JPH09179305A - Photosensitive composition, pattern formation and formation of colored film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive compsn. having high exposure sensitivity, good sectional shape and excellent resolution by incorporating specific polysilane and a compd. which generates a radical or acid by irradiation with chemical radiations into this compsn. SOLUTION: The polysilane having the monomer expressed by formula as a repeating unit and the compd. which generates the radical or the acid by the irradiation with the chemical radiations are incorporated into the compsn. In the formula, R<1> denotes a substd. or unsubstd. arom. group. The pattern forming method comprises applying the photosensitive compsn. contg. the polysilane having the monomer expressed by formula as the repeating unit and the compd. which generates the radical or the acid by the irradiation with the chemical radiations on a substrate and drying the coating to form a photosensitive compsn. film and exposing the photosensitive compsn. by irradiation with desired pattern light, then developing the film with an aq. alkaline soln.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition used for pattern formation applied to the production of electronic elements such as semiconductor devices and liquid crystal display devices, a pattern forming method and a colored film forming method. .

[0002]

2. Description of the Related Art In manufacturing semiconductor devices and liquid crystal display devices, various processes using a resist pattern as a mask are performed. For example, a photosensitive composition containing polysilane is exposed alone (for example, selective irradiation with electron beam, X-ray, etc.)
It decomposes or crosslinks, and dissolves in a polar solvent such as alcohol or ketone to enable development and patterning.

However, when a pattern is formed using the above-mentioned photosensitive composition consisting of polysilane alone, an exposure dose of several J / cm ² is required, and the cross-sectional shape and resolution of the obtained pattern are poor. Becomes insufficient.

[0004]

DISCLOSURE OF THE INVENTION The present invention is intended to provide a photosensitive composition having a high exposure sensitivity, a good cross-sectional shape, and an excellent resolution. Further, the present invention is intended to provide a pattern forming method having a good cross-sectional shape and high accuracy. Furthermore, the present invention is intended to provide a method for forming a colored film having a smooth surface, which is excellent in durability and mechanical strength.

[0005]

A photosensitive composition according to the present invention generates a radical or an acid by irradiation with polysilane having a monomer of the general formula (I) shown below as a repeating unit and actinic radiation. It is characterized by containing a compound.

[0006]

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However, R ¹ in the formula represents a substituted or unsubstituted aromatic group. The pattern forming method according to the present invention comprises applying a photosensitive composition containing a polysilane having a monomer of the general formula (I) as a repeating unit and a compound capable of generating a radical or an acid upon irradiation with actinic radiation onto a substrate, The method is characterized by comprising a step of forming a photosensitive composition film by drying and a step of irradiating the photosensitive composition film with a desired pattern of light to expose it and then developing it with an aqueous alkaline solution. is there.

Another pattern forming method according to the present invention is
A photosensitive composition containing a polysilane having a monomer of the general formula (I) as a repeating unit and a compound that generates a radical or an acid by actinic radiation is applied on a substrate and dried to form a photosensitive composition film. The method is characterized by comprising a step and a step of irradiating the photosensitive composition film with a desired pattern of light for exposure, heat treatment, and developing with an organic solvent.

The method for forming a colored film according to the present invention is a substrate comprising a photosensitive composition containing a polysilane having a monomer of the general formula (I) as a repeating unit and a compound capable of generating a radical or an acid upon irradiation with actinic radiation. A step of coating and drying to form a photosensitive composition film, exposing the photosensitive composition film to a desired pattern of light, and exposing the photosensitive composition film after exposure to a dye component. The method is characterized by comprising a step of selectively immersing in a solution containing the material and selectively coloring, and a step of heating and drying the photosensitive composition film after coloring to cure the film.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The photosensitive composition according to the present invention comprises a compound (hereinafter referred to as a radical generator) which generates a radical upon irradiation with actinic radiation and a polysilane having the monomer of the general formula (I) as a repeating unit or actinic radiation. It is prepared by including a compound that generates an acid upon irradiation (hereinafter referred to as an acid generator), and dissolving these components in a desired solvent.

