JPH09172009A - Insulating film forming method and insulating film pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an insulating film excellent in film quality by applying to a substrate a solution containing polysilane having a monomer, expressed by the formula, in its main chain as a repeating unit, and heating the substrate in an atmosphere containing oxygen to make the polysilane take on oxygen bridge formation three-dimensional structure. SOLUTION: A solution containing polysilane having a monomer, expressed by the formula, in its main chain as a repeating unit is applied to a substrate. The substrate is dried, and then heated in an atmosphere containing oxygen. Then the polysilane takes on oxygen bridge formation three-dimensional structure. R<1> in the formula represents a substituted or non-substituted aromatic group, and the heat treatment is performed at a temperature of 100-600 deg.C. Exposure is performed in an oxygen atmosphere after the application of the solution containing polysilane to the substrate and before the heat treatment in the oxygen atmosphere. Since a substituted or non-substituted aromatic group, such as phenyl group, is introduced into the R<1> of polysilane in the formula, a formed insulating film has appropriate softness, which enables the prevention of cracking and the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming an insulating film and a method of forming an insulating film pattern, which are applied to the manufacture of electronic devices such as semiconductor devices and liquid crystal display devices, and more particularly to wirings formed on a substrate. The present invention relates to a method of forming an insulating film and a method of forming an insulating film pattern that cover the step portion.

[0002]

2. Description of the Related Art In manufacturing a semiconductor device or a liquid crystal display device, an insulating film is formed on a wiring of a semiconductor device or a liquid crystal display device. By the way, the insulating film covering the wiring is conventionally (1) a method of depositing a silicon compound by a CVD method, and (2) a solution containing an alkoxy group-containing polysiloxane in which an alkoxyl group is substituted on a side chain of polysiloxane is applied. , The side chain alkoxy group is eliminated by moisture and SiO
A method of producing H and condensing to form a Si-O-Si bond to crosslink, (3) applying an alkoxy group-substituted silane such as tetraethoxysilane or an organosilica sol of an alkoxy group-containing siloxane having a low molecular weight. , A method of heating and drying, (4) applying a solution containing polysilane having an alkoxy group on the side chain, desorbing the side chain alkoxy group with water to generate SiOH, condensing and photooxidizing the polysilane main chain. (5) A solution containing a polymer in which polysilane is two-dimensionally spread is applied, and then dried by heating after photooxidation to form a Si-O-Si bond. Method.

However, there is a problem that the flatness of the surface of the insulating film formed by the above-mentioned (1) CVD method is poor. In contrast, the methods (2) to (5) can easily form an insulating film having a flat surface and a desired film thickness. However, in the above method (2), a large alkoxy group is detached along with crosslinking during the heating and drying step, and the volume is significantly shrunk. In addition, there is a problem that storage stability is poor because it is gradually hydrolyzed during storage. In the method (3), a group having a large alkoxy group is detached along with the crosslinking during the heating and drying step, and the volume is significantly shrunk. In particular, since it is a cross-link from a low molecular weight substance, cracks occur in the insulating film formed with the shrinkage. Moreover,
Since the organosilica sol is gradually hydrolyzed during storage, it has a problem of lacking storage stability. (4) above
In methods (5) and (5), it is difficult to form a coating film because the solution (prepolymer) used tends to gel. Moreover, it lacks storage stability.

On the other hand, when a contact hole is formed in the insulating film formed by the above method to obtain a pattern,
Usually, after forming the insulating film, it is necessary to go through the steps of forming a resist pattern, etching using this pattern as a mask, and peeling off the resist pattern, which makes the process complicated. Since the molecular weight of polysilane used as a resist is reduced by exposure to ultraviolet rays, it can be developed and patterned by dissolving it in a polar solvent such as alcohol or ketone. However, the obtained insulating film pattern is not sufficiently satisfactory in terms of adhesion to a substrate or the like and heat resistance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming an insulating film which has excellent surface flatness and prevents cracking due to volume contraction and has good film quality. Another object of the present invention is to provide a method capable of easily forming an insulating film pattern having high adhesion to a substrate and good heat resistance.

