JPH0915864A - Resist, pattern forming method using it, silicon polymer composite, and manufacture of insulating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist consisting of a polysilane which can precisely form an alkali-developable fine pattern with high sensitivity, and a pattern forming method using this resist. SOLUTION: A resist consisting of a polysilane having a repeat unit represented by a formula is used to form a positive type pattern by alkali development. In the formula, Ar represents a substituted or non-substituted aryl group having 6-24 carbon atoms.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist capable of forming a positive pattern and a pattern forming method using the resist.

The present invention also relates to a silicon polymer composition for producing an insulating film applicable to the production of electronic elements such as semiconductor devices and liquid crystal display devices, and a method for producing the insulating film.

[0003]

2. Description of the Related Art Microfabrication technology by photoetching is used for manufacturing electronic parts such as semiconductor devices and integrated circuits. For example, a resist film is formed on a silicon single crystal wafer or the like by spin coating, a mask having a desired pattern is overlaid thereon, and exposure, development, and rinsing are performed to form a resist film pattern, and then line formation is performed by etching. We are opening windows. In the microfabrication technology used here, the accuracy of the product depends largely on the performance of the resist used, that is, the resolution on the substrate, the accuracy of the photosensitivity, the adhesion to the substrate or the resistance to etching. .

In recent years, expectations for polysilane as such a resist have been increasing, and for example, JP-A-60-228 is used.
No. 542 discloses a technique of forming a positive pattern using polysilane. This is because in a resist made of a silicon-containing compound such as polysilane, oxygen reactive ion etching (oxygen RI
This is because a film like SiO ₂ is formed on the resist surface at the time of E), so that it has a feature of being excellent in oxygen RIE resistance.

However, here, a pattern is formed by irradiating polysilane with actinic rays to generate a volatile photodepolymerization product and volatilizing the generated photodepolymerization product, and such a dry development is performed. It is very difficult to accurately form a fine pattern. Further, in the conventional pattern formation using polysilane, there is a problem that the sensitivity is still insufficient.

On the other hand, in the manufacture of a semiconductor device or a liquid crystal display device, an insulating film is usually formed on the surface of the semiconductor element or the liquid crystal display element or on the wiring in order to ensure insulation from other regions. There is. The insulating film for covering the wiring is formed by, for example, depositing a silicon compound by CVD, applying organosilica sol or the like, and then heating and drying.

In some cases, it is required to pattern the insulating film formed on the wiring to form the contact hole, but the insulating film formed by such a method cannot be easily patterned. . That is, a resist pattern is formed on the formed insulating film,
After patterning the insulating film using this resist pattern as an etching mask, the resist pattern must be removed. Since the process is complicated as described above, the insulating film pattern cannot be obtained at low cost.

On the other hand, a technique has been proposed in which the photosensitivity of polysilane is used to form a polysilane pattern and then the pattern is heated and insulated to simplify the process. That is, since polysilane has a property that its molecular weight is reduced by exposing it to ultraviolet rays, it is possible to form a polysilane film and selectively expose it to a polar solvent such as alcohol or ketone. A pattern is formed by selectively dissolving and developing.
Subsequently, if necessary, the pattern is irradiated with ultraviolet rays, and then heated and dried to polysiloxane siloxane to obtain an insulating film pattern.

However, since the pattern here is composed of one-dimensional siloxane obtained by heating and drying polysilane, there is a problem in reliability such as heat resistance when used as an insulating film. . Moreover, the obtained pattern did not have sufficient adhesion to the substrate.

[0010]

As described above, pattern formation using polysilane as a resist has been attempted, but in the case of a resist made of polysilane, it is difficult to form a fine pattern with high accuracy, and The sensitivity is often insufficient. On the other hand, if pattern formation by alkali development is possible, improvement in pattern accuracy can be expected, but since polysilane is generally insoluble in an alkaline aqueous solution, pattern formation by alkali development cannot be performed.

On the other hand, an insulating film formed of polysilane has the following problems in terms of reliability such as adhesion to a substrate.
I'm still not satisfied.

In view of these problems, the present invention provides a polysilane-containing resist which can be developed with an alkali and can form a fine pattern with high accuracy and high sensitivity, and a pattern forming method using this resist. The first purpose is to provide.

A second object of the present invention is to provide a silicon polymer composition which is excellent in adhesion to a substrate and heat resistance and which can produce an insulating film having high resistance and high strength.

A third object of the present invention is to provide a method capable of easily forming an insulating film having excellent adhesion to a substrate and heat resistance and having high resistance and high strength.

[0015]

The first invention made to achieve the above object is a resist comprising polysilane having a repeating unit represented by the following general formula (1), and a resist containing this polysilane. A pattern forming method comprising a step of forming a film on a substrate, a step of exposing a desired region of a resist film on the substrate, and a step of developing the exposed resist film with an aqueous alkaline solution. That is, the first
The resist of the invention is characterized in that polysilane having a repeating unit represented by the following general formula (1) is used.

[0016]

[Chemical 6]

(In the formula, Ar represents a substituted or unsubstituted aryl group having 6 to 24 carbon atoms.) The second invention is a polysilane having a repeating unit represented by the following general formula (2), and SiO. _There is provided a silicon polymer composition containing ₂ fine powder and at least one fine powder of SiN fine powder.

[0018]

Embedded image

(In the formula, R ¹ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group.) The third invention is a repeating unit represented by the following general formula (2). A step of forming an organosilicon compound film mainly containing polysilane, an exposure step of irradiating a predetermined region of the organosilicon compound film with ultraviolet rays, and an SiO ₂ microscopic film on the exposed part of the organosilicon compound film. There is provided a method for forming an insulating film, which comprises a step of impregnating at least one of powder and SiN fine powder, and a three-dimensional step of heating and drying the organosilicon compound film impregnated with the fine powder.

[0020]

Embedded image

(In the formula, R ¹ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group.) The present invention will be described in detail below.

In the resist of the first invention, by irradiating with energy rays such as light, electron beam and X-ray, the hydrogen atom introduced into one of the side chains of polysilane is changed to a hydroxyl group and Si- An OH bond is formed. The Si-Si main chain of polysilane can also absorb the above-mentioned energy rays and decompose, and then take in oxygen and water in the atmosphere or in the coating film of the resist to form a Si-OH bond.

Here, when the aryl group is introduced into the other side chain of the polysilane as in the first aspect of the invention, the silanol hydroxyl group thus produced has a very high acidity and a large solubility in an alkaline aqueous solution. Indicates. Moreover, compared to the case where an alkyl group is introduced into the side chain, the generated silanol hydroxyl groups are less likely to react with each other and are stabilized without being crosslinked with each other. Therefore, the solubility in the alkaline aqueous solution is completely different between the unexposed portion and the exposed portion, which are made of polysilane that does not have a silanol hydroxyl group,
It is possible to selectively dissolve and remove the exposed portion by alkali development to obtain a positive pattern.