R of the polysilane represented by the general formula (I) represents a substituted or unsubstituted aromatic ring, and examples thereof include a substituted or unsubstituted phenyl group, a naphthyl group and an anthranyl group. Such polysilane may be a homopolymer or a copolymer. However, in the case of a copolymer, it is desirable that the monomer of the general formula (I) is contained in an amount of 30% or more, more preferably 50% or more.

The molecular weight of the polysilane is not particularly limited, but is preferably 500 to 100,000, more preferably 1,
It is desirable that it is 000 to 10,000. If the molecular weight of the polysilane is less than 500, the durability of the formed insulating film may be reduced. On the other hand, if the molecular weight of the polysilane exceeds 100,000, the solvent solubility may decrease. As such a polysilane, specifically, one represented by the following chemical formula 14 is used.

[0013]

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Photosensitive Component The radical generator or the acid generator is not particularly limited as long as it can generate a radical or an acid upon irradiation with actinic radiation. However, it is preferable to use a radical generator as a photosensitive component in the photosensitive composition of the present invention. This activates the hydrogen atoms in the side chains of the polysilane to facilitate silanol (Si
This is because the --OH) bond can be generated, resulting in higher sensitivity to actinic radiation.

Examples of the radical generator include azo compounds such as azobisisobutylnitrile, peroxides such as benzoi peroxide and ditertiarybutyl peroxide, benzoin, benzoin alkyl ethers, benzoyl alkylaryl thioethers, benzoyl aryl ethers, Examples thereof include benzoylalkylaryl thioethers, benzylalalkylethanols, phenyl-glyoxal alkylacetals, alkylaryl ketones such as benzoyloxime, and organic halides represented by the following chemical formula 15.

[0016]

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Among the above organic halides, the trihalomethyl-groups described in US Pat. No. 3,779,778.
Preferred are s-triazines, that is, compounds represented by the general formula (II) shown below. Specifically, 2,
4-bis (trichloromethyl) -6-methyl-s-triazine, 2,4,6-tris (trichloromethyl) -s
-Triazines.

[0018]

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[0019] However, Q in the formula is bromine or chlorine, P is ^{_{-CQ 3, -NH 2, -NHR 3}} , -N (R 3) 2, -
OR ³ , a substituted or unsubstituted phenyl group (wherein Q is bromine or chlorine, R ³ is a phenyl group, a naphthyl group or a lower alkyl group having 6 or less carbon atoms), and R ² is -C.
^{_{Q 3, -NH 2, -NHR 3}} , -N (R 3) 2, -OR
^{3, - (CH = CH)} n -W, substituted or unsubstituted phenyl group (wherein Q is bromine or chlorine, R ³ is a phenyl group, a naphthyl group, or more than 6 lower alkyl group having a carbon
n is an integer of 1 to 3, W is an aromatic ring, a heterocycle or the following formula 1
It is a group represented by the general formula (III) shown in FIG. ).

[0020]

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However, Z in the formula is oxygen or sulfur, and R
⁴ represents a lower alkyl group or a phenyl group. In the general formula (II), the aromatic ring or heterocycle represented by W may be further substituted. Examples of such a substituent include chlorine, bromine, phenyl, a lower alkyl group having 6 or less carbon atoms, a nitro group, a phenoxy group, an alkoxy group,
Examples thereof include acetoxy group, acetyl group, amino group and alkylamino group.

Among the above organic halides, compounds further substituted with vinylhalomethyl-s-triazine disclosed in US Pat. No. 3,987,037 are preferable.
The vinylhalomethyl-s-triazine compound is a photodegradable s-triazine compound having at least one trihalomethyl group and a group conjugated with a triazine ring by at least one ethylenically unsaturated bond, and as R ² in the general formula (II) - a (CH = CH) _{compound n} -W has been introduced. Specific examples of the trihalomethyl-s-triazines represented by the general formula (II) are shown in Chemical formula 18 below, and other radical generators are shown in Chemical formulas 19 to 23 below.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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Examples of the acid generator include onium salts, halogen-containing compounds, orthoquinonediazide compounds, sulfone compounds, sulfonic acid compounds and nitrobenzyl compounds. Among these, onium salts and orthoquinonediazide compounds are preferable.

