JPH0684432B2 - Polysilane and photosensitive composition using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a polysilane and a photosensitive composition using the same.

(Prior Art) Microfabrication technology by photoetching is used for manufacturing electronic components such as semiconductor elements and integrated circuits. For example, a photoresist layer is formed on a silicon single crystal wafer by spin coating, a mask having a desired pattern is overlaid thereon, and exposure, development, and rinsing are performed. After image formation, a line with a width of several μm is formed by etching. Forming and opening windows. In the above microfabrication technology, the accuracy of the product depends on the performance of the photoresist, which is mostly used,
For example, it depends on the resolution on the substrate, the accuracy of photosensitivity, the adhesiveness with the substrate, the resistance to etching and the like.

Polysilane-based polymers have attracted attention as photoresists. As such a device, JP-A-60-228542
There is one described in the Gazette. The polysilane of the present invention photodepolymerizes upon irradiation with actinic radiation to produce a volatile product. By utilizing this property, it can be used as a photoresist for forming a positive pattern. However, such dry development has a drawback that a fine pattern cannot be accurately formed.

(Problems to be Solved by the Invention) As described above, the polysilane photoresist has a drawback in that a fine pattern cannot be accurately formed. As one method for solving such a drawback, it is possible to carry out alkali development. However, since polysilane is insoluble in alkaline solutions,
There was a problem that alkaline development was not possible.

The present invention has been made in view of the above problems, and an object thereof is to provide a polysilane having good alkali solubility and a photosensitive composition using the same.

[Structure of Invention]

(Means and Actions for Solving Problems) First, the first invention is a polysilane represented by the following formula.

(In the formula, R _{1 to} R ₃ may be the same or different,
Respectively hydrogen atom, alkyl group having 1 to 10 carbon atoms or 6 carbon atoms
~ 14 unsubstituted or substituted aryl groups. R ₄ represents an alkylene group having 1 to 10 carbon atoms or an unsubstituted or substituted phenylene group having 6 to 14 carbon atoms. R _{5 to} R ₉ may be the same or different and each is a hydrogen atom, a hydroxyl group, an alkoxy group, an alkyl group having 1 to 10 carbon atoms, or a carbon number of 6 to 14
Represents an unsubstituted or substituted aryl group, wherein at least one is a hydroxyl group. n and k are positive integers, and m is a positive integer including 0. ) In the formula, the alkyl group having 1 to 10 carbon atoms means methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-
It means butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like, and an unsubstituted or substituted aryl group having 6 to 14 carbon atoms is phenyl, p-tolyl, p-methoxyphenyl, p-chlorophenyl, p- Trifluoromethylphenyl, o-tolyl, o-methoxyphenyl, p-trimethylsilylphenyl, p-butylphenyl, 1-naphthyl, 2
-Naphthyl, 6-methyl-2-naphthyl, 6-methoxy-2
-Means naphthyl and the like.

In particular, And so on.

The polysilane of the present invention has a number average molecular weight of 4,000 to 500,000.
Is preferred. If it is less than 2000, a good coating film cannot be obtained when it is dissolved in a solvent and applied, and if it exceeds 1,000,000, the solubility in the solvent becomes poor.

The polysilane of the present invention can be easily obtained by reacting dichlorosilane having a phenolic hydroxyl group protected with silyl ether with sodium metal in xylene. For example, they are synthesized by the following method. m-
Protect the hydroxyl groups of phenoldichlorosilane with trimethylsilyl groups and react with metallic sodium in triene or xylene. After the reaction, the protective group is removed by hydrolysis to obtain a polysilane having a phenolic hydroxyl group. To obtain the copolymer, dichlorosilane such as dimethyldichlorosilane or phenylmethyldichlorosilane is added and reacted with sodium metal.

The polysilane of the present invention is decomposed by high energy rays such as light, electron rays and X-rays.

By utilizing this property, it can be used as a resist material. At that time, both positive type and negative type patterns can be formed depending on the combination of the type of high-energy ray to be irradiated and the substituent of polysilane. It is decomposed by irradiation with high energy rays, and when polysilane having a low molecular weight has higher solubility in an alkaline solution than that before irradiation, active species newly formed by the decomposition by irradiation react with each other to have a higher molecular weight. This is because the alkali solubility may be low.