Moreover, in the resist of the first invention,
Since the polysilane in the unexposed area is essentially insoluble in the alkaline aqueous solution, the Si-Si main chain of the polysilane is not always decomposed when irradiated with energy rays, and the difference in the molecular weight between the exposed area and the unexposed area is caused. No need. Therefore, the pattern as described above can be formed with particularly high sensitivity.

Examples of the aryl group introduced into the side chain of the polysilane in the first invention include a phenyl group, a naphthyl group and an anthranyl group. Further, such a polysilane may be a homopolymer or a copolymer, and may be a copolymer with a repeating unit other than the repeating unit represented by the general formula (1). However, in the case of a copolymer, the repeating unit represented by the general formula (1) is 30
% Or more, more preferably 50% or more. The molecular weight of the polysilane is not particularly limited, but the molecular weight is 500 to 100,000, and further 1.00
The thing of 0-10,000 is preferable. If the molecular weight of the polysilane is too low, it is difficult to form a coating film with sufficient durability, and if the molecular weight of the polysilane is too high, the solubility in a solvent decreases, and the formation of a coating film, etc. It tends to be complicated. Here, specific examples of the polysilane that can be used in the first invention will be shown.

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

In the formula, n, m and k indicate the degree of polymerization, and PS is a polysilane skeleton.

Further, such a polysilane can be synthesized by a reductive coupling reaction of RSiHCl _{2 in} the presence of a sodium catalyst, electrolytic polymerization and the like. The copolymer may be synthesized as described above. For example, when the copolymer is synthesized by a reductive coupling reaction, R′R ″ SiCl ₂ (R
′ And R ″ represent a substituted or non-substituted hydrocarbon group.) Further, from the viewpoint of controlling the degree of polymerization, R
SiHACl (A represents a terminal group) or the like may be appropriately copolymerized. However, when polysilane is synthesized by a reductive coupling reaction, the sodium catalyst may remain in the polysilane as ionic impurities.

On the other hand, the above-mentioned polysilane can be synthesized by the dehydrogenation reaction of RSiH _{3 in} the presence of a titanium or zirconium catalyst. At this time, in particular, the polysilane synthesized through the dehydrogenation reaction using a zirconium catalyst does not contain any ionic impurities, and the silanol-containing hydroxyl group bonded to the silicon atom at the polymer terminal is not generated, and the resist As a result, it is very advantageous in forming a fine pattern by alkali development.

In the first invention, a resist comprising the above-mentioned polysilane and a cross-linking agent for polysilane is prepared, and a pattern is formed using this resist, and then the polysilane in the pattern is cross-linked to obtain a resist. The strength and heat resistance of the formed pattern can be improved. As the crosslinking agent, a compound capable of thermally reacting with a hydrogen atom introduced into the side chain of polysilane, specifically, having at least two unsaturated groups in a molecule such as tetravinylsilane or phenylenedialdehyde Unsaturated compounds may be used. At this time, the unsaturated compound is 1 wt% with respect to the polysilane.
%, But if the blending amount is too large, the components that do not contribute to the crosslinking of the polysilane may increase and conversely the heat resistance of the pattern may decrease, so the upper limit of the blending amount of the unsaturated compound is It is preferably set to 30 wt%.

Further, in the resist of the first invention, when the above-mentioned unsaturated compound is blended with polysilane, a radical generator or an ionic catalyst capable of promoting the reaction between polysilane and the unsaturated compound serves as a crosslinking agent. Usually used together. Radical generators that can be used at this time include azobisisobutyronitrile, benzoyl peroxide, dicumyl peroxide, triphenyl t-butyl peroxide, and the like. Ionic catalysts include chloroplatinic acid and chloroplatinic acid. Examples thereof include complexes in which unsaturated groups are coordinated. Moreover, the blending amount of these is 1 for the radical generator.
It is desirable to set it to ˜30 wt%, and 0.1 to 5 wt% with an ionic catalyst. What happens is that the reaction between the polysilane and the unsaturated compound is difficult to proceed when the amount of the radical generator or the ionic catalyst is too small, and conversely, when the amount is too large, the heat resistance of the pattern may be deteriorated. Because.

In the first invention, it is also possible to blend the polysilane as described above and an alkali-soluble organic compound to prepare a resist. In this case, while polysilane which is insoluble in the alkaline aqueous solution serves as a dissolution inhibitor for the alkali-soluble organic compound, when irradiated with an energy ray, the polysilane forms silanol hydroxyl groups and is solubilized in the alkaline aqueous solution. Therefore, the exposed portion can be selectively dissolved and removed by alkali development to form a positive pattern.

As such an alkali-soluble organic compound, an oligomer or polymer having a phenolic hydroxyl group or a carboxylic acid residue can be used. For example, phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol. , M-cresol, p-cresol, bisphenol A, novolac resin obtained by condensation of formaldehyde with phenol such as 4-chloro-3-cresol, poly (p-vinylphenol), poly (p- Isopropenylphenol), poly (m-isopropenylphenol), copolymer of p-hydroxystyrene and methyl methacrylate, copolymer of p-hydroxystyrene and methyl acrylate, p-isopropenylphenol and acrylic acid Copolymer with methyl, p-hydroxys Copolymers of alkylene and methacrylic acid, and the polyamic acid. Here, specific examples of the alkali-soluble organic compound that can be used in the first invention will be shown.

[0038]

Embedded image

[0039]

Embedded image

In the formula, n represents the degree of polymerization.

In the first invention, when the resist is prepared by blending polysilane and the alkali-soluble organic compound, the blending amount of the alkali-soluble organic compound is 95 wt.
It is preferable to set it to be not more than%. This is because if the amount of the alkali-soluble organic compound is too large, the sensitivity of the resist tends to decrease. In order to sufficiently impart the performance of the alkali-soluble organic compound to the resist, it is desirable that the blending amount of the alkali-soluble organic compound be 0.01 wt% or more.

The resist of the first invention is usually prepared by dissolving the above-mentioned polysilane and a polysilane crosslinking agent, which is optionally blended, and an alkali-soluble organic compound in an appropriate organic solvent. Specific examples of the organic solvent here include toluene, xylene, dimethylformamide, dimethylacetamide, methylcellosolve, and o-.
Dichlorobenzene, chloroform, ethanol, i-propyl alcohol, cyclopentanone, cyclohexanone, ethyl cellosolve acetate, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate and the like are exemplified, and these can be used alone or in the form of a mixture.