[0006]

A method for forming an insulating film according to the present invention is a method in which a solution containing polysilane having a monomer of the general formula (I) represented by the following chemical formula 4 as a repeating unit in its main chain is formed on a substrate. After coating, it is characterized by three-dimensionally oxygen cross-linking by heat treatment in an oxygen-containing atmosphere.

[0007]

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However, R ¹ in the formula represents a substituted or unsubstituted aromatic group such as a phenyl group, a naphthyl group and an anthranyl group. In the method for forming an insulating film according to the present invention, it is allowed to perform exposure in an oxygen atmosphere after applying the solution containing the polysilane onto the substrate and before the heat treatment in the oxygen atmosphere.

The method of forming an insulating film pattern according to the present invention comprises the steps of coating a substrate with a photosensitive composition containing polysilane having the monomer of the general formula (I) as a repeating unit in the main chain and drying it. After selectively exposing the photosensitive composition film to light, it is developed with an aqueous alkaline solution, and the photosensitive composition film pattern after development is heat-treated.

In the method of forming an insulating film pattern according to the present invention, it is allowed to expose the photosensitive composition film pattern after development to the entire surface prior to the heat treatment. Further, in the method for forming an insulating film pattern according to the present invention, it is allowed to immerse the photosensitive composition film after development after the whole surface exposure and before the heat treatment in a sol containing a metal alkoxide.

Another method of forming an insulating film pattern according to the present invention is to coat a substrate with a photosensitive composition containing a polysilane having the above-mentioned monomer of the general formula (I) as a repeating unit in the main chain and dry it. It is characterized by comprising a step and a step of selectively exposing the photosensitive composition film to heat treatment, and then developing with an organic solvent.

In another method of forming an insulating film pattern according to the present invention, the photosensitive composition may further contain an organometallic compound. Further, in another method for forming an insulating film pattern according to the present invention, the pattern after the development is allowed to be heat-treated.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The method for forming an insulating film according to the present invention will be described in detail below. (First Step) First, a solution containing polysilane having the monomer of the general formula (I) as a repeating unit in the main chain is applied onto a substrate by, for example, a spin coating method.

The polysilane is 500-100,000.
A molecular weight of 0, more preferably 1,000 to 10,000
It is desirable to have a molecular weight of 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 the polysilane, for example, (A-1) to (A-12) shown in Chemical formulas 5 and 6 below can be used.

[0015]

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[0016]

[Chemical 6]

As the organic solvent for the polysilane, for example, toluene or xylene can be used. A compound that generates an acid by heating (hereinafter referred to as a thermal acid generator) is allowed to be added to the solution. Examples of such a thermal acid generator include compounds represented by the general formula (II) shown below. The thermal acid generator is preferably added in an amount of 0.05 to 5% by weight based on the polysilane. When the blending amount of the thermal acid generator is less than 0.05% by weight, it becomes difficult to sufficiently reduce the heating temperature and the heating time when the coating film containing polysilane is thermally crosslinked. On the other hand, the blending amount of the thermal acid generator is 20% by weight.
If it exceeds the above range, it becomes difficult to form the coating film, and the electrical characteristics of the insulating film formed by heating the coating film may deteriorate.

[0018]

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However, R ² in the formula represents a substituted or unsubstituted alkyl group or aryl group. 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 coating film on the substrate is heat-treated in an oxygen-containing atmosphere to three-dimensionally oxygen crosslink to form an insulating film.

The oxygen-containing atmosphere may be a gas atmosphere containing oxygen, and an atmosphere containing 1% or more of oxygen is particularly preferable. The heat treatment is preferably performed at a temperature of 100 to 600 ° C. If the heat treatment is performed at less than 100 ° C., sufficient oxidation is not performed, and it becomes difficult to sufficiently perform three-dimensional oxygen crosslinking. On the other hand, when the heat treatment temperature exceeds 600 ° C., the volume shrinkage becomes too large,
A crack may occur in the formed insulating film. A more preferable heat treatment temperature is 200 to 500 ° C.

It is allowed to perform exposure in an oxygen atmosphere after applying the solution containing the polysilane onto the substrate and before the heat treatment in the oxygen atmosphere. This exposure is
The wavelength is 150 to 400 nm, more preferably 200 to 3
It is desirable to use light of 00 nm. The irradiation dose during exposure is 10 mJ to 10 J, more preferably 100 mJ.
It is desirable to set it to J to 3J.