Specific examples of onium salts include iodonium salts, sulfonium salts, phosphonium salts, cyazonium salts and ammonium salts. Preferably, the compounds represented by the following chemical formulas 24 to 26 can be mentioned.

[0031]

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[0032]

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[0033]

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Specific examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds, and the compounds represented by the following chemical formulas 27 and 28 are particularly preferable. .

[0035]

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[0036]

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Specific examples of the quinonediazide compound include a diazobenzoquinone compound and a diazonaphthoquinone compound.
Compounds represented by are preferred.

[0038]

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[0039]

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[0040]

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[0041]

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Specific examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone and the like, and a compound represented by the following chemical formula 33 is particularly preferable.

[0043]

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Specific examples of the nitrobenzyl compound include a nitrobenzyl sulfonate compound and a dinitrobenzyl sulfonate compound, and a compound represented by the following chemical formula 34 is particularly preferable.

[0045]

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Specific examples of the sulfonic acid compound include alkyl sulfonic acid ester, haloalkyl sulfonic acid ester, aryl sulfonic acid ester, imino sulfonate, and the like. Compounds and the like are preferable.

[0047]

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[0048]

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[0049]

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The mixing ratio of the radical generator and / or the acid generator to the polysilane represented by the general formula (I) is 0.1 parts by weight of the radical generator and / or the acid generator based on 100 parts by weight of the polysilane. It is desirable to add 30 to 30 parts by weight, more preferably 1 to 10 parts by weight.
If the mixing ratio of the radical generator and / or the acid generator is less than 0.1 parts by weight, the reaction between the radical or acid generated during exposure and the polysilane may be insufficient.
On the other hand, if the mixing ratio of the radical generator and / or the acid generator exceeds 30 parts by weight, the solubility of the exposed portion in the alkali developing solution may be lowered in the formation of a positive pattern, for example. However, when the above-mentioned halomethyl-s-triazine is used as the radical generator, 0.01 to 3 parts by weight, preferably 1 to 2 of halomethyl-s-triazine are added to 100 parts by weight of the polysilane.
It is possible to obtain a photosensitive composition in which the sensitivity is sufficiently improved even in a small amount such as a weight fraction.

Examples of the solvent include toluene, xylene, dimethylformamide, dimethylacetamide,
Dimethylacetamide, cellosolve, methyl methoxyacetate and the like are used.

Next, the pattern forming method according to the present invention will be described. (First Step) First, a photosensitive composition prepared by dissolving polysilane having a monomer of the general formula (I) as a repeating unit and the radical generator and / or acid generator in the solvent. Is coated on a substrate by, for example, a spin coating method, and then dried to form a photosensitive composition film.

As the substrate, for example, a semiconductor substrate having wiring formed on its surface, a glass substrate having the wiring formed thereon, or the like can be used. (Second Step) Next, the photosensitive composition film is selectively exposed to light and then developed with an aqueous alkali solution to form a positive pattern.

The exposure is carried out through Deep UV, KrF excimer laser light, electron beam, through a desired mask pattern.
It is done by irradiating with X-rays. The irradiation dose at the time of exposure is 10 mJ to 10 J, more preferably 100 mJ to 3
It is desirable to set it to J.

As the alkaline aqueous solution, for example, organic amines such as tetromethylammonium hydroxide and choline, and inorganic alkalis such as KOH and NaOH can be used. The positive pattern after development is washed with pure water.

Next, another pattern forming method according to the present invention will be described. (First Step) First, a photosensitive composition prepared by dissolving polysilane having a monomer of the general formula (I) as a repeating unit and the radical generator and / or acid generator in the solvent. Is coated on a substrate by, for example, a spin coating method, and then dried to form a photosensitive composition film.

(Second Step) Next, the photosensitive composition film is selectively exposed to light, heat-treated, and developed with an organic solvent to form a negative pattern.

In the exposure, Deep UV, KrF excimer laser light, an electron beam, and a desired mask pattern are used.
It is done by irradiating with X-rays. The irradiation dose at the time of exposure is 10 mJ to 10 J, more preferably 100 mJ to 3
It is desirable to set it to J.