Next, a pattern forming method using the resist of the first invention will be described. First, the resist solution prepared as described above is applied onto a predetermined substrate. Next, by prebaking the obtained coating film, the organic solvent is evaporated to some extent to form a resist film. Then, the surface of the resist film is irradiated with energy rays such as ultraviolet rays, KrF excimer laser light, electron beams and X-rays through a desired mask pattern. As the energy rays, ultraviolet rays having a wavelength of 400 nm or less are preferable, and the irradiation dose is 0.1 m.
It is desirable to be set to about ^{J / cm 2 ~5J / cm 2} . At this time, any of the contact exposure and the projection exposure can be adopted.

Since the polysilane in the exposed portion produces silanol hydroxyl groups and is solubilized in the alkaline aqueous solution as described above, the exposed portion of the resist film is selectively dissolved by subsequent alkali development. Then, the positive pattern is formed. At this time, as the alkaline aqueous solution, an organic alkaline aqueous solution such as tetramethylammonium hydroxide or choline, or an inorganic alkaline aqueous solution such as potassium hydroxide or sodium hydroxide may be used.
A method such as a spray method can be adopted. Here, it is also possible to form a positive pattern using a hydrofluoric acid aqueous solution instead of the alkaline aqueous solution.

The pattern forming method of the first invention as described above is particularly preferably applied to the multilayer resist system shown below. That is, in this case, first, a flattening agent is applied on the substrate and then usually at 50 to 250 ° C., preferably 80 to 220 ° C. for 0.5 to 120 minutes, preferably 1 to 90.
It is dried for a minute to form a flattening layer having a desired thickness. Examples of the substrate used here include a silicon wafer, a silicon wafer having various insulating films, electrodes, wirings and the like formed on the surface thereof and having a step, a blank mask, and the like.
Further, the flattening agent may be any material as long as it has a purity that does not cause a problem in the manufacture of a semiconductor integrated circuit or the like. Examples of such a flattening agent include a positive resist made of substituted naphthoquinonediazide and a novolak resin, polystyrene, polymethylmethacrylate,
Examples thereof include polyvinyl phenol, novolac resin, polyester, polyvinyl alcohol, polyethylene, polypropylene, polyimide, polybutadiene, polyvinyl acetate and polyvinyl butyral. These resins are used alone or in the form of a mixture.

Then, a resist solution is applied onto the flattening layer thus obtained, and then the temperature is 50 to 200 ° C., preferably 80 to 120.
Prebaking is performed at 0.5 ° C. for 0.5 to 120 minutes, preferably 1 to 60 minutes to form a resist film having a desired thickness. Here, as a method of applying the resist liquid, a spin coating method using a spinner, a dipping method, a spraying method, a printing method, or the like can be adopted. Further, the thickness of the resist film can be arbitrarily adjusted depending on the coating method, the polysilane concentration in the resist solution, the viscosity, and the like.

Subsequently, the resist film is exposed and developed as described above to form a positive pattern,
If necessary, heat treatment at 50 to 200 ° C. for about 0.5 to 120 minutes, preferably step baking is performed. By performing such a heat treatment, when a polysilane crosslinking agent is blended in the resist of the first invention, the silicon atoms of the polysilane in the pattern are bonded through the crosslinking agent and the crosslinking of the polysilane progresses. Strength, heat resistance, etc. are improved. Even when a polysilane cross-linking agent is not blended, since the silicon atoms of the polysilane can be bonded via oxygen atoms by taking in oxygen in the air or the like, the strength of the pattern based on the cross-linking of the polysilane, improvement in heat resistance, etc. Can be expected.

Further, at this time, the pattern formed before the heat treatment as described above is exposed to pre-induce photooxidation of polysilane, radical generation from a radical generator, etc. to crosslink the polysilane during the heat treatment. You may encourage progress. Here, even if the crosslinking agent for polysilane is not particularly blended, the silicon atom of polysilane can strongly crosslink three-dimensionally after taking in oxygen in the atmosphere or the like. Moreover, by performing such exposure, when the main chain of polysilane is cut, silicon atoms are recombined through oxygen atoms, and a glass matrix having excellent strength and heat resistance can be formed. The glass matrix pattern obtained as above can be used as it is as a surface protective film, an insulating film, or the like.

Next, the flattening layer exposed by using the formed pattern as a mask is etched using oxygen gas plasma or a suitable solvent. At this time, an oxygen reactive ion etching method (oxygen RIE method) using oxygen gas plasma is more preferable, and is usually 1 × 10 ⁻⁴ to 1
× 10 ⁻¹ Torr, 0.01 to 10 w / cm ² and 1-1
Treat for 20 minutes. Here, the pattern formed by using the resist of the first invention is exposed to oxygen RIE to form silicon dioxide (SiO ₂ ) or a film similar thereto on the surface layer, and the exposed planarization is performed. 10 layers
-100 times more resistant to oxygen RIE. Therefore, the flattening layer portion exposed from the pattern is oxygen RIE.
The pattern is selectively removed by the method to obtain the optimum pattern profile.

Finally, the substrate is etched by using the pattern thus obtained as a mask. As an etching method at this time, for example, a wet etching method or a dry etching method is adopted, but when a fine pattern of 3 μm or less is formed, the dry etching method is preferable. As the wet etching agent, an aqueous solution of hydrofluoric acid, an aqueous solution of ammonium fluoride, etc. when the silicon oxide film is an etching target, an aqueous solution of phosphoric acid, an aqueous acetic acid solution, an aqueous nitric acid solution, etc. when the aluminum is an etching target, When the chromium-based film is the etching target, an aqueous solution of cerium ammonium nitrate or the like is used.
As the dry etching gas, CF ₄ , C ₂ F ₆ ,
CCl ₄ , BCl ₃ , Cl ₂ , HCl, H _{2 and the} like can be mentioned. These gases are used in combination as required. As the etching conditions, the concentration of the wet etching agent in the reaction tank, the concentration of the dry etching gas, the reaction temperature, and the reaction time are based on the combination of the type of material used to form the fine pattern and the resist used. Etc., but the method is not particularly limited.

After the etching as described above, the pattern formed by using the flattening layer remaining on the substrate and the resist of the first invention is peeled off by, for example, Nagase Kasei's trade name: J-100. Remove with chemicals, oxygen gas plasma, etc.

It should be noted that, in addition to the above steps, it does not matter at all that additional steps may be added depending on the purpose. For example,
For the purpose of improving the adhesion between the resist film made of the resist of the first invention and the flattening layer or the flattening layer and the substrate, a pretreatment step performed before the application of each liquid, and the developer removed after the development of the resist film Examples include a rinsing step performed for the purpose and an ultraviolet ray re-irradiation step performed before dry etching. The case where the resist of the first invention is applied to the multilayer resist system has been described above.
The resist of the present invention can be applied to a conventional single layer resist.