According to the present invention described above, a solution containing a polysilane having a monomer of the general formula (I) as a repeating unit in the main chain is applied onto a substrate, dried, and then heat-treated in an oxygen-containing atmosphere. By doing so, the polysilane is three-dimensionally oxygen-crosslinked. At this time, the general formula (I)
Since a substituted or unsubstituted aromatic group such as a phenyl group is introduced into R ¹ of the polysilane, it is possible to impart appropriate flexibility to the formed insulating film and prevent cracks and the like from being generated. .

The solution containing the polysilane represented by the above general formula has excellent storage stability. Furthermore, if a solution containing a thermal acid generator in addition to polysilane is used as the solution, this solution is applied onto a substrate, and the formed coating film is subjected to heat treatment in an oxygen-containing atmosphere to obtain the thermal acid. The generator decomposes to generate acid. The generated acid contributes to the change of the hydrogen atom of the side chain of the polysilane to the hydroxyl group. Therefore, as compared with the case of using the solution of polysilane alone, the silicon atom of polysilane can be formed into a three-dimensional crosslinked structure having a Si—O—Si bond by a heat treatment at a low temperature for a short time.

Further, prior to the heat treatment of the coating film applied on the substrate, the polysilane in the coating film is decomposed by exposing the entire surface in an atmosphere containing oxygen, and silanol (Si-OH) having a high acidity is decomposed. ) Is selectively generated. After such exposure, heat treatment is carried out in an oxygen-containing atmosphere to obtain a siloxane bond (Si-
O-Si) is generated. Therefore, an insulating film having high adhesion to a substrate and good heat resistance can be easily formed by heat treatment at a low temperature as compared with the above-described method which does not pass through the exposure step.

Next, the method for forming an insulating film pattern according to the present invention will be described in detail. (First Step) First, a photosensitive composition containing a polysilane having a main chain of the monomer of the general formula (I) as a repeating unit is applied on a substrate by, for example, a spin coating method, and then dried. A photosensitive composition film is formed.

The polysilane is used in the range of 500 to 100,000 for the same reason as described in the method of forming the insulating film.
It is desirable to have a molecular weight of, more preferably 1,000 to 10,000. Examples of the polysilane include (A-1) to (A
-12) can be used.

In the photosensitive composition, the following chemical formulas
Alkali-soluble resins (B-1) to (B-8) obtained by copolymerizing the monomer of the general formula (I) shown in (1) with a monomer having a phenol, a carboxylic acid residue or an ether bond are mixed. May be. Such an alkali-soluble resin is preferably mixed in the photosensitive composition in an amount of 95% by weight or less. If the amount of the alkali-soluble resin exceeds 95% by weight, it becomes difficult to form a highly accurate insulating film pattern.

[0029]

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[0030]

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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 has a wavelength of 150 to 400 nm,
More preferably, it is desirable to use light of 200 to 300 nm. The irradiation dose during exposure is 10 mJ to 10 J,
More preferably, it is desirable to set it to 100 mJ to 3J.

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 photosensitive composition film after development is washed with pure water.

(Third Step) Next, the photosensitive composition film pattern after development is exposed on the entire surface, if necessary, and then heat-treated to form an insulating film pattern.

Light having the same wavelength as that of the selective exposure is used for the overall exposure. The heat treatment is 100 to 600.
It is desirable to carry out at a temperature of ℃, preferably 200 to 500 ℃.

After the whole surface exposure and before the heat treatment, Zr,
Immersion in a sol of metal alkoxide such as Al or Ti is allowed. According to the present invention described above, a photosensitive composition containing a polysilane having a monomer of the general formula (I) as a repeating unit in the main chain is coated on a substrate, dried, and then selectively exposed to light. Polysilane in the photosensitive composition film is decomposed and silanol (Si—OH) having high acidity is selectively generated in the exposed area. By developing with an alkaline aqueous solution after such exposure, the exposed part of the photosensitive composition film is selectively dissolved and removed to form a positive pattern. Then, the photosensitive composition film pattern is exposed to the entire surface as necessary to generate silanol (Si-OH) on the entire surface, and then heat-treated to form a siloxane bond (Si-O) having a high crosslinking density on the entire pattern. -Si) 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, after the whole surface exposure and before the heat treatment, by immersing in a sol of a metal alkoxide such as Zr, Al or Ti, silanol (Si-OH) generated by the whole surface exposure and Zr, Al, A metal such as Ti is bonded, and the subsequent heat treatment makes it possible to form an insulating film pattern with further improved adhesion to the substrate and heat resistance with an extremely high crosslinking density.