The heat treatment is preferably performed at a temperature of 100 to 150 ° C. Examples of the organic solvent include aromatic solvents such as toluene and xylene, or alcohol solvents such as methanol and ethanol, acetone,
Ketone solvents such as methyl ethyl ketone, methyl acetate,
Examples of polar solvents include ketone solvents such as ethyl acetate and butyl acetate.

According to the photosensitive composition of the present invention described above, a polysilane having a monomer of the general formula (I) as a repeating unit and a radical generator such as trihalomethyl-s-triazine and / or Since it contains an acid generator, a photosensitive composition film is formed on the substrate as described in the above-mentioned pattern forming method, and by selectively exposing it, trihalomethyl-in the exposed portion of the photosensitive composition film.
A radical generator and / or an acid generator such as s-triazine is decomposed to generate a radical or an acid, and the radical or acid serves as a catalyst to form the Si-Si main chain of the polysilane of the general formula (I). Cleavage and activation of the -H group occur to lower the molecular weight and selectively generate stable silanol (Si-OH). When an acid generator is used as the photosensitive component, it is preferable to bake before the development processing.
By treating with an alkali developing solution after such exposure, the exposed part of the photosensitive composition film is selectively dissolved and removed to form a positive pattern.

The positive type pattern is entirely exposed to generate silanol (Si-OH) on the entire surface, and then heat treatment is performed to form a siloxane bond (Si-O-Si) having a high cross-linking density on the entire pattern. Is generated. Therefore, it is possible to easily form a highly accurate insulating film pattern that is made of a glass matrix, has high adhesion to the substrate, and has good heat resistance.

Further, according to the photosensitive composition of the present invention, a polysilane having a monomer of the general formula (I) as a repeating unit and a radical generator such as trihalomethyl-s-triazine and / or an acid generator. As described above in the another pattern forming method, the photosensitive composition film is formed on the substrate and selectively exposed, so that trihalomethyl-s is contained in the exposed portion of the photosensitive composition film. A radical generator such as a triazine and / or an acid generator is decomposed to generate a radical or an acid, and the radical or acid serves as a catalyst to form Si of the polysilane of the general formula (I).
Cleavage of the -Si main chain and activation of the -H group occur to lower the molecular weight and selectively generate stable silanol (Si-OH). Further, the heat treatment produces a siloxane bond (Si-O-Si) having a high cross-linking density, which is less soluble in an organic solvent than the polysilane. By performing a development treatment with an organic solvent after such a heat treatment, the unexposed portion of the photosensitive composition film is selectively dissolved and removed to form a negative pattern.

Therefore, according to the photosensitive composition of the present invention, a positive type or negative type pattern can be easily formed. In particular, when a positive type pattern is formed by using halomethyl-s-triazines as a radical generator, the formation of silanol bond in the exposed area is promoted as compared with the conventional photosensitive composition containing only polysilane, and the formation of a silanol bond to the developing solution is promoted. The solubility is increased. Therefore, the cross-sectional shape of the finally formed pattern becomes good, and the resolution is also improved.

Next, the pattern of the colored film according to the present invention will be described in detail. (First Step) First, a photosensitive composition prepared by dissolving polysilane having a monomer of the general formula (I) as a repeating unit and the radical generator and / or acid generator in the solvent. Is coated on a substrate by, for example, a spin coating method, and then dried to form a photosensitive composition film.

(Second Step) After the photosensitive composition film is exposed by irradiating it with a desired pattern of light, the photosensitive composition film is immersed in a solution containing a dye component to be selectively colored.

The exposure is performed by irradiating ultraviolet rays such as deep UV through a desired mask pattern. As the coloring component, for example, a basic dye, an oil-soluble dye, a disperse dye, a pigment or the like can be used. Specific examples of the basic dye include Basic Red 12, Basic Red 27, Basic
Mention may be made of Violet 7, Basic Violet 10, Basic Violet 40, Basic Blue 1, Basic Blue 7, Basic Blue 26, Basic Blue 77, Basic Green 1 and Basic Yellow 21. As the oil-soluble dye, specifically, Solvent Red 125, Solvent Red 132, Solvent Red 83, Solvent Red 109, Solvent Blue 67, Solvent Blue 25, Solvent Yellow 25, Solvent Yellow 89. , Solvent Yellow 149
Can be mentioned. Specific examples of the disperse dye include Desperse Red 60, Desperse Red 72, Desperse Blue 56, Desperse Blue 60 and Desperse Yellow 60. Specific examples of the pigment include Pigment Red 220, Pigment Red 221, Pigment Red 53: 1, Pigment Blue 15: 3, Pigment Blue 60, Pigment Green 7, and Pigment Violet 37. You can