Next, the second invention will be described in detail.

The polysilane which can be used in the silicon polymer composition of the second invention is a compound having a repeating unit represented by the following general formula (2).

[0055]

Embedded image

(In the formula, R ¹ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group.) The aryl group introduced into the side chain of this polysilane includes a phenyl group and a naphthyl group. , Anthranyl group and the like, and the alkyl group includes, for example, a methyl group,
Examples thereof include an ethyl group, a propyl group and a hexyl group. Such polysilane may be a homopolymer or a copolymer, and may be a copolymer with a repeating unit other than the repeating unit represented by the general formula (2). However, in the case of a copolymer, it is preferable that the repeating unit represented by the general formula (2) is contained in an amount of 30% or more, further 50% or more. The molecular weight of the polysilane is not particularly limited, but those having a molecular weight of 500 to 100,000, more preferably 1,000 to 10,000 are preferable. If the molecular weight of polysilane is less than 500,
It becomes difficult to form a coating film having good film quality. On the other hand, if the molecular weight of the polysilane exceeds 100,000, the solubility of the solvent may decrease. Here, in the silicon polymer composition of the second invention, the following polysilane can be used in addition to the polysilane that can be used in the above-mentioned first invention.

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

In the formula, n, m and k indicate the degree of polymerization, and PS is a polysilane skeleton.

In the above general formula (2), when a substituted or unsubstituted aryl group such as a phenyl group is introduced into R ¹ , it is formed by using the silicon polymer composition of the second invention. It is preferable because the insulating film to be formed can be provided with appropriate flexibility and the occurrence of cracks can be surely prevented. However, in the second invention, the crack resistance of the insulating film is improved by adding SiO ₂ fine powder and / or SiN fine powder, as compared with the case of using polysilane alone.
It does not matter if R ¹ is a substituted or unsubstituted alkyl group.

The SiO ₂ fine powder and / or SiN fine powder used in the second invention is not particularly limited, but from the viewpoint of forming a coating film having good flatness and uniformity,
A diameter of 10 μm or less is preferable. The diameter of the fine powder is more preferably 0.1 μm or less.

In the second invention, the compounding amount of the fine powder as described above is preferably 1 to 70 wt%, more preferably 10 to 50 wt% with respect to the polysilane. That is, 1w
If it is less than t%, it is difficult to expect a certain degree of densification or higher resistance in the insulating film to be formed, while if it exceeds 70 wt%, it may be difficult to form a coating film with good film quality.

Furthermore, an organometallic compound may be added to the silicon polymer composition of the second invention. That is,
Such an organometallic compound serves as a cross-linking agent for polysilane and contributes to the improvement of the adhesion to the substrate when the insulating film is formed. Furthermore, in forming the insulating film, when the film of the silicon polymer composition is exposed to light before being dried by heating, the organometallic compound absorbs ultraviolet rays to easily open the ring to form a silanol ( Since it combines with Si-OH), it also functions as a catalyst for expanding the exposure sensitivity and the exposure wavelength region.

Examples of the organic metal compound include compounds in which various organic groups are directly bonded to metals such as aluminum, titanium, chromium, zirconium, copper, iron, manganese, nickel, vanadium and cobalt, or complexes of the above metals. Can be mentioned. Among these organometallic compounds, organozirconium compounds, organoaluminum compounds, and organotitanium compounds are particularly useful, and as the ligand for forming the above-described organic group and complex,
1) alkoxy group, 2) phenoxy group, 3) acyloxy ligand, 4) β-diketone ligand, 5) o-carbonylphenolate ligand and the like. Specifically, an organometallic compound having the following substituents or ligands bonded to a metal atom 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, ethylacetoacetato, propylacetoacetato, butylacetoacetato, diethylmalato, dibivaloylmethanato. Etc. can be mentioned.

4) β-diketone ligand Examples of the β-diketone ligand include acetylacetonato, trifluoroacetylacetonato, hexafluoroacetylacetonate, and (C-1) to (C-1) shown in Chemical Formula 20 below.
The ligand of (C-3) etc. can be mentioned.

[0070]

Embedded image

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, diacetylacetonatobis divinyl Varo yl meth diisocyanatohexane aluminum or below of 21, is shown in Chemical formula 22 (D-1) may include compounds such as the ~ (D-6).

[0073]

Embedded image

[0074]

Embedded image

Further, in the silicon polymer composition of the second invention, a radical generating agent is used as a sensitizer when exposing the film before heating and drying the film for forming an insulating film or forming a pattern. Agents or acid generators can also be added. The radical generator is a compound that generates a radical upon irradiation with actinic radiation, and the acid generator is a compound that generates an acid upon irradiation with actinic radiation.

Examples of the radical generator include azo compounds such as azobisisobutyl nitrile, peroxides such as benzoyl peroxide and ditertiary butyl peroxide, benzoin, benzoin alkyl ether, benzoin alkylaryl thioether, benzoyl aryl ether, and the like. Examples thereof include benzoylalkylaryl thioethers, benzylaralkylethanols, phenyl-glyoxal alkylacetals, alkylaryl ketones such as benzoyloxime, and organic halides represented by the following chemical formula 23.

[0077]

Embedded image

Among the above organic halides, the trihalomethyl-s-triazines described in US Pat. No. 3,779,778, that is, the compounds represented by the general formula (3) shown in the following chemical formula 24 are preferable. Specifically, 2,
4-bis (trichloromethyl) -6-methyl-s-triazine and 2,4,6-tris (chloromethyl) -s-triazine can be mentioned.

[0079]

Embedded image

[0080] However, Q in the formula is a bromine atom or a chlorine atom, P is ^{_{-CQ 3, -NH 2, -NHR 3}} , -N
(R ³⁾ _2, -OR ^3, substituted or unsubstituted phenyl group (wherein, Q is a bromine atom or a chlorine atom, R ³ is a phenyl group, a naphthyl group, or more than 6 lower alkyl group having a carbon.) , R ² is —CQ ₃ , —NH ₂ , —NH
^{R 3, -N (R 3)} 2, -OR 3, - (CH = CH) n
-W, a substituted or unsubstituted phenyl group (wherein Q is a bromine atom or a chlorine atom, 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 And an aromatic group, a heterocyclic group, or a group represented by the general formula (4) shown below.

[0081]

Embedded image

However, in the formula, Z represents an oxygen atom or a sulfur atom, and R ⁴ represents a lower alkyl group or a phenyl group.