In addition, by introducing a functional group that polymerizes by high energy rays such as acryloyl group (methacryloyl group, vinyl group, benzyl group) into phenolic OH group or phenyl group, it can be used as a negative resist material. You can In this case, the exposed part becomes high molecular weight,
Solubility in the alkaline solution is lower than in other parts.

Since the polysilane of the present invention becomes SiC when heated at a high temperature, it can be used as a ceramic material.

The second invention is (a) a polysilane represented by the following formula: (In the formula, R _{1 to} R ₃ may be the same or different,
Respectively hydrogen atom, alkyl group having 1 to 10 carbon atoms or 6 carbon atoms
~ 14 unsubstituted or substituted aryl groups. R ₄ represents an alkylene group having 1 to 10 carbon atoms or an unsubstituted or substituted phenylene group having 6 to 14 carbon atoms. R _{5 to} R ₉ may be the same or different and each is a hydrogen atom, a hydroxyl group, an alkoxy group, an alkyne group having 1 to 10 carbon atoms, or a carbon number of 6 to
Represents 14 unsubstituted or substituted aryl groups, at least one of which is a hydroxyl group. n and k are positive integers, m is 0
Represents a positive integer including. ) (B) A photosensitive composition containing an organic solvent.

The organic solvent used in the present invention may be any one as long as it can dissolve polysilane and is not particularly limited, but a polar organic solvent is preferable.

For example, there are ketone type solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, cellosolve type solvents such as methyl cellosolve, methyl cellosolve acetate and ethyl cellosolve acetate, ester type solvents such as ethyl acetate, butyl acetate and isoamyl acetate. Each solvent may be used alone or as a mixed solvent of two or more kinds.

The composition of the present invention may optionally contain additives such as an ultraviolet absorber, a surfactant and a sensitizer.

In the present invention, an alkali-soluble resin may be contained.
Any alkali-soluble resin may be used as long as it is soluble in an alkaline solution, and examples thereof include novolak resins obtained by condensation of phenols and formaldehyde. Examples of the phenols include phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, m-cresol, p-
Examples include cresol and bisphenol A, 4-chloro-3-cresol. The above-mentioned novolak resin can be obtained by condensing one or more of these with formalin, but the resin is not limited to the novolak resin, and poly (p-vinylphenol), poly (p-isophenol) Propenylphenol), poly (m-isopropenylphenol), copolymer of p-hydroxystyrene and methyl methacrylate, copolymer of p-hydroxystyrene and methyl acrylate, p-isopropenylphenol and methyl acrylate Any resin may be used as long as it has an aromatic ring and a hydroxy group in its structural unit, such as a copolymer with p-hydroxystyrene and a copolymer of p-hydroxystyrene and methacrylic acid. Preferred are poly (p-vinylphenol) and copolymers of poly (p-vinylphenol) and methyl methacrylate. These resins are used alone or in a mixture of two or more.

If the mixing ratio of the alkali-soluble resin is less than 10 parts by weight, the film-forming property is poor, and if it exceeds 2000 parts by weight, the sensitivity is poor. Therefore, it is 10 to 2000 parts by weight.

The photosensitive composition of the present invention, if necessary, a thermal polymerization inhibitor for ensuring storage stability, an antihalation agent for preventing halation from the substrate, and an adhesion for improving the adhesion to the substrate. A property improver and the like may be blended.

A third invention is (a) a polysilane represented by the following formula: (In the formula, R _{1 to} R ₃ may be the same or different,
Respectively hydrogen atom, alkyl group having 1 to 10 carbon atoms or 6 carbon atoms
~ 14 unsubstituted or substituted aryl groups. R ₄ represents an alkylene group having 1 to 10 carbon atoms or an unsubstituted or substituted phenylene group having 6 to 14 carbon atoms. R _{5 to} R ₉ may be the same or different and each is a hydrogen atom, a hydroxyl group, an alkoxy group, an alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms.
It represents 14 unsubstituted or substituted phenylene groups, at least one of which is a hydroxyl group. n and k are positive integers, and m is a positive integer including 0. (B) Photosensitizer (c) Organic solvent is contained in the photosensitive composition.