The solution containing the dye component is prepared by dissolving the dye component in alcohol. The concentration of such a solution is preferably 1 to 10% by weight. When the concentration of the solution is less than 1% by weight, it becomes difficult to form a sufficiently colored colored film. On the other hand, if the concentration of the solution exceeds 10% by weight, the formed colored film may have uneven color.

(Third Step) The colored film is formed by heating and drying the photosensitive composition film after coloring.

The heat drying is carried out at 50 to 150 ° C. for 5 to 3
It is preferable to perform it for about 0 minutes. According to the method for forming a colored film of the present invention described above, a polysilane having a monomer of the general formula (I) as a repeating unit and a radical generator such as trihalomethyl-s-triazine and / or an acid generator. By exposing the photosensitive composition film containing the agent to a desired pattern light such as ultraviolet rays,
In the exposed portion of the photosensitive composition film, trihalomethyl-s-
A radical generator such as a triazine and / or an acid generator is decomposed to generate a radical or an acid, and the radical or acid serves as a catalyst to produce S of the polysilane of the general formula (I).
The main chain of i-Si is cleaved and the -H group is activated to lower the molecular weight, and stable silanol (Si-OH) is selectively produced. By immersing in the solution of the dye component after this exposure, the dye component is selectively adsorbed to the exposed portion where silanol is produced and colored. Then, the organic solvent in the solution of the dye component is removed by heating and drying, and the silanol (Si-OH) reacts with each other to form a siloxane bond (Si-O-Si) having a high cross-linking density. A silicon-based matrix having a three-dimensional structure is formed. Therefore, it is possible to form a colored film in which the pigment component is contained in the silicon-based matrix and which has excellent durability and mechanical strength and which has a smooth surface.

By carrying out the first and second steps respectively with a solution of a red dye component, a solution of a blue dye component and a solution of a green dye component, a colored film having colored portions of three primary colors can be formed. .

[0071]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below. (Example 1) First, on the substrate,
100 parts by weight of polysilane A and f shown in Chemical Formula 18 above.
1 part by weight of trihalomethyl-s-triazines in Example 1 was applied by a spin coating method (photosensitive composition) and dried to form a photosensitive composition film having a thickness of 0.3 μm. Subsequently, KrF was selectively exposed to the photosensitive composition film through a mask under the condition of 200 mJ / cm ² . Continue to pre-bake at 100 ° C for 2 minutes, then develop with a 2.38% concentration, 25 ° C tetromethylammonium hydroxide aqueous solution for 90 seconds, rinse with pure water, and heat-dry the water to form a positive pattern. did.

(Examples 2 to 10) Using the photosensitive composition having the composition shown in Table 1 below, except that the exposure and development conditions shown in Table 1 were used, 9 kinds of positives were prepared in the same manner as in Example 1. A mold pattern was formed. The resolution and the cross-sectional shape of the obtained positive patterns of Examples 1 to 10 were examined. The results are shown in Table 1 below.

[0073]

[Table 1]

(Comparative Example) First, a toluene solution (photosensitive composition) containing the polysilane A of Chemical formula 14 was applied on a substrate by a spin coating method and dried to a thickness of 0.
A 3 μm thick photosensitive composition film was formed. Next, KrF
Through the mask to the photosensitive composition film at 300 mJ / c
It was exposed selectively under the condition of m ² . Then, after pre-baking at 100 ° C. for 2 minutes, it is developed with an aqueous solution of 2.38% concentration of tetromethylammonium hydroxide at 25 ° C. for 90 seconds, rinsed with pure water, and dried by heating to form a positive pattern. Formed.