In the general formula (3), the aromatic ring or heterocycle represented by W may be further substituted.
Examples of such substituents include chlorine atom, bromine atom, phenyl group, lower alkyl group having 6 or less carbon atoms, nitro group, phenoxy group, alkoxy group, acetoxy group, acetyl group, amino group and alkylamino group. Can be mentioned.

Among the above organic halides, the compounds further substituted with vinylhalomethyl-s-triazine disclosed in US Pat. No. 3,987,037 are preferable. The vinylhalomethyl-s-triazine compound is
A photodecomposable s-triazine having at least one trihalomethyl group and a group conjugated with a triazine ring by at least one ethylenically unsaturated bond, wherein R ² in the general formula (3) is It is a compound in which-(CH = CH) _n- W is introduced.

Specific examples of the trihalomethyl-s-triazines represented by the general formula (3) are shown below in Chemical formula 26, and other radical generators are shown in Chemical formulas 27 to 31 below.

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

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, diazonium salts, ammonium salts and the like. Preferably, the compound represented by the following chemical formula 32 can be mentioned.

[0094]

Embedded image

(In the formula, R ^{9 to} R ¹¹ may be the same or different from each other, and each represents a hydrogen atom, an amino group,
Nitro group, cyano group, substituted or unsubstituted alkyl group or alkoxy group, X is SbF ₆ , AsF ₆ , P
F ₆ , BF ₄ , CF ₃ CO ₂ , ClO ₄ , CF ₃ S
O ₃ , or selected from the group shown below. )

Embedded image

(Provided that R ¹² is a hydrogen atom, an amino group, an anilino group, a substituted or unsubstituted alkyl group or an alkoxy group, R ¹³ and R ¹⁴ may be the same or different, and are substituted or An unsubstituted alkoxy group, R ¹⁵ represents a hydrogen atom, an amino group, an anilino group, a substituted or unsubstituted alkyl group or an alkoxy group.) Furthermore, the compounds represented by the following Chemical Formulas 34 and 35 are also
It is mentioned as a preferable onium salt.

[0097]

Embedded image

In the formula, R ⁹ , R ¹⁰ and X are the same as above.

[0099]

Embedded image

In the formula, R ⁹ , R ¹⁰ and X are as defined above.

Specific examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, and the like. In particular, the compounds represented by the chemical formulas 36 and 37 below. Is preferred.

[0102]

Embedded image

(In the formula, R ¹⁶ represents a trichloromethyl group, a phenyl group, a methoxyphenyl group, a naphthyl group or a methoxynaphthyl group.)

Embedded image

(In the formula, R ^{17 to} R ¹⁹ may be the same or different and each represents a hydrogen atom, a halogen atom, a methyl group, a methoxy group or a hydroxyl group.) The quinonediazide compound is specifically, Specific examples thereof include diazobenzoquinone compounds and diazonaphthoquinone compounds, and the compounds represented by the following Chemical Formulas 38 to 41 are particularly preferable.

[0105]

Embedded image

[0106]

Embedded image

[0107]

Embedded image

(In the formula, R ²⁰ is --CH _2- , --C (C
_{H 3) 2 -, - C} (= O) -, or -SO ₂ - indicates, q is an integer from 1 to 6, the sum of r is an integer of 0 to 5, and q and r are 1-6 . )

Embedded image

(In the formula, R ²¹ is a hydrogen atom or a methyl group,
R ²² is _{-CH 2 -, - C (CH} 3) 2 -, - C (= O)
-, or -SO ₂ - indicates, s is an integer from 1 to 6, t is the sum of the 0-5 integer, s and t is 1-6. ) Specific examples of the sulfone compound include β-ketosulfone and β-sulfonylsulfone.
In particular, a compound represented by the chemical formula shown below in Chemical Formula 42 is preferable.

[0110]

Embedded image

(In the formula, R ^{23 to} R ²⁶ may be the same or different, and each is a substituted or unsubstituted alkyl group or a halogen atom, and Y is —C (═O) — or —SO ₂ ). -Indicates-, and u is an integer of 0 to 3.) Specific examples of the nitrobenzyl compound include a nitrobenzyl sulfonate compound and a dinitrobenzyl sulfonate compound. The compounds represented are preferred.

[0112]

Embedded image

(Wherein R ²⁷ is a substituted or unsubstituted alkyl group, R ²⁸ is a hydrogen atom or a methyl group, R ²⁹ is a group selected from the group shown below, and v is an integer of 1 to 3) is there.)

Embedded image

(However, R ³⁰ is a hydrogen atom or a methyl group, R ³¹ and R ³² may be the same or different and each represents a substituted or unsubstituted alkoxy group.) As the sulfonic acid compound Are specifically alkyl sulfonates, haloalkyl sulfonates,
Examples thereof include aryl sulfonates and imino sulfonates, and the compounds represented by the following chemical formulas 45 to 47 are particularly preferable.

[0115]

Embedded image

(In the formula, R ³³ and R ³⁴ may be the same or different from each other, and a hydrogen atom or a substituted or unsubstituted alkyl group, R ³⁵ and R ³⁶ may be the same or different from each other. And each represents a hydrogen atom, a substituted or unsubstituted alkyl group or aryl group.)

Embedded image

(In the formula, R ³⁷ is a hydrogen atom or a substituted or unsubstituted alkyl group, and R ³⁸ and R ³⁹ may be the same or different from each other, and each is a substituted or unsubstituted alkyl group or aryl group. And R ³⁸ and R ³⁹ may be bonded to each other to form a ring structure.)

Embedded image

(In the formula, Z represents a fluorine atom or a chlorine atom.) The compounding amount of the sensitizer as described above is 0 with respect to 100 parts by weight of the polysilane represented by the general formula (2). ．
It is preferably 1 to 30 parts by weight, more preferably 1 to 10 parts by weight. If the compounding amount of the sensitizer is less than 0.1 part by weight, the reaction between radicals or acids generated during exposure and polysilane may be insufficient. On the other hand, if the blending amount of the sensitizer exceeds 30 parts by weight, the solubility of the exposed portion in the alkaline developer tends to be lowered in the formation of a positive pattern, for example. When halomethyl-s-triazines are used as the sensitizer, 0.01 to 3 parts by weight, preferably 1 to 2 parts by weight of this compound is added to 100 parts by weight of the polysilane. However, a silicon polymer composition with sufficiently improved sensitivity can be obtained.

The silicon polymer composition of the second invention comprises the above-mentioned polysilane, fine powder of at least one of SiO ₂ fine powder and SiN fine powder, and an organometallic compound, a radical generator and Acid generator,
It is prepared by dissolving in a suitable organic solvent. Examples of the organic solvent that can be used here include toluene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl acetate cellosolve, butyrolactone, and butyl lactic acid, and these may be used alone or in the form of a mixture. it can. At this time, the fine powder is preferably dispersed using a dispersant such as silica sol, various kinds of surfactants, polymers having a polar group or a functional group.