The photosensitizer used in the present invention may be one that forms a positive image such as a diazo compound or one that forms a negative image such as an azide compound, and is commonly known as a photosensitizer. If there is no particular limitation.

Examples of the photosensitizer include naphthoquinone diazide compounds and azide compounds. Examples of the naphthoquinonediazide compound include 1,2-naphthoquinone-2
-Diazide-5-sulfonic acid chloride and a sulfonic acid ester synthesized from a compound having a phenolic hydroxyl group, examples of the compound having a phenolic hydroxyl group, for example, 3,4,5-trihydroxybenzoic acid ethyl ester, 2,3,4-trihydroxybenzophenone, 2,4,
Examples include 2 ', 4'-tetrahydroxybenzophenone, quercetin, morin alizarin, quinizarin, purpurin. Examples of the azide compound include 3,3'-diazidodiphenyl sulfone, 2-methoxy-4'-azidochalcone, 1- (p-azidophenyl) -4- (2-furyl) -1,3-butadiene. To be Among these, solubility in a solvent is required and sensitivity to the wavelength of the light source of the exposure apparatus is required. Since 436 nm light source is used in the stepper widely used at present, bis (1,2-naphthoquinone-2-diazide-5-sulfonic acid) -2,3,4-trihydroxy is applicable for 436 nm. Benzophenone ester, 1- (p-azidophenyl) -4- (2-furyl) -1,3-butadiene and the like are preferable. These azide compounds are used alone or in a mixture of two or more.

If the compounding ratio of this photosensitizer is less than 5 parts by weight, the difference in solubility between the exposed part and the unexposed part will be small, and a good pattern will not be given. It is preferably 10 to 50 parts by weight.

The composition of the present invention may optionally contain additives such as an ultraviolet absorber, a surfactant and a sensitizer.

The organic solvent used in the present invention may be any one as long as it dissolves the polysilane and the photosensitizer, but a polar organic solvent is preferable, and those mentioned in the second invention are also used in the present invention. .

Further, in the present invention, an alkali-soluble resin as described in detail in the second invention may be contained.

The photosensitive composition of the present invention comprises, if necessary, a thermal polymerization inhibitor for storage stability, an antihalation agent for preventing halation from the substrate, and an adhesion for improving the adhesion to the substrate. A property improver and the like may be blended.

Next, examples of use of the photosensitive composition of the present invention will be described.

First, a commercially available resist is applied as a flattening agent to a predetermined thickness on a material for producing a fine pattern. The flattening agent may be any one as long as it has a purity that does not cause any trouble in the production of semiconductor elements.
Examples of the resin include a positive resist made of a substituted o-quinonediazide and a novolac resin, polystyrene,
Polymethylmethacrylate, polyvinylphenol, novolac resin, polyester, polyvinyl alcohol,
Examples thereof include polyethylene, polypropylene, polybutadiene, polyvinyl acetate, polyvinyl butyral polyisid and the like. These resins are used alone or in a mixed system. Then, after the coating layer is baked and hardened at 100 to 250 ° C. for 30 to 150 minutes, the above-mentioned photosensitive composition is coated thereon. As a coating method, a spin coating using a spinner, dipping, spraying, printing and the like can be used. Next, the thickness of the coating film formed by drying at an appropriate temperature (usually 150 ° C. or less, preferably 70 to 120 ° C.) can be adjusted by the application means, the resin concentration of the solution, the viscosity, and the like.

Examples of the material for producing the fine pattern include a silicon oxide film, and a substrate on which chromium, aluminum, copper or the like is deposited.

By exposing a desired portion of the photosensitive composition coated on the above substance, the solubility of the exposed portion in an aqueous alkaline solution is increased. Optimum exposure amount required at this time, varies depending on the composition, are generally within the range of ^{1mJ / cm 2 ~1000mJ / cm 2} .

In irradiation, a pattern can be manufactured by either an adhesion method or a projection method. Then, using a hot plate, heat at 50 to 120 ° C. for 30 seconds to 15 minutes. As a result, bubbles are formed in the exposed portion. After that, in the developing step of manufacturing the resist pattern by removing the exposed portion where the bubbles are generated in the alkaline aqueous solution, a tetraalkylammonium aqueous solution such as a tetramethylammonium aqueous solution or an inorganic alkali such as sodium hydroxide or potassium hydroxide is used. Use an aqueous solution. The concentration of these aqueous solutions is usually 15% by weight or less.