The resolution of the positive type pattern of the obtained comparative example and the sectional shape of the pattern were examined. As a result, the resolution was 0.7 μm and the cross-sectional shape of the pattern was trapezoidal. As is apparent from the above comparative example and Table 1, polysilane A and trihalomethyl-s- were added to Examples 1 to 10.
It can be seen that the photosensitive composition containing triazines has higher sensitivity than the photosensitive composition containing only polysilane of Comparative Example. Further, it can be seen that the patterns formed by the photosensitive compositions containing polysilane A and trihalomethyl-s-triazines in Examples 1 to 10 have excellent resolution and cross-sectional shape.

Example 11 First, as shown in FIG. 1A, an aluminum wiring 12 having a width of 2 μm and a thickness of 1 μm was formed on a substrate 11 with a space width of 2 μm. Subsequently, as shown in FIG. 1B, the aluminum wiring 1
A photosensitive composition similar to that of Example 1 was applied on a substrate 11 containing No. 2 by spin coating and dried to form a photosensitive composition film 13 having a thickness of 2 μm.

Then, as shown in FIG. 1C, ultraviolet rays from a low pressure mercury lamp as a light source were selectively exposed to the photosensitive composition film 13 through a mask 14 under the condition of 500 mJ / cm ² . Subsequently, a heat treatment was carried out at 130 ° C. for 10 minutes, followed by development with xylene for 40 seconds to form a negative pattern. Subsequently, the glass matrix shown in FIG. 1 (d) is formed by heat treatment at 400 ° C. for 1 hour, and 0.7 is formed at a portion corresponding to the wiring 12.
An insulating film pattern 16 was formed in which through holes 15 having a size of μm × 1 μm were formed.

The obtained insulating film pattern 16 has cracks,
No swelling or the like was observed, and it adhered well to the substrate 11, and no reflow or the like was observed around the opening of the through hole 15. In addition, the specific resistance of the insulating film pattern was measured and found to be 5 × 10 ¹⁴ Ωcm.

(Example 12) First, a photosensitive composition having the same composition as in Example 1 was applied onto a transparent substrate made of glass by a spin coating method, and then dried to form a photosensitive composition film having a thickness of 2 μm. (Photosensitive polysilane compound film) was formed. Subsequently, a mask for a color filter was placed on the photosensitive polysilane compound film, and ultraviolet rays from a low-pressure mercury lamp as a light source were applied to the photosensitive polysilane compound film at 600 mJ /
It was exposed selectively under the condition of cm ² . Subsequently, the transparent substrate was immersed at 25 ° C. for 5 minutes in an acetonitrile solution containing 1% by weight of Victoria Blue BH (manufactured by Hodogaya Chemical Co., Ltd .; triphenylmethane dye) as a pigment component. After washing with water, it was dried by heating at 100 ° C. for 30 minutes. As a result, the UV-irradiated part of the photosensitive polysilane compound film was dyed blue.

Next, a mask was placed on the photosensitive polysilane compound film so that the blue dyed portion was covered, and a mask was placed thereon, and ultraviolet rays from a low-pressure mercury lamp as a light source were applied to the photosensitive polysilane compound film at 600 mJ / cm ^2. Exposure was selectively performed under the conditions of. Astrafluoxin FF (manufactured by Hodogaya Chemical Co., Ltd .; methine dye) as a pigment component
2% of the transparent substrate in an acetonitrile solution containing 1% by weight of
It was immersed at 5 ° C. for 5 minutes. After washing with water, it was dried by heating at 100 ° C. for 30 minutes. As a result, the UV-irradiated part of the photosensitive polysilane compound film was dyed red.

Next, a mask is placed on the photosensitive polysilane compound film by shifting the position so as to cover the blue dyed part and the red dyed part, and ultraviolet rays from a low pressure mercury lamp as a light source are applied to the photosensitive polysilane compound film. 600 mJ /
It was exposed selectively under the condition of cm ² . Continuing, 1 wt% of Brilliant Basic Cyanine 6GH (manufactured by Hodogaya Chemical Co., Ltd .; Tonophenylmethane dye) as a pigment component
The transparent substrate was immersed in the containing acetonitrile solution at 25 ° C. for 5 minutes. After washing with water, it was dried by heating at 100 ° C. for 30 minutes. As a result, the UV-irradiated part of the photosensitive polysilane compound film is dyed in green, and a predetermined area is formed into a smooth film colored in red (R), blue (B) and green (G). did it.