In producing an insulating film using such a silicon polymer composition, first, a solution containing this composition is prepared and applied on a predetermined substrate by spin coating or the like, and then 50-150. It is dried at a temperature of about ° C to volatilize the solvent to form an organic silicon compound film mainly containing organic polysilane.

Here, as the substrate, for example, a transparent substrate made of translucent glass or resin, a semiconductor substrate having wiring formed on its surface, a glass substrate having the wiring formed thereon, or the like can be used.

Next, the coating film on the substrate is heat-treated in an oxygen-containing atmosphere to three-dimensionally crosslink with oxygen 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. When the heat treatment temperature is lower 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, and cracks may occur in the formed insulating film. A more preferable heat treatment temperature is 200 to 500 ° C.

In the insulating film thus obtained by using the silicon polymer composition of the second invention, vitrified silicon having a three-dimensional structure of Si--O--Si bond by oxygen crosslinking three-dimensionalization as described above. Since the system matrix is formed, the adhesion to the substrate and the heat resistance are very excellent. Moreover, the silicon polymer composition of the second invention contains SiO
_Since at least one of ₂ fine powder and SiN fine powder is blended, an insulating film having excellent characteristics such as high resistance and high strength can be produced by using this composition. That is, by mixing the SiO ₂ fine powder, the density of the film is increased, and a film having high resistance, high strength and dielectric breakdown resistance can be formed. Also,
By mixing the SiN fine powder, the density of the film is increased, and an insulating film having high resistance, high strength, an ion trapping property, and a H ₂ O barrier property can be formed.

After the solution containing the above-mentioned silicon polymer composition is applied onto the substrate to form a film, it is preferable that the entire surface is exposed to ultraviolet rays in an oxygen-containing atmosphere before the film is heat-treated. In this exposure step, the wavelength of ultraviolet rays may be about 150 to 400 nm, but especially 2
Irradiation with ultraviolet rays having a wavelength of 00 to 300 nm is preferable. The irradiation dose is 10 mJ to 10 J, and further 10
It is preferably set to about 0 mJ to 3J.

By performing the entire surface exposure in this way,
Polysilane in the film is decomposed to generate a silanol bond (Si-OH) having high acidity. By heating the organosilicon compound film after such exposure, a siloxane bond (Si-O-Si) having a high cross-linking density is entirely formed.
Are quickly formed. Therefore, heat treatment can be performed at a lower temperature than in the case where the exposure step is not performed, and an insulating film having high adhesion to a substrate and good heat resistance can be easily formed.

The organosilicon compound film after the whole surface exposure is
Before the heat treatment, it may be immersed in a sol of a metal alkoxide such as silicon, zirconium, aluminum or titanium. As a result, the silanol (Si-OH) generated by the overall exposure is bonded to the metal such as silicon, zirconium, aluminum, and titanium, and the heat treatment after that results in an extremely high crosslink density, adhesion to the substrate, and heat resistance. It is possible to obtain an insulating film having an improved state.

It is also possible to manufacture a patterned insulating film by using the silicon polymer composition of the second invention. The methods for obtaining the positive pattern and the negative pattern will be described in detail below.

The positive type pattern can be formed when polysilane in which R ¹ is a substituted or unsubstituted aryl group in the general formula (2) is used. That is, first, such polysilane, SiO ₂ fine powder, and SiN
At least one of the fine powders and, if necessary, components such as an organometallic compound are mixed to prepare a silicon polymer composition in the same manner as described above, and a solution containing this composition is applied onto a substrate. To form an organosilicon compound film.

Then, a predetermined region of this organosilicon compound film is irradiated with ultraviolet rays to selectively expose it. The pattern exposure here can be performed under the same conditions as described above. The wavelength of ultraviolet rays may be about 150 to 400 nm, but it is particularly preferable to irradiate ultraviolet rays having a wavelength of 200 to 300 nm. The irradiation dose is 10 mJ to 10 J,
Further, it is preferably set to about 100 mJ to 3J.

The organic silicon compound film after pattern exposure is
The exposed area is selectively dissolved and removed by developing with an alkaline aqueous solution. As the alkaline aqueous solution, for example, an organic alkali such as tetramethylammonium hydroxide and choline; an inorganic alkali such as KOH and NaOH can be used. It is also possible to dissolve and remove the exposed portion by using a hydrofluoric acid aqueous solution. The organic silicon compound film after development is washed with pure water as appropriate.

After that, the organosilicon compound film is exposed to the whole surface in an oxygen-containing atmosphere, if necessary, and then 1
By performing heat treatment at a temperature of 00 to 600 ° C., preferably 200 to 500 ° C., a patterned insulating film is obtained.

The entire surface exposure can be performed under the same conditions as the above-mentioned pattern exposure.

In the formation of the positive type pattern as described above, the polysilane in the film is decomposed by selectively exposing the organic silicon compound film to light, and the silanol group (Si) having a high acidity is exposed in the exposed area. -OH) is selectively formed. By developing with an alkaline aqueous solution after such exposure, the exposed portion of the organosilicon compound film is selectively dissolved and removed to form a positive pattern. Then, the organosilicon compound film pattern is exposed on the entire surface if necessary, so that the silanol group (S
i-OH) is formed, and heat treatment is performed thereafter to form a siloxane bond (S
i-O-Si) is formed. Therefore, it is possible to easily form a highly precise pattern made of a glass matrix and having high adhesion to the substrate and good heat resistance.

On the other hand, the negative pattern can be formed not only when R ¹ in the general formula (2) is an aryl group but also when this group is an alkyl group. In forming the negative pattern, first, the organosilicon compound film is selectively exposed to light, heat-treated, and then developed with an organic solvent to selectively dissolve and remove the unexposed portion.

The pattern exposure can be performed under the same conditions as described above. That is, the wavelength of ultraviolet rays is 150 to 40
It may be about 0 nm, but it is particularly preferable to irradiate with ultraviolet rays having a wavelength of 200 to 300 nm. The irradiation dose is preferably set to about 10 mJ to 10 J, and more preferably about 100 mJ to 3 J.

The heat treatment before development is preferably carried out at a temperature of 100 to 150 ° C., though it depends on the heating time. If the temperature is lower than 100 ° C., the cross-linking in the exposed area where the silanol hydroxyl group is generated may be insufficient.
If the temperature exceeds ℃, the crosslinking of the silicon polymer may proceed even in the unexposed area, and in any case, it becomes difficult to pattern the organosilicon compound film with high accuracy.