The development is performed by a dipping method, a spray developing method or the like.

Next, the planarizing layer is etched by oxygen RIE using the formed resist pattern as a mask.

At that time, the unexposed area is exposed to oxygen RIE to form a silicon dioxide (SiO ₂ ) film on the surface layer, which is 10 to 100 times more oxygen resistant than the flattening layer exposed in the exposed area. You will have an RIE. The flattening layer under the exposed area is entirely oxygen RI
An optimal pattern profile can be obtained by etching with E.

The substrate is etched using the pattern formed as described above as a mask. As the etching, wet etching, dry etching, or the like is performed, and dry etching is preferable when a fine pattern of 3 μm or less is formed.

As a wet etching agent, in the case of a silicon oxide film, an aqueous solution of hydrofluoric acid, an aqueous solution of ammonium fluoride, in the case of aluminum, an aqueous solution of phosphoric acid, an aqueous solution of acetic acid, an aqueous solution of nitric acid, and in the case of chromium, cerium ammonium nitrate. Aqueous solution is used.

The gas for dry etching is CF ₄ , C ₂ F ₆ , CCl ₄ , B
Cl ₃ , Cl ₂ , HCl, H _2, etc. are used in combination as needed.

Etching conditions are determined by the combination of the type of material for producing a fine pattern and the photosensitive composition, the concentration of the wet etching agent in the reaction tank, the concentration of the dry etching gas, the reaction temperature, the reaction time, etc. Especially, the method is limited.

After etching, the unexposed portion remaining on the substrate is
It is removed from the above substances by a stripping agent such as J-100 (manufactured by Nagase Kasei Co., Ltd.) or oxygen gas plasma.

In addition to the above steps, additional steps may be added depending on the purpose. For example, a rinsing step (usually using water) performed for the purpose of washing and removing the developing solution from the above substance after development, and before the coating for the purpose of improving the adhesive between the photosensitive composition and the substance on which the fine pattern is to be produced. Examples include a pretreatment step to be performed, a baking step to be performed before or after development, and a re-irradiation step to ultraviolet rays to be performed before dry etching. The photosensitive composition of the present invention may be used as a conventional single layer resist.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

(Examples) Example 1. 135 g of metaisopropenylphenol and 109 g of trimethylsilyl chloride are dissolved in dehydrated ether (500 g), and 101 g of triethylamine is added dropwise. After the salt was swallowed, the oral solution was concentrated and then distilled to obtain trimethylsilyl metaisopropenyl phenyl ether (hereinafter abbreviated as "I").

181 g of [I], 177 g of phenyldichlorosilane and 5 g of chloroplatinic acid were reacted in xylene and then distilled to obtain [II] as shown on the right.

17.9 g of [II], 7.2 g of dimethyldichlorosilane and sodium are reacted in 100 ml of dehydrated xylene at 130 ° C. for 20 hours. The reaction product is poured into methanol, the insoluble matter is filtered, and then the oral solution is concentrated. Water was further added, and the insoluble matter was filtered, acidified with aqueous hydrochloric acid solution, extracted with ether, and concentrated to obtain polysilane.

Mn; 230000, MW; 560000, Fig. 1 shows the IR spectrum of polysilane, and Fig. 2 shows the NMR spectrum.

These indicate that polysilane has a structure as shown in [III].

This polysilane was an aqueous solution of methanol, THF and NaOH. On the other hand, polysilane of the same structure having no OH group was insoluble in methanol, THF and NaOH aqueous solution.

Examples 2 to 4 A vinyl compound was reacted in the same manner as in Example 1 to obtain polysilanes of Examples 2 to 4 as described above. These were soluble in methanol, THF and NaOH aqueous solution. H ¹ -NMR of Example 2
The spectrum is shown in FIG. 3, the H ¹ -NMR spectrum of Example 3 is shown in FIG. 4, and the H ¹ -NMR spectrum of Example 4 is shown in FIG.

