficient (absorbance at a film thickness of 1 cn) of this compound is 1740
Met.

Synthesis Example 6 Into a 1000 ml separable flask were added 26 (l) of 5-methylenebicyclo[2,2,2,2-heptin-2-ene and dehydrated xylene 5001 as a solvent, and the mixture was heated for 50 mL under a nitrogen stream.
The mixture was stirred well until the system became homogeneous. Then, 24.5 Q of maleic anhydride was added to this mixture, 0.121 g of dibenzoyl peroxide was added, and the reaction was allowed to proceed for 3 hours at 90°C under a nitrogen stream. went.

A xylene solution of N-phenyl-2-naphthylamine was then added to the mixture, and the system was cooled to room temperature.

After filtering the precipitated polymer, it was purified by dissolving in tetrahydrofuran and precipitation with methyl alcohol. then 7
The mixture was dried at 0° C. for 24 hours to obtain the desired 5-methylenebicyclo[2,2,2,2,2,2-heptogen-maleic anhydride copolymer CM-123, gg.

The weight average molecular weight (Hw) of this polymer was determined to be 6,000 by gel permeation chromatography (GPC method) using monodisperse polystyrene as a standard. Also, the ratio of weight average molecular weight to number average molecular weight (Hv/Hn) is 1.4
It was 2. Also, the copolymerization ratio was approximately 1:1 according to 'II-NHR measurement. Further, the extinction coefficient (absorbance at a film thickness of 1 cm) of this compound was 1,880.

Synthesis Example 7 Into a 100,011-volume separable flask, 26 g of 5-methylenebicyclo[2,2,1]hebdo-2-ene and 5001 dehydrated xylene were added as a solvent, and the mixture was heated for 50 minutes under a nitrogen stream.
The mixture was stirred well at 0°C until the system became homogeneous. Then 43. N-(hydroxyphenyl)maleimide was added to this mixture.
Add 8 g, dibenzoyl peroxide 0.121
! II was added, and the reaction was carried out at 90° C. for 3 hours under a nitrogen stream. Thereafter, a xylene solution of tophyl-2-naphthylamine was added to the mixture, and the system was cooled to room temperature.

After filtering the precipitated polymer, it was purified by dissolving in tetrahydrofuran and precipitation with methyl alcohol. then 7
Dry at 0°C for 24 hours to obtain the desired 5-methylenebicyclo[2,2,1]hept-2-ene-N-(p-hydroxyphenyl)maleimide copolymer C14-227.
,8(] was obtained.

The weight average molecular weight (Hw) of this polymer was determined to be 4,800 by gel permeation chromatography (GPC method) using monodisperse polystyrene as a standard. Also, the ratio of weight average molecular weight to number average molecular weight (Hw/Hn) is 1.4
It was 2. Moreover, the copolymerization ratio was about 1:1 according to l11-NHR measurement. In addition, the extinction coefficient of this compound (film thickness 1
The absorbance (in cm) was 2750.

Synthesis Example 8 29.5 g of 5-ethylidenebicyclo[2,2,1]hept-2-ene and 24.5 g of maleic anhydride were dissolved in dehydrated xylene 400111, and 0.24 g of dibenzoyl peroxide was added as a radical initiator. by adding
After completion of the 6 reactions in which the reaction was carried out at 90° C. for 1 hour, the polymer was precipitated with methyl alcohol and purified by dissolving in tetrahydrofuran and precipitating the methyl alcohol. Thereafter, it was dried for 24 hours at EO'C to obtain the desired 5-ethylidenebicyclo[2,2,1]hept-2.
-en-maleic anhydride copolymer NH-126,4 (l
I got it. The weight average molecule i (MW) of this polymer was determined to be 5300 by gel permeation chromatography (GPC method) using monodisperse polystyrene as a standard.

Also, the ratio of weight average molecular weight to number average molecular weight (Hw/Mn)
was 1.68.

In addition, the extinction coefficient of this compound (absorbance at a film thickness of 1 cm)
was 1810.

Example 1 Bicyclo[2,2,1]hep1~- obtained in Synthesis Example 1
2.5-diene-maleic anhydride copolymer DH-18゜0g and 2.3-naphthoquinone-(2)- as a photosensitizer.
diazido-5-sulfonic acid chloride and 2.3.4-)
A resist solution was prepared by dissolving the photosensitive composition of the present invention consisting of 2.09 g of a condensation reaction product of -lyhydroxybenzophenone in 22 ml of ethyl cellosolve acetate.

This resist solution was applied to a silicon wafer 2,000,000 times using a spin coater, and prebaked at 80°C for 20 minutes to obtain a 1.0 μl coating film. Then,
The above coating film was passed through a chrome mask with a pattern, and
:1 KrF laser exposure was performed using a reduction projection exposure method. This was developed with a 1.0x aqueous solution of tetramethylammonium hydroxide for 1 minute to dissolve the exposed areas and obtain a pattern. Further, a characteristic curve of irradiation amount and residual film rate was obtained by performing a post bake at 100° C. for 30 minutes and measuring the film thickness, and a sensitivity of 86 mj/− was obtained. Furthermore, when the formed pattern was observed using an electron microscope, it was found that a rectangular fine positive pattern could be resolved.