As the organic solvent, for example, an aromatic solvent such as toluene or xylene, or methanol,
Examples thereof include alcohol solvents such as ethanol, ketone solvents such as acetone and methyl ethyl ketone, and polar solvents such as ester solvents such as methyl acetate, ethyl acetate and butyl acetate. Further, R ^{1 in the} above general formula (2) is
When a polysilane in which is a substituted or unsubstituted aryl group is used, the organosilicon compound film is irradiated with ultraviolet rays in advance to develop silanol-containing hydroxyl groups before development, and development with an aqueous alkaline solution or aqueous hydrofluoric acid solution is performed. It is also possible to do

The organic silicon compound film after development is 100 to 600 ° C., preferably 200 to 50 in an oxygen-containing atmosphere.
By performing heat treatment at a temperature of 0 ° C., a patterned insulating film is obtained.

In the formation of the negative pattern as described above, by selectively exposing the organosilicon compound film, polysilane in the film is decomposed and silanol-containing hydroxyl groups (Si-OH) are selected in the exposed area. To generate. After such exposure, a relatively low temperature (for example, 100 to 150) is used.
The silanol-containing hydroxyl group (Si-OH) is selectively crosslinked by heat treatment at (° C). As a result, a siloxane bond (Si-O-Si) having a crosslink density that is insoluble in the solvent
Are formed in the exposed portion, and selective solubility appears between the exposed portion and the unexposed portion. Then, by developing with an organic solvent, the unexposed portion is selectively dissolved and removed to form a negative pattern. Thereafter, the entire patterned organosilicon compound film is heat-treated at a relatively high temperature (for example, 200 to 500 ° C.), so that a siloxane bond (Si—O—Si) having a high crosslink density is generated throughout. Therefore, it is possible to easily form an insulating film pattern made of a vitrified silicon-based matrix, which has high adhesion to the substrate and has good heat resistance.

The shape of the obtained pattern is superior to the negative type pattern, but the positive type pattern has an advantage that an alkaline aqueous solution which has little influence on the environment can be used.

The silicon polymer composition of the second invention contains polysilane having a hydrogen atom directly bonded to a silicon atom in a side chain, and one fine powder of either SiO ₂ fine powder or SiN fine powder. It is characterized by. Therefore, by using this composition, Si
It is composed of a vitrified silicon-based matrix having a three-dimensional structure of —O—Si bond, and Si is contained in the matrix.
An insulating film impregnated with either one of O ₂ fine powder and SiN fine powder can be manufactured. Since the obtained insulating film contains the fine powder as described above, the density of the film is increased, the resistance is high, and the strength is high.
When fine powder of iO ₂ is used, the dielectric breakdown resistance can be further enhanced. Further, when SiN fine powder is used, ion trapping property and H ₂ O barrier property can be imparted.

Next, the method of manufacturing the insulating film of the third invention will be described in detail.

In the production method of the third invention, polysilane having a repeating unit represented by the following general formula (2) can be used as the silicon polymer.

[0145]

Embedded image

(In the formula, R ¹ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group.) That is, the same as the polysilane in the silicon polymer composition of the second invention described above. Compounds can be used. When a film containing such polysilane is irradiated with ultraviolet rays on a predetermined region thereof and then immersed in a solution containing fine powder such as SiO ₂ , the fine powder is selectively impregnated in the ultraviolet irradiation part. In general, when polysilane absorbs ultraviolet energy, Si-Si bond is broken, and then oxygen and moisture in the air are taken in and oxidized, so that two silanol-containing hydroxyl groups (Si-OH) are contained in each silicon atom. Since it can be generated, the fine powder is selectively adsorbed on the ultraviolet irradiation portion of the polysilane based on the interaction between the silanol-containing hydroxyl group and the fine powder.

Further, in the polysilane having the repeating unit represented by the above general formula (2), the hydrogen atom directly bonded to the silicon atom in its side chain is also converted into a silanol group by irradiation with ultraviolet rays. Therefore, as the sensitivity to ultraviolet rays increases, three silanol-containing hydroxyl groups can be generated for each silicon atom, and as a result, the speed at which fine powder is adsorbed is significantly increased, and the time required for impregnation is greatly increased. It can be shortened.

On the other hand, in the third invention, as the fine powder to be impregnated in the silicon-based matrix mainly composed of the photo oxide of polysilane, the same SiO as in the second invention is used.
₂ Fine powder and SiN fine powder can be used, and the particle size thereof is preferably 10 μm or less, more preferably 0.1 μm or less for the same reason as described above.

The solvent used when preparing the solution containing such fine powder includes water, alcohol, etc., and the concentration of the fine powder in the solution is 1 to 10 wt.
% Is preferable. That is, the concentration is 1 wt%
If it is less than the above range, it becomes difficult to obtain an insulating film containing a sufficient amount of fine powder, and if the concentration exceeds 10 wt%, the composition of the obtained insulating film may be uneven.

Further, a sol solution of a metal alkoxide or a decomposition product thereof may be used and fine powder may be mixed therein. The metal alkoxide here may be a semi-metal alkoxide, for example, ethoxide such as silicon, aluminum, zirconium, or titanium is dissolved or dispersed in a mixed solution of alcohol and water, and then acid is added to form a sol. After that, it is prepared by blending SiO ₂ fine powder and the like. The amount of the metal alkoxide compounded may be appropriately set within the range where the fluidity of the solution is not impaired, and is specifically about 70 wt% or less with respect to the solvent.

In the third invention, after irradiating a predetermined region of the polysilane-based organosilicon compound film with ultraviolet rays, it is immersed in the sol containing the above-mentioned SiO ₂ fine powder and the ultraviolet irradiation portion If the fine powder is poorly dispersible in water, alcohol, etc., the fine powder can be favorably dispersed in the sol and then adsorbed.

Further, regarding the sol solution of silicon alkoxide or its decomposition product, when the organic silicon compound film is immersed, the silicon alkoxide or its decomposition product is adsorbed together with the fine powder to form the organic silicon compound film. When heated and dried, they interact with the silanol hydroxyl groups generated by irradiation of polysilane with ultraviolet rays. Therefore, it directly participates in the three-dimensional structure of the Si-O-Si bond as a cross-linking component and contributes to the improvement of the durability of the insulating film. Here, a catalyst that accelerates the reaction between the alkoxide of silicon or its decomposition product and the silanol hydroxyl group generated by irradiation of polysilane with ultraviolet rays may be added to the sol solution.