[0082]

As described above in detail, according to the present invention, it is possible to provide a photosensitive composition having a high exposure sensitivity, a good cross-sectional shape and an excellent resolution. Further, according to the present invention, a pattern having a good cross-sectional shape and high precision can be formed, and by extension, it can be effectively applied to the manufacture of electronic elements such as semiconductor devices and liquid crystal display devices.

Furthermore, according to the present invention, a colored film having excellent durability and mechanical strength and having a smooth surface can be formed and can be effectively used for forming a color filter of a liquid crystal display device.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a process of forming an insulating film pattern according to Example 11 of the present invention.

[Explanation of symbols]

11 ... Substrate, 12 ... Wiring, 13 ... Photosensitive composition film, 15
… Through hole, 16… Insulating film pattern.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shuji Hayase 1 Komukai Toshiba-cho, Sachi-ku, Kawasaki-shi, Kanagawa Incorporated Toshiba Research and Development Center

Claims (12)

[Claims] 1. A photosensitive composition comprising a polysilane having a monomer of the general formula (I) shown below as a repeating unit and a compound capable of generating a radical or an acid upon irradiation with actinic radiation. . Embedded image However, R ¹ in the formula represents a substituted or unsubstituted aromatic group. 2. The compound which generates a radical or an acid upon irradiation with actinic radiation is represented by the general formula (II) shown below.
The photosensitive composition according to claim 1, which is an organic halide represented by: Embedded image However, in the formula, Q is bromine or chlorine, P is -CQ ₃ ,-
^{_{NH 2, -NHR 3, -N (}} R 3) 2, -OR 3, substituted or unsubstituted phenyl group (wherein, Q is bromine or chlorine, R ³ is a phenyl group, a naphthalene group or having 6 or less carbon A lower alkyl group), R ² is —CQ ₃ , —N.
^{_{H 2, -NHR 3, -N (}} R 3) 2, -OR 3, - (C
H = CH) _n -W, a substituted or unsubstituted phenyl group (wherein Q is bromine or chlorine, R ³ is a phenyl group, a naphthyl group or a lower alkyl group having 6 or less carbon atoms, n is an integer of 1 to 3, W is an aromatic ring, a heterocycle or a general formula shown in the following chemical formula 3.
It is a group represented by (III). ). Embedded image However, Z in the formula represents oxygen or sulfur, and R ⁴ represents a lower alkyl group or a phenyl group. 3. The photosensitive composition according to claim 2, wherein the compound that generates a radical or an acid upon irradiation with actinic radiation is blended in an amount of 0.01 to 3% by weight based on the polysilane. 4. A photosensitive composition containing a polysilane having a monomer of the general formula (I) shown below as a repeating unit and a compound capable of generating a radical or an acid upon irradiation with actinic radiation is coated on a substrate. A pattern comprising a step of drying to form a photosensitive composition film, and a step of irradiating the photosensitive composition film with a desired pattern of light to expose it, and then developing with an alkaline aqueous solution. Forming method. Embedded image However, R ¹ in the formula represents a substituted or unsubstituted aromatic group. 5. The compound, which is contained in the photosensitive composition and generates a radical or an acid upon irradiation with actinic radiation, is an organic halide represented by the general formula (II) shown below. The pattern forming method according to claim 4, which is characterized in that. Embedded image However, in the formula, Q is bromine or chlorine, P is -CQ ₃ ,-
^{_{NH 2, -NHR 3, -N (}} R 3) 2, -OR 3, substituted or unsubstituted phenyl group (wherein, Q is bromine or chlorine, R ³ is a phenyl group, a naphthyl group or having 6 or less carbon A lower alkyl group), R ² is —CQ ₃ , —NH.
^{_{2, -NHR 3, -N (R}} 3) 2, -OR 3, - (CH
= CH) _n -W, a substituted or unsubstituted phenyl group (wherein Q is bromine or chlorine, R ³ is a phenyl group, a naphthyl group or a lower alkyl group having 6 or less carbon atoms, n is an integer of 1 to 3, W Is an aromatic ring, a heterocycle or a general formula shown in the following chemical formula 6.