Next, another method for forming an insulating film pattern according to the present invention will be described in detail. (First Step) First, a photosensitive composition containing a polysilane having a main chain of the monomer of the general formula (I) as a repeating unit is applied on a substrate by, for example, a spin coating method, and then dried. A photosensitive composition film is formed.

The polysilane is used in the range of 500 to 100,000 for the same reason as described in the method of forming the insulating film.
It is desirable to have a molecular weight of, more preferably 1,000 to 10,000. Examples of the polysilane include (A-1) to (A
-12) can be used.

Further, an organometallic compound may be added to the photosensitive composition. Examples of the organometallic compound include those in which various organic groups are directly bonded to a metal such as aluminum, titanium, chromium, zirconium, copper, iron, manganese, nickel, vanadium, and cobalt, or a complex of the metal. it can. Of these organometallic compounds, organozirconium compounds,
Organoaluminum compounds and organotitanium compounds are useful, in particular, 1) alkoxy groups described below for the metal atom,
2) phenoxy group, 3) acyloxy ligand, 4) β-
A complex compound having a diketone ligand, 5) an o-carbonylphenolate ligand and the like bound thereto is preferable.

1) Alkoxy group As the alkoxy group, those having 1 to 10 carbon atoms are preferable, and examples thereof include a methoxy group, an isopropoxy group and a pentoxy group.

2) Phenoxy group Examples of the phenoxy group include a phenoxy group, an o-methylphenoxy group, an o-methoxyphenoxy group, a p-nitrophenoxy group and a 2.6-dimethylphenoxy group.

3) Acyloxy Ligand Examples of the acyloxy ligand include acetato, propionato, isopropylate, butyrato, stearat, ethylacetoacetate, propylacetoacetato, butylacetoacetate, diethylmalato, dibivaloylmethanato. Etc. can be mentioned.

4) β-diketone ligand Examples of the β-diketone ligand include acetylacetonato, trifluoroacetylacetonate, hexafluoroacetylacetonate, and (C-1) to
The ligand of (C-3) etc. can be mentioned.

[0045]

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5) O-Carbonylphenolate Ligand Examples of the o-carbonylphenolate ligand include salicylaldehyde.

Specific examples of the organoaluminum compound include trismethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, trisphenoxyaluminum, trisparamethylphenoxyaluminum, isopropoxydiethoxyaluminum, trisbutoxyaluminum, trisacetoxyaluminum, trisisosodium. Auropionato aluminum, tris acetyl acetonato aluminum, tris trifluoroacetyl acetonato aluminum, tris hexafluoro acetyl acetonato aluminum, tris ethyl acetyl acetonato aluminum, tris diethyl malato aluminum, tris propyl acetyl acetonato aluminum, tris butyl acetoacetate Tanato aluminum, tris divivaro ilme Diisocyanato aluminum, diacetyl acetate shelf closed Viva acryloyl meth diisocyanatohexane aluminum or below of 11, is shown in Chemical Formula 12 (D-1) may include compounds such as the ~ (D-6).

[0048]

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[0049]

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(Second Step) The photosensitive composition film is selectively exposed to light, heat-treated, and then developed with an organic solvent to form a negative insulating film pattern. Thereafter, heat treatment may be performed as necessary.

The exposure has a wavelength of 150 to 400 nm,
It is more desirable to use light of 200 to 300 nm. Irradiation dose during exposure is 10 mJ-10
J, more preferably 100 mJ to 3 J is desirable.

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.