Example 2 Bicyclo[2,2°1]hept-2 obtained in Synthesis Example 2
,5-diene-maleic anhydride copolymer DH-28°O
q, and a condensation reaction product 2.09 of 2,3-naphthoquinone-(2)-diazido-5-sulfonic acid chloride and 2.3.4-)lyhydroxybenzophenone as a photosensitizer. The resist composition was dissolved in ethyl cellosolve acetate 2211 to prepare a resist solution.

This resist solution was coated onto a silicon wafer using a spin coater 1,800,800 times, and prebaked at 80° C. for 20 minutes to obtain a coating film of 1.0 μm. Then, the above coating film was passed through a chrome mask having a pattern, 5:
1 F laser exposure was performed using the reduction projection exposure method. This was developed with a 1.0% aqueous solution of tetramethylammonium hydroxide for 1 minute to dissolve the exposed area and obtain a pattern. A characteristic curve of irradiation dose and 8M rate was obtained by performing a 30-minute boost bake and measuring the film thickness, and a sensitivity of 98 mj/- was obtained.The formed pattern was observed with an electron microscope and a rectangular fine positive was found. It was found that patterns can be resolved.

Example 3 5-vinylbicyclo[2,2,1] obtained in Synthesis Example 3
Hept-2-ene-maleic anhydride copolymer VN-18
, Og and 2,3-naphthoquinone-(2) as a photosensitizer
-diazide-5-sulfonic acid chloride and 2.3.4-
) The photosensitive composition of the present invention consisting of the condensation reaction product 2.09 of lyhydroxybenzophenone was dissolved in ethyl cellosolve acetate 2211 to prepare a resist solution.

This resist solution was coated on a silicon wafer with a spin coater 2300300 times and prebaked at 80'C for 40 minutes to obtain a coating film of 1.0 μm. Next, the above coating film is passed through a chrome mask with a pattern,
KrF laser exposure was performed using a 5:1 reduction projection exposure method. This was developed with a 1.0% aqueous solution of tetramethylammonium hydroxide for 1 minute to dissolve the exposed areas and obtain a pattern. Further, a characteristic curve of irradiation amount and residual film rate was obtained by performing a post bake at 100° C. for 30 minutes and measuring the film thickness, and a sensitivity of 90 mj/− was obtained. Furthermore, when the formed pattern was observed using an electron microscope, it was found that a rectangular fine positive pattern could be resolved.

Example 4 5-vinylbicyclo[2,2,1] obtained in Synthesis Example 4
Hept-2-ene-maleic anhydride copolymer VN-28
,0g and 2,3-naphthoquinone-(2) as a photosensitizer.
-diazide-ti-sulfonic acid chloride and 2.3.4-
A resist solution was prepared by dissolving the photosensitive composition of the present invention comprising 2.0 g of a condensation reaction product of trihydroxybenzophenone in 22 ml of ethyl cellosolve acetate.

This resist solution was spin-coated onto a silicon wafer using a spin coater at 2100 rpm, and prebaked at 80° C. for 20 minutes to obtain a coating film of 1.0 μm. Next, pass the coating film through a chrome mask having a pattern, 5;
1 F laser exposure was performed using the reduction projection exposure method. This was developed with a 1.0% aqueous solution of tetramethylammonium hydroxide for 1 minute to dissolve the unexposed areas and obtain a pattern. Bost bake for 30 minutes at C and measure the film thickness to determine the characteristic curve of irradiation dose and residual film rate.
%) was obtained. Further, as a result of observing the formed pattern with an electron microscope, it was found that a rectangular FIA4 positive pattern was resolved.

Example 5 5-vinylbicyclo[2,2°1J obtained in Synthesis Example 5
Hept-2-ene-maleimide copolymer VN-38,0
A resist solution was prepared by dissolving the photosensitive composition of the present invention consisting of 9 and 2.09 of 3,3-diazidodiphenylsulfone as a photosensitizer in ethyl cellosolve acetate 281.

This resist solution was spin-coated onto a silicon wafer using a spin coater at 4,300 rpm, and prebaked at 80° C. for 20 minutes to obtain a 1.0 μl coating film. Then,
The above coating film was passed through a chrome mask with a pattern, and
KrF laser exposure was performed using a 1 m small projection exposure method. This was developed with a 1.0x aqueous solution of tetramethylammonium hydroxide for 1 minute to dissolve the unexposed areas and obtain a pattern. Further, a characteristic curve of irradiation dose and residual film rate was obtained by performing a post bake at 100'C for 30 minutes and measuring the film thickness.
%) sensitivity. Furthermore, when the formed pattern was observed using an electron microscope, it was found that a fine rectangular negative pattern could be resolved.