Example 5 206 g of [I], 115 g of methyldichlorosilane, 5 chloroplatinic acid
g was reacted in triene and then distilled to obtain [IV].

80 g of [IV] and 30 g of dispersed sodium were reacted in 200 ml of dehydrated toluene at 110 ° C. for 1.5 hours. The reaction product is filtered and concentrated, and then methanol is poured and stirred to hydrolyze trimethylsilyl ether. The reaction product was concentrated, dissolved in a small amount of methanol, and reprecipitated in water to obtain 10 g of polysilane [V].
Got

Mn; 22000, Mw; 39000, Fig. 6 shows the IR spectrum of polysilane, and Fig. 7 shows the H'-NMR spectrum.

Examples 6-8 The chlorosilane [IV] used in Example 5 was reacted with dimethyldichlorosilane to give the polymer of Example 6 [IV].
Example 7 by reacting with methylphenyldichlorosilane
The polymer of Example 8 was reacted with o-tolylmethyldichlorosilane to obtain the polymer of Example 8. The reaction conditions and the like are the same as in Example 5. The H'-HMR spectra of 6,7,8 are shown in FIGS. 8,9,10, respectively.

Example 9 A solution of a novolak resin dissolved in cellosolve acetate was applied onto a silicone wafer with a spinner and heated at 220 ° C. for 1 hour to form a lower layer. A solution prepared by dissolving 5 g of polysilane [V] in 10 g of cyclohexanone was coated on the lower layer with a spinner and dried on a hot plate at 120 ° C. for 5 minutes to give 0.40.
A .mu.m photosensitive coating was formed.

Then, it was exposed to monochromatic light of 250 nm, developed with a 0.6% NaOH aqueous solution for 40 seconds, and dried at 80 ° C. for 30 minutes to form a resist pattern on the upper layer. The oxygen RIE (2.0 × 10 ^-2 Torr 0.06 W / cm
As a result of etching the lower layer for ² minutes in ² ), 0.5 μm lines and spaces were formed.

Example 10 5 g of the polysilane of Example 6 was dissolved in 10 g of cyclohexanone, and the filtered solution was applied onto the lower layer prepared in the same manner as in Example 9 to form a 0.60 μm photosensitive coating film.

Then, expose with 249 nm monochromatic light and 40
The resist pattern was formed on the upper layer by developing for 1 second and drying at 90 ° C. for 30 minutes. Then, as a result of etching the lower layer with oxygen RIE using the formed pattern, a line and a space of 0.5 μm were formed on the upper layer.

Example 11 The polysilane of Example 7 was dissolved in cyclohexanone, and a line and space of 0.6 μm were formed by the same method as in Example 10.

Example 12 The polysilane of Example 8 was dissolved in cyclohexanone, and by the same method as in Example 10, 0.6 μm lines and spaces were formed.

Example 13 (In the formula, x: y = 1: 1) 5 g of a polymer having a number average molecular weight of 7000, m, p-cresol novolac resin (number average molecular weight: 1200) 5 g and di (1,2-naphthoquinone) -2-diazide-5-sulfonic acid) -2,3,4-trihydroxybenzophenone ester 4
g was dissolved in 100 g of cyclohexanone, mixed and stirred to obtain a photosensitive composition of the present invention.

Next, the substrate coated with a sufficiently thickening agent is applied at 200 ° C for 1 hour.
Heat for a period of time, then apply the photosensitive composition of the present invention to a thickness of 0.6 μm through a 0.2 μm filter, and apply at 80 ° C. for 5 minutes.
After pre-baking for a minute, it was exposed (50 mJ / cm ² ) at 436 nm. Then, it was heated on a hot plate at 80 ° C. for 5 minutes, and then developed with a 3.0 wt% tetramethylammonium hydroxide aqueous solution for 1 minute. After that, the planarizing layer was etched by oxygen RIE using the formed resist pattern as a mask. After that, when the cross section was observed with a scanning electron microscope, it was found that the film thickness was 1.5 μm and the line and space had a steep profile at 0.5 μm.