The heat treatment after forming the insulating film pattern is
It is desirable to carry out at a temperature of 100 to 600 ° C, preferably 400 to 500 ° C. According to another method of the present invention described above, a photosensitive composition containing a polysilane having a monomer of the general formula (I) as a repeating unit in the main chain is coated on a substrate, dried, and then selectively Upon exposure, the polysilane in the photosensitive composition film is decomposed and silanol (Si—OH) is selectively generated in the exposed area. After such exposure, the silanol (Si-OH) is selectively cross-linked by heat treatment at a relatively low temperature (for example, 100 to 150 ° C), so that a siloxane bond (Si-O-) having a cross-linking density insoluble in an organic solvent is obtained. Si) is generated in the exposed portion, and selective solubility between the exposed portion and the unexposed portion appears. Subsequently, by developing with an organic solvent, the unexposed portion is selectively dissolved and removed to form a negative type insulating film pattern. After this,
The insulating film pattern is formed at a relatively high temperature (for example, 400 to
By heat treatment at 500 ° C., siloxane bonds (Si—O—Si) having a high cross-linking density are formed 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.

By incorporating an organometallic compound into the photosensitive composition, light (for example, ultraviolet rays) is absorbed in the exposure step and easily cleaved to bond with Si--O. It functions not only as a catalyst for expanding the exposure wavelength region but also as a crosslinking agent. As a result, it is possible to form an insulating film pattern with improved adhesion to the substrate with higher precision.

[0055]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below. Example 1 First, polyphenylsilane having a molecular weight of 5400 was dissolved in xylene to prepare a 20% concentration solution.
Subsequently, this solution was spin-coated on a silicon wafer and baked at 100 ° C. for 5 minutes to give a thickness of 2 μm.
Was formed. Subsequently, the wafer was gradually heated from 100 ° C. to 350 ° C. in an air atmosphere to obtain an insulating film made of a crack-free oxygen-crosslinked silicon body.

The obtained insulating film had an IR spectrum of 100.
Since large absorption due to stretching vibration of Si—O—Si was observed at ⁰ to 1100 cm ⁻¹ , it was confirmed that the structure was crosslinked with oxygen. The volume resistivity of the insulating film was measured and found to be on the order of 10 ¹⁵ Ω · cm.

Further, when the solution was stored at room temperature for 1 month, no progress of gelation was observed. Example 2 First, polyphenylsilane having a molecular weight of 5400 was dissolved in xylene to prepare a 20% concentration solution.
Subsequently, this solution was spin-coated on a silicon wafer and baked at 100 ° C. for 5 minutes to give a thickness of 2 μm.
Was formed. Subsequently, the polysilane film on the wafer is exposed to 500 W deepU in an air atmosphere.
The entire surface was exposed with a V lamp for 1 minute. Thereafter, the wafer was gradually heated from 100 ° C. to 350 ° C. in an air atmosphere to obtain an insulating film made of a crack-free oxygen-crosslinked silicon body.

The volume resistivity of the obtained insulating film was measured and found to be on the order of 10 ¹⁵ Ω · cm. (Example 3) First, 2 g of polyphenylsilane having a molecular weight of 5400 and 0.5 g of a compound (thermal acid generator) having a structure represented by the following Chemical Formula 13 were dissolved in 10 g of xylene. Then, spin coat this solution on a silicon wafer,
By baking at 100 ° C. for 5 minutes, a polysilane film having a thickness of 2 μm was formed. Subsequently, the polysilane film on the wafer was entirely exposed to a 500 W deep UV lamp for 1 minute in an air atmosphere. After that, the wafer was gradually heated from 100 ° C. to 300 ° C. in an air atmosphere to obtain an insulating film made of a crack-free oxygen-crosslinked silicon body.

[0059]

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Comparative Example 1 First, polymethylsilane having a molecular weight of 7400 was dissolved in xylene to prepare a 20% concentration solution. Subsequently, this solution was spin-coated on a silicon wafer and baked at 100 ° C. for 5 minutes to form a polysilane film having a thickness of 1.7 μm. Subsequently, the wafer is gradually heated in an air atmosphere from 100 ° C. to 3
By raising the temperature to 50 ° C., an insulating film having a crack on the surface was obtained.