Example 6 5-methylenebicyclo[2,2,1
]Hept-2-ene-maleic anhydride copolymer CM-1
8,0(l) and 2,3-naphthoquinone-( as a photosensitizer)
2)-Diazido-5-sulfonic acid chloride and 2.3.
Condensation compound of 4-trihydroxybenzophenone! II!
A resist solution was prepared by dissolving 12 □0 g of the photosensitive composition of the present invention in 22 nl of ethyl cellosolve acetate. This resist solution was applied to a silicon wafer using a spin coater at 3200 rpm, and
Prebaking was performed at C for 20 minutes to obtain a coating film of 1.0 μm. Next, the coating film was exposed to KrF laser through a patterned chrome mask using a 5:1 reduction projection exposure method. This was developed with a 1.0% aqueous solution of tetramethylammonium hydroxide for 1 minute to dissolve the exposed areas and obtain a pattern. Furthermore, by performing Bost Beta at 100°C for 30 minutes and measuring the film thickness, a characteristic curve of irradiation dose and residual film rate was obtained, and a sensitivity of 74 mj/afl was obtained. Furthermore, when the formed pattern was observed using an electron microscope, it was found that a rectangular fine positive pattern could be resolved.

Example 7 5-methylenebicyclo[2,2,1
1 hept-2-ene-N-(hydroxyphenyl)maleide copolymer CH-28,0(] and 2 as a photosensitizer.
, 3-naphthoquinone-(2)-diazido-5-sulfonic acid chloride and 2.3.4-trihydroxybenzophenone condensation reaction product 2.og was dissolved in 22 ml of ethyl cellosolve acetate. death,
A resist solution was prepared.

This resist solution was spin-coated onto a silicon wafer using a spin coater at 3000 rpm, and prebaked at 80'C for 40 minutes to obtain a 1.0 μm coating film. Then,
The above coating film was passed through a chrome mask with a pattern, and
:1 F laser exposure was performed using the reduction projection exposure method. This was developed with a 1.0% aqueous solution of tetramethylammonium hydroxide for 1 minute to dissolve the exposed area and obtain a pattern. A characteristic curve of irradiation amount and residual film rate was obtained by post-baking at C for 30 minutes and measuring the film thickness, and a sensitivity of 92 mj/aa was obtained.

Furthermore, by observing the formed pattern with an electron microscope, it was found that a rectangular @fine positive pattern could be resolved.

Example 8 5-ethylidenebicyclo[2,2,
1] Hept-2-ene-maleic anhydride copolymer NH-
18.0g and 2,3-naphthoquinone-(
2) 20 g of condensation reaction product of -diazide-5-sulfonic acid chloride and 2,3°4-trihydroxybenzophenone
A resist solution was prepared by dissolving the photosensitive composition of the present invention consisting of the following in 22 ml of ethyl cellosolve acetate.

This resist solution was spin-coated onto a silicon wafer using a spin coater at 2300 rpm, and prebaked at 80° C. for 40 minutes to obtain a coating film of 1.0 μm. Then, the above coating film was passed through a chrome mask having a pattern, 5:
F laser exposure was performed using the 1 ia small projection exposure method. This was developed with a 1.Ox aqueous solution of tetramethylammonium hydroxide for 1 minute to dissolve the exposed area and obtain a pattern. By post-baking for 30 minutes and measuring the film thickness, a characteristic curve of irradiation dose and residual film rate was obtained, and a sensitivity of 72 mj/cJ was obtained.Furthermore, the formed pattern was observed with an electronic m-mirror, and a rectangular fine shape was found. It was found that positive patterns can be resolved.

Claims (1)

[Scope of Claims] 1. A photosensitive composition comprising a copolymer of a compound containing a norbornene skeleton and a maleic acid derivative, and a photosensitizer. 2 Compounds containing norbornene skeleton are bicyclo[2.2
．． 1] The photosensitive composition according to claim 1, which is hepto-2,5-diene. 3 A compound containing a norbornene skeleton has the following general formula (I
) The photosensitive composition according to claim 1, which is a compound represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (R_1, R_2, and R_3 in the formula represent -H or an alkyl group having 1 to 5 carbon atoms, and may be the same or different from each other.) 4 Norbornene The compound containing the skeleton has the following general formula (II)
The photosensitive composition according to claim 1, which is a compound represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (R_4 and R_5 in the formula represent -H or an alkyl group having 1 to 5 carbon atoms, and may be the same or different from each other.) 5 Maleic acid derivative The photosensitive composition according to claim 1, wherein is a compound represented by the following general formula (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (X in the formula represents -O-, -NH-, or -NR_6-, and R_6 is an alkyl group or an aryl group) 6 The photosensitizer is naphthoquinone- Claims 1 and 2, characterized in that the compound is a compound selected from 1,2-diazide sulfonic acid ester, azide compound, diazomeltramic acid compound, ortho-nitrobenzyl compound,
The photosensitive composition according to Items 3, 4, and 5. 7 The content of photosensitizer is 5 to 8 per 100 parts by weight of copolymer.
The photosensitive composition according to claims 1, 2, 3, 4, 5 and 6, characterized in that the amount of the photosensitive composition is 0 parts by weight.