It is a group represented by (III). ). [Chemical 6] However, Z in the formula represents oxygen or sulfur, and R ⁴ represents a lower alkyl group or a phenyl group. 6. The pattern forming method according to claim 5, wherein the compound that generates a radical or an acid upon irradiation with the actinic radiation is blended in an amount of 0.01 to 3% by weight with respect to the polysilane. 7. A photosensitive composition containing a polysilane having a monomer of the general formula (I) shown below as a repeating unit and a compound capable of generating a radical or an acid upon irradiation with actinic radiation is coated on a substrate. A step of forming a photosensitive composition film by drying, irradiating the photosensitive composition film with a desired pattern of light to expose it, heat-treating it, and developing it with an organic solvent. A characteristic pattern forming method. Embedded image However, R ¹ in the formula represents a substituted or unsubstituted aromatic group. 8. The compound which generates a radical or an acid upon irradiation with actinic radiation contained in the photosensitive composition is an organic halide represented by the following general formula (II). The pattern forming method according to claim 7, which is characterized in that. Embedded image However, in the formula, Q is bromine or chlorine, P is -CQ ₃ ,-
^{_{NH 2, -NHR 3, -N (}} R 3) 2, -OR 3, substituted or unsubstituted phenyl group (wherein, Q is bromine or chlorine, R ³ is a phenyl group, a naphthyl group or having 6 or less carbon A lower alkyl group), R ² is —CQ ₃ , —NH.
^{_{2, -NHR 3, -N (R}} 3) 2, -OR 3 or -
(CH = CH) _n -W, a substituted or unsubstituted phenyl group (wherein Q is bromine or chlorine, R ³ is a phenyl group, a naphthyl group or a lower alkyl group having 6 or less carbon atoms, and n is 1 to 1).
An integer of 3, W is an aromatic ring, a heterocycle or a group represented by the general formula (III) shown in the following Chemical formula 9. ). Embedded image However, Z in the formula represents oxygen or sulfur, and R ⁴ represents a lower alkyl group or a phenyl group. 9. The pattern forming method according to claim 7, wherein the compound that generates a radical or an acid upon irradiation with the actinic radiation is blended in an amount of 0.01 to 3% by weight with respect to the polysilane. 10. A substrate is coated with a photosensitive composition containing a polysilane having a monomer of the general formula (I) shown below as a repeating unit and a compound capable of generating a radical or an acid upon irradiation with actinic radiation. A step of forming a photosensitive composition film by drying, exposing the photosensitive composition film to a desired pattern of light, and exposing the photosensitive composition film after exposure to a solution containing a dye component. A method for forming a colored film, comprising a step of dipping and selectively coloring, and a step of heating and drying the photosensitive composition film after coloring to cure the film. Embedded image However, R ¹ in the formula represents a substituted or unsubstituted aromatic group. 11. The compound, which is contained in the photosensitive composition and generates a radical or an acid upon irradiation with actinic radiation, is an organic halide represented by the following general formula (II). The method for forming a colored film according to claim 10, wherein the colored film is formed. Embedded image However, in the formula, Q is bromine or chlorine, P is -CQ ₃ ,-
^{_{NH 2, -NHR 3, -N (}} R 3) 2, -OR 3, substituted or unsubstituted phenyl group (wherein, Q is bromine or chlorine, R ³ is a phenyl group, a naphthyl group or having 6 or less carbon A lower alkyl group), R ² is —CQ ₃ , —NH.
^{_{2, -NHR 3, -N (R}} 3) 2, -OR 3, - (CH
= CH) _n -W, a substituted or unsubstituted phenyl group (wherein Q is bromine or chlorine, R ³ is a phenyl group, a naphthyl group or a lower alkyl group having 6 or less carbon atoms, n is an integer of 1 to 3, W Is an aromatic ring, a heterocycle or a general formula shown in Chemical formula 12 below.
It is a group represented by (III). ). Embedded image However, Z in the formula represents oxygen or sulfur, and R ⁴ represents a lower alkyl group or a phenyl group. 12. The method for forming a colored film according to claim 11, wherein the compound that generates a radical or an acid upon irradiation with the actinic radiation is blended in an amount of 0.01 to 3% by weight with respect to the polysilane. .