When the solution was stored at room temperature for 1 month, it was found to gel. Example 4 <Synthesis of Polysilane A> First, in an argon atmosphere, −2
At 0 ° C., 60 ml of dry diethyl ether and 5.35 g of zirconocene dichlore were stirred, to which 1.5M was added.
Of methyllithium was added little by little and stirred for 70 minutes. Subsequently, the mixture was stirred at 0 ° C. for 30 minutes, diethyl ether was removed, and the produced solid was sublimated to obtain zirconocene dimethyl as a catalyst. The zirconocene dimethyl was added to phenylsilane in a molar amount of 50: 1 to carry out polymerization. The polyphenylsilane having the obtained composition was dissolved in toluene, and methanol was added dropwise with stirring to reprecipitate the polyphenylsilane. Similarly, reprecipitation is carried out twice in methinol to obtain a weight average molecular weight of several hundreds.
Synthesize polyphenylsilane of 0, and further 80-90 ℃
Polysilane A was obtained by drying under reduced pressure.

<Pattern Formation> First, as shown in FIG. 1A, an aluminum wiring 2 having a width of 2 μm and a thickness of 1 μm was formed on a substrate 1 with a space width of 2 μm. Then,
As shown in FIG. 1B, a 15% toluene solution of polysilane A is applied onto a substrate 1 containing the aluminum wiring 2 by a spin coating method and dried to form a photosensitive composition film 3 having a thickness of 2 μm. Was formed.

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 3 through a mask 4 under the condition of 500 mJ / cm ² . Subsequently, a positive type pattern was formed by developing for 40 seconds with an aqueous solution of 2.38% and 25 ° C. tetromethylammonium hydroxide. Subsequently, after rinsing with pure water and heating and drying the water, a low pressure mercury lamp was used. The entire surface was exposed to ultraviolet light as a light source under the condition of 1 J / cm ² , and further 450
An insulating film pattern 6 made of a glass matrix shown in FIG. 1 (d) by heating at 1 ° C. for 1 hour and having a through hole 5 of 0.7 μm × 1 μm formed at a position corresponding to the wiring 2. Was formed.

The insulating film pattern 6 thus obtained had no cracks or swelling, was well adhered to the substrate 1, and no reflow was observed around the openings of the through holes 5. In addition, the specific resistance of the insulating film pattern was measured and found to be 5 × 10 ¹⁴ Ωcm.

(Example 5) After the entire surface was exposed according to the same steps as in Example 4, it was immersed in a sol of aluminum alkoxide and further heat-treated at 450 ° C for 1 hour. As a result, it was possible to form an insulating film pattern that was more closely adhered to the substrate than in Example 4.

Example 6 First, as shown in FIG. 2A, 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. Then,
As shown in FIG. 2B, 1 of polysilane A synthesized in Example 4 was formed on the substrate 11 including the aluminum wiring 12.
A 5% toluene solution was applied by spin coating and dried to form a photosensitive composition film 13 having a thickness of 2 μm.

Then, as shown in FIG. 2C, ultraviolet rays from a low pressure mercury lamp as a light source were selectively exposed to the photosensitive composition film 13 through the mask 14 under the condition of 500 mJ / cm ² . Subsequently, after a heat treatment at 130 ° C. for 10 minutes, a negative pattern was formed by developing with xylene for 40 seconds. Subsequently, a heat treatment was performed at 450 ° C. for 1 hour to form a glass matrix shown in FIG.
An insulating film pattern 16 in which a through hole 15 having a dimension of m × 1 μm was formed was 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.

Comparative Example 2 Similar to Example 6, aluminum wiring having a width of 2 μm and a thickness of 1 μm was formed with a space width of 2 μm on the substrate, and the polysilane synthesized in Example 4 was formed on the substrate including the aluminum wiring. A 15% toluene solution of A was applied by a spin coating method and dried to form a photosensitive composition film having a thickness of 2 μm. Subsequently, the photosensitive composition film was selectively exposed to UV light from a low-pressure mercury lamp as a light source through a mask under the condition of 500 mJ / cm ² , and then heat-treated at 130 ° C. for 10 minutes without adding 40 ml of isopropyl alcohol. Developed for seconds. as a result,
The photosensitive composition film was completely dissolved and no pattern was obtained.