Example 14 (In the formula, x: y = 1: 1) 10 g of a polymer having a number average molecular weight of 7000 and di (1,2-naphthoquinone-2-diazide-5-sulfonic acid) -2,3, 4-trihydroxybenzophenone ester 4
g was dissolved in 100 g of cyclohexanone, mixed and stirred to obtain a photosensitive composition of the present invention.

Example 16 (In the formula, x: y = 1: 1) 10 g of a polymer having a number average molecular weight of 30000, and di (1,2-naphthoquinone-2-diazide-5-sulfonic acid) -2,3, 4-trihydroxybenzophenone ester 4
g was dissolved in 100 g of cyclohexanone, mixed and stirred to obtain a photosensitive composition of the present invention.

Using the compositions obtained in Examples 14 to 16, the same operation as in Example 1 was carried out, and the formed pattern was observed. The sensitivity was 50 mJ / cm ² , and a sharp profile of 0.5 μm lines and spaces was obtained. Was to get.

Example 17 With a number average molecular weight of: 3000 polymer 5g, m, p-cresol novolac resin (number average molecular weight: 1200) 5g and di (1,2-naphthoquinone-2-diazide-5-sulfonic acid) -2,3 , 4-Trihydroxybenzophenone ester 4
g was dissolved in 100 g of cyclohexanone, mixed and stirred to obtain a photosensitive composition of the present invention.

When the formed pattern was observed by the same operation as in Example 13, the sensitivity was 60 mJ / cm ² and a steep profile was obtained at a line and space of 0.5 μm.

Example 18 16 g of a polymer having a number average molecular weight of 40,000 and di (1,2-naphthoquinone-2-diazide-5-sulfonic acid) -2,3,4-trihydroxybenzophenone ester 4
g was dissolved in 50 g of cyclohexanone, mixed and stirred to obtain a photosensitive composition of the present invention.

Next, a solution of novolac resin dissolved in cellosolve acetate was applied on a silicon wafer by a spinner and heated at 220 ° C. for 1 hour to form a lower layer having a thickness of 1.5 μm. The photosensitive composition of the present invention was applied thereon to a thickness of 0.6 μm, prebaked at 90 ° C. for 5 minutes, and then exposed at 436 nm (50 mJ / cm ² ).
Then, development was performed for 60 seconds with a 3.0% by weight aqueous solution of tetramethylanthenium hydroxide. After that, the flattening layer was etched by oxygen RIE using the formed resist pattern as a mask. After that, when the cross section was observed with a scanning electron microscope, it was found that the film thickness was 1.5 μm and the line had a steep profile in 0.5 μm lines and spaces.

Example 19 (In the formula, x: y = 1: 1) 20 g of a polymer having a number average molecular weight of 50,000 and di (1,2-naphthoquinone-2-diazide-5-sulfonic acid) -2,3,4 -Trihydroxybenzophenone ester 5
g was dissolved in 50 g of cyclohexanone, mixed and stirred to obtain a photosensitive composition of the present invention.

Example 20 (In the formula, x: y = 1: 1) 20 g of a polymer having a number average molecular weight of 10,000, and di (1,2-naphthoquinone-2-diazide-5-sulfonic acid) -2,3,4 -Trihydroxybenzophenone ester 5
g was dissolved in 50 g of ethyl cellosolve acetate, mixed and stirred to obtain a photosensitive composition of the present invention.

Example 21 (In the formula, x: y = 2: 1) 20 g of a polymer having a number average molecular weight of 10,000, and di (1,2-naphthoquinone-2-diazide-5-sulfonic acid) -2,3,4 -Trihydroxybenzophenone ester 5
g was dissolved in 50 g of ethyl cellosolve acetate, mixed and stirred to obtain a photosensitive composition of the present invention.

Example 22 (In the formula, x: y = 4: 1) 20 g of a polymer having a number average molecular weight of 15000, and di (1,2-naphthoquinone-2-diazide-5-sulfonic acid) -2,3,4 -Trihydroxybenzophenone ester 5
g was dissolved in 70 g of cyclohexanone, mixed and stirred to obtain the photosensitive composition of the present invention.

Example 23 (In the formula, x: y = 2: 1) 20 g of a polymer having a number average molecular weight of 20000, and di (1,2-naphthoquinone-2-diazide-5-sulfonic acid) -2,3,4 -Trihydroxybenzophenone ester 5
g was dissolved in 70 g of cyclohexanone, mixed and stirred to obtain the photosensitive composition of the present invention.