Example 7 First, aluminum wiring having a width of 2 μm and a thickness of 1 μm was formed on a substrate with a space width of 2 μm. Then, a photosensitive composition obtained by adding 5% by weight of acetylacenatozirconium to a 15% toluene solution of polysilane A synthesized in Example 4 on the substrate including the aluminum wiring by spin coating, and drying. To form a photosensitive composition film having a thickness of 2 μm.

Then, 250 mJ / cm 2 was applied to the photosensitive composition film through ultraviolet rays from a low pressure mercury lamp as a light source.
Exposure was selectively performed under the conditions of ² . Then at 150 ° C for 10
After performing a heat treatment for 0.5 minute, the resultant is developed with xylene for 40 seconds, so that a portion corresponding to the wiring is 0.7 μm × 1 μm.
A negative pattern in which a through hole having a dimension of m was opened was formed. Subsequently, a heat treatment was performed at 450 ° C. for 1 hour to form an insulating film pattern made of a glass matrix.

No cracks or swellings were observed in the obtained insulating film pattern, and the through hole was well adhered to the substrate, and a through hole having a sharp sectional shape without reflow was formed around the opening. Was there. Also,
When the specific resistance of the insulating film pattern was measured, 2 × 1
0 ¹⁴ Ωcm.

Example 8 First, aluminum wiring having a width of 2 μm and a thickness of 1 μm was formed on a substrate with a space width of 2 μm. Then, a photosensitive composition obtained by adding 5% by weight of acetylacenatozirconium to a 15% toluene solution of polysilane A synthesized in Example 4 on the substrate including the aluminum wiring by spin coating, and drying. To form a photosensitive composition film having a thickness of 2 μm.

Next, 400 mJ / cm of the photosensitive composition film was passed through a mask using ultraviolet rays from a low pressure mercury lamp as a light source.
Exposure was selectively performed under the conditions of ² . Subsequently, after a heat treatment at 150 ° C. for 5 minutes, development was performed with xylene for 40 seconds, so that a portion corresponding to the wiring was 0.7 μm × 1 μm.
The negative type pattern in which the through-hole of the size of was opened was formed. Subsequently, a heat treatment was performed at 450 ° C. for 1 hour to form an insulating film pattern made of a glass matrix.

The obtained insulating film pattern had no cracks or swellings, was well adhered to the substrate, and was formed with a through hole having a sharp cross-sectional shape around the opening without reflow. Was there. Also,
When the specific resistance of the insulating film pattern was measured, 2 × 1
0 ¹⁴ Ωcm.

Example 9 First, aluminum wiring having a width of 2 μm and a thickness of 1 μm was formed on a substrate with a space width of 2 μm. Then, a photosensitive composition obtained by adding 25% by weight of acetylacenatozirconium to a 15% toluene solution of polysilane A synthesized in Example 4 on a substrate including the aluminum wiring by spin coating, and drying. To form a photosensitive composition film having a thickness of 2 μm.

Next, 250 mJ / cm of the photosensitive composition film was passed through a mask through ultraviolet rays from a low pressure mercury lamp as a light source.
Exposure was selectively performed under the conditions of ² . Subsequently, after a heat treatment at 150 ° C. for 5 minutes, development was performed with xylene for 40 seconds, so that a portion corresponding to the wiring was 0.7 μm × 1 μm.
The negative type pattern in which the through-hole of the size of was opened was formed. Subsequently, a heat treatment was performed at 450 ° C. for 1 hour to form an insulating film pattern made of a glass matrix.

The obtained insulating film pattern was free from cracks and swelling, had good adhesion to the substrate, and had a through hole having a sharp cross-sectional shape around the opening with no reflow. Was there. Also,
When the specific resistance of the insulating film pattern was measured, 2 × 1
0 ¹⁴ Ωcm.

(Embodiment 10) First, a width of 2 μm was formed on a substrate.
Aluminum wiring having a thickness of 1 μm was formed with a space width of 2 μm. Subsequently, a photosensitive composition obtained by adding 5% by weight of triacetylacenatoaluminum to a 15% toluene solution of polysilane A synthesized in Example 4 was applied on the substrate including the aluminum wiring by a spin coating method and dried. Thus, a photosensitive composition film having a thickness of 2 μm was formed.

Then, 400 mJ / cm 2 was applied to the photosensitive composition film through ultraviolet rays from a low pressure mercury lamp as a light source.
Exposure was selectively performed under the conditions of ² . Subsequently, after a heat treatment at 150 ° C. for 5 minutes, development was performed with xylene for 40 seconds, so that a portion corresponding to the wiring was 0.7 μm × 1 μm.
The negative type pattern in which the through-hole of the size of was opened was formed. Subsequently, a heat treatment was performed at 450 ° C. for 1 hour to form an insulating film pattern made of a glass matrix.

The obtained insulating film pattern was free from cracks and swelling, had good adhesion to the substrate, and formed a through hole having a sharp cross-sectional shape around the opening without reflow. Was there. Also,
When the specific resistance of the insulating film pattern was measured, 2 × 1
0 ¹⁴ Ωcm.

[0082]

As described in detail above, according to the present invention, it is possible to form an insulating film having excellent surface flatness and preventing cracks due to volume contraction and having good film quality. The present invention has remarkable effects such as being applicable to the production of the electronic device.

Further, according to the present invention, it is possible to easily form an insulating film pattern having a high adhesiveness to a substrate, a flat surface, and good heat resistance, and by extension, an electronic element such as a semiconductor device or a liquid crystal display device. There are remarkable effects such as effective use in the process of forming an insulating film having a contact hole in manufacturing.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a process of forming an insulating film pattern according to a fourth embodiment of the present invention.

FIG. 2 is a cross-sectional view showing a process of forming an insulating film pattern according to a sixth embodiment of the present invention.

[Explanation of symbols]

 1, 11: Substrate, 2, 12: Wiring, 3, 13: Photosensitive composition film, 5, 15: Through hole, 6, 16: Insulating film pattern.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Maho Ito 33 Shinisogo-cho, Isogo-ku, Yokohama-shi, Kanagawa Prefecture

Claims (9)

[Claims] 1. A solution containing a polysilane having a monomer of the general formula (I) represented by the following chemical formula 1 as a repeating unit in its main chain is coated on a substrate and then heat-treated in an oxygen-containing atmosphere to obtain oxygen. A method for forming an insulating film, which comprises cross-linking into a three-dimensional structure. Embedded image However, R ¹ in the formula represents a substituted or unsubstituted aromatic group. 2. The method for forming an insulating film according to claim 1, wherein the heat treatment is performed at a temperature of 100 to 600 ° C. 3. The formation of an insulating film according to claim 1, wherein after the solution containing the polysilane is applied on the substrate and before the heat treatment in the oxygen atmosphere, exposure is performed in the oxygen atmosphere. Method. 4. A step of coating a substrate with a photosensitive composition containing polysilane having a monomer of the general formula (I) represented by the following chemical formula 2 as a repeating unit in a main chain and drying the composition, and the photosensitive composition. A method for forming an insulating film pattern, comprising: a step of selectively exposing the film, followed by development with an alkaline aqueous solution; and a step of heat-treating the photosensitive composition film pattern after development. Embedded image However, R ¹ in the formula represents a substituted or unsubstituted aromatic group. 5. The method for forming an insulating film pattern according to claim 4, wherein the photosensitive composition film pattern after the development is subjected to the entire surface exposure before the heat treatment. 6. The method for forming an insulating film pattern according to claim 5, wherein the photosensitive composition film pattern is immersed in a sol containing a metal alkoxide after the entire surface exposure and before the heat treatment. 7. A step of applying a photosensitive composition containing a polysilane having a main chain of a monomer of the general formula (I) represented by the following chemical formula 3 as a repeating unit onto a substrate and drying the composition, said photosensitive composition A method of forming an insulating film pattern, comprising the steps of selectively exposing the film, heat-treating it, and developing it with an organic solvent. Embedded image However, R ¹ in the formula represents a substituted or unsubstituted aromatic group. 8. The method for forming an insulating film pattern according to claim 7, wherein the photosensitive composition further contains an organometallic compound. 9. The method for forming an insulating film pattern according to claim 7, wherein the photosensitive composition film pattern after development is further subjected to heat treatment.