Example 24 30 g of a polymer having a number average molecular weight of 30000, and di (1,2-naphthoquinone-2-diazide-5-sulfonic acid) -2,3,4-trihydroxybenzophenone ester 1
0 g was dissolved in 100 g of cyclohexanone, mixed and stirred to obtain the photosensitive composition of the present invention.

Example 25 (In the formula, x: y = 1: 1) 20 g of a polymer having a number average molecular weight of 40,000, and di (1,2-naphthoquinone-2-diazide-5-sulfonic acid) -2,3,4-tri Hydroxybenzophenone ester 5
g was dissolved in 50 g of cyclohexanone, mixed and stirred to obtain a photosensitive composition of the present invention.

The same operation as in Example 18 was performed using the compositions obtained in Examples 19 to 25, and the formed pattern was observed. The sensitivity was 50 mJ / cm ² and the sharp profile of 0.5 μm lines and spaces was obtained. It was something that had.

〔The invention's effect〕

According to the present invention, it is possible to obtain polysilane having a good solubility in alkali dissolution.

The photosensitive composition of the present invention has excellent sensitivity and resistance to oxygen plasma. Further, since it is not affected by the step of the substrate, the film thickness can be reduced, and as a result, the pattern resolution is improved, which is extremely convenient for fine processing. Further, since development can be performed with an alkaline solution, it is less likely to swell than when development is performed with an organic solvent, and a fine pattern can be formed.

[Brief description of drawings]

FIG. 1 and FIG. 2 are diagrams showing 1H-NMR spectrum and IR spectrum of one example of the present invention, and FIGS.
FIG. 10 is a diagram showing an IR spectrum and a 1 H-NMR spectrum of another example.

Claims (5)

[Claims] 1. A polysilane represented by the following formula: In the formula (R _{1 to} R ₃ may be the same or different,
Each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ₄
Represents an alkylene group having 1 to 10 carbon atoms or an unsubstituted or substituted phenylene group having 6 to 14 carbon atoms. R _{5 to} R ₉ may be the same or different, and each is a hydrogen atom, a hydroxyl group,
It represents an alkoxy group, an alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 14 carbon atoms, at least one of which is a hydroxyl group. n and k are positive integers, m
Represents a positive integer including 0. ) 2. A polysilane represented by the following formula: (In the formula, R _{1 to} R ₃ may be the same or different,
Respectively hydrogen atom, alkyl group having 1 to 10 carbon atoms or 6 carbon atoms
~ 14 unsubstituted or substituted aryl groups. R ₄ represents an alkylene group having 1 to 10 carbon atoms or an unsubstituted or substituted phenylene group having 6 to 14 carbon atoms. R _{5 to} R ₉ may be the same or different and each is a hydrogen atom, a hydroxyl group, an alkoxy group, an alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms.
Represents 14 unsubstituted or substituted aryl groups, at least one of which is a hydroxyl group. n and k are positive integers, m is 0
Represents a positive integer including. ) (B) A photosensitive composition containing an organic solvent. 3. A polysilane represented by the following formula: (In the formula, R _{1 to} R ₃ may be the same or different,
Respectively hydrogen atom, alkyl group having 1 to 10 carbon atoms or 6 carbon atoms
~ 14 unsubstituted or substituted aryl groups. R ₄ represents an alkylene group having 1 to 10 carbon atoms or an unsubstituted or substituted phenylene group having 6 to 14 carbon atoms. R _{5 to} R ₉ may be the same or different and each is a hydrogen atom, a hydroxyl group, an alkoxy group, an alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms.
Represents 14 unsubstituted or substituted aryl groups, at least one of which is a hydroxyl group. n and k are positive integers, and m is a positive integer including 0. ) (B) Photosensitizer (c) A photosensitive composition containing an organic solvent. 4. The photosensitive composition according to claim 2, which contains an alkali-soluble resin. 5. The photosensitive composition according to claim 3 or 4, wherein (b) the photosensitizer is 5 to 100 parts by weight with respect to 100 parts by weight of the polysilane of (a). .