At this time, it is possible to accelerate the adsorption rate of the fine powder in the impregnation step by appropriately using a hydrophilic organic solvent such as acetonitrile, dioxane, or tetrahydrofuran. However, when a water-soluble organic solvent is used in combination, the amount is preferably set to 20 wt% or less. The reason for this is that when the amount of the water-soluble organic solvent in the solution is large, the elution of the film in the impregnation step tends to be promoted.

In particular, the sol solution of the silicon alkoxide or its decomposition product may be impregnated into the organic silicon compound film after the step of impregnating the fine powder without blending the fine powder. In this case, the exposed portion of the organic silicon compound film is impregnated with fine powder such as SiO ₂ and then the sol solution is impregnated into the organic silicon compound film prior to the step of heating and drying. Also in this case, since the silicon alkoxide or its decomposition product becomes a cross-linking component and is incorporated into the silicon-based matrix having a three-dimensional structure of Si—O—Si bond, as a result, an insulating film having excellent durability and the like can be obtained. It becomes possible to obtain.

When the insulating film of the present invention is manufactured using the polysilane and the fine powder as described above, first, a solution containing polysilane is prepared and a transparent substrate or a semiconductor substrate made of translucent glass or resin. After applying on 50
It is dried at a temperature of about 150 ° C. to volatilize the solvent and form an organosilicon compound film mainly containing polysilane. At this time, as a solvent for polysilane, toluene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl acetate cellosolve, butyrolactone, butyl lactic acid, etc. can be used. After filtering with a filter of about 1 μm, it may be applied onto the substrate by spin coating or the like.

The solution containing polysilane used here contains the organometallic compound as described in the second invention, the radical generator as a sensitizer and the acid generator. Good. In this case, it is preferable that the blending amount of these components is approximately the same as the above-mentioned amounts.

Then, a predetermined region of the organic silicon compound film on the substrate is irradiated with ultraviolet rays from a high pressure mercury lamp, a xenon lamp, an excimer laser or the like. By irradiating with ultraviolet rays in this manner, the polysilane used in the third invention absorbs the energy of ultraviolet rays to break the Si-Si bond, and then is oxidized by taking in oxygen and moisture in the atmosphere, A silanol-containing hydroxyl group is formed with a hydrogen atom directly bonded to a silicon atom in a side chain.

In the exposure process as described above, the wavelength of ultraviolet rays may be about 150 to 400 nm, but when the organic silicon compound film is irradiated with ultraviolet rays having a wavelength of 200 to 300 nm, the film is sufficiently insulated. An insulating film can be easily obtained. The irradiation dose is preferably set to 10 mJ to 10 J, and more preferably 100 mJ to 3 J. That is, when the irradiation amount exceeds 10 J, the exposure time becomes long and the manufacturability is deteriorated, and pinholes and the like tend to occur to deteriorate the film quality. On the other hand, if it is less than 10 mJ, the exposure of the polysilane to the ultraviolet-irradiated portion of the polysilane may be insufficient due to insufficient exposure.

Next, the organic silicon compound film is applied to a solution containing fine powder such as SiO _{2 at} a temperature of 0 to 50 ° C. for 0.5 to
Soak for about 10 minutes. Here, the fine powder is selectively adsorbed on the ultraviolet irradiation portion of the organosilicon compound film in which the silanol-containing hydroxyl group is generated. The organic silicon compound film after impregnation is washed with water as appropriate. Then, the organic silicon compound film is applied to 50 to 15
By heating and drying at 0 ° C. for about 5 to 30 minutes, the solvent that has penetrated into the organic silicon compound film is removed, and a large number of silanol hydroxyl groups generated during the exposure process interact with each other, resulting in Si. A silicon-based matrix having a three-dimensional structure of —O—Si bonds is formed. Therefore,
It is possible to obtain an insulating film having excellent durability and mechanical strength, in which fine powder such as SiO ₂ is contained in the silicon-based matrix.

When the above-mentioned exposure of the organosilicon compound film is not the whole surface exposure, after exposing the exposed part of the silicon compound film to fine powder such as SiO _{2 and} before heat-treating this film. You may perform the whole surface exposure by ultraviolet rays. In this exposure process, the wavelength of ultraviolet rays is 150-
It may be about 400 nm, but especially 200 to 300 n
It is preferable to irradiate ultraviolet rays having a wavelength of m. The irradiation dose is preferably set to about 10 mJ to 10 J, and more preferably about 100 mJ to 3 J.

Further, after the step of impregnating the exposed portion of the organosilicon compound film with the fine powder and before the heat treatment, the organosilicon compound film may be immersed in the sol solution of the metal alkoxide as described above. By soaking in the sol solution in this way, the silanol hydroxyl group generated in the entire exposure step and the metal of the metal alkoxide adsorbed on the organosilicon compound film are bonded, and the substrate is treated with a very high cross-linking density to give a substrate. It is possible to form an insulating film having further improved adhesiveness to and heat resistance.

Further, also in the manufacturing method of the third invention,
It is possible to selectively dissolve and remove a predetermined region of the organosilicon compound film to form a patterned insulating film. Hereinafter, a method for manufacturing a patterned insulating film will be described in detail.

First, the organosilicon compound film formed on the substrate is irradiated with ultraviolet rays under the same conditions as described above through a mask having a predetermined pattern, and then the organosilicon compound film is exposed using an alkaline aqueous solution. The patterned organosilicon compound film is obtained by selectively removing the portion by dissolution.

In order to obtain an organosilicon compound film patterned by such a method, the polysilane used must have R ¹ in the above general formula (2) as a substituted or unsubstituted aryl group. is there.

As the alkaline aqueous solution used here, the same aqueous solution as in the case of forming the positive type pattern in the above-mentioned second invention can be mentioned. That is, for example, an organic alkali such as tetramethylammonium hydroxide or choline; an inorganic alkali such as KOH or NaOH can be used. It is also possible to dissolve and remove the exposed portion by using a hydrofluoric acid aqueous solution. The organic silicon compound film after development is washed with pure water as appropriate.

Then, the patterned organosilicon compound film is irradiated with ultraviolet rays under the same conditions as described above to generate silanol-containing hydroxyl groups (Si-OH), and subsequently, the patterned organosilicon compound film is formed. SiO ₂
And so on to adsorb the fine powder. Finally, the organosilicon compound film is heat-treated under the same conditions as described above to obtain a patterned insulating film.

Before the heat treatment step, the heat resistance and the like of the insulating film can be further improved by immersing it in the same sol solution of metal alkoxide as described above.

Further, the patterned insulating film is formed by selectively exposing a predetermined region of the organosilicon compound film to light, and then impregnating the exposed portion with a fine powder such as SiO ₂ to carry out the steps of heat treatment and development treatment. It can also be formed by passing through.
In this case, first, pattern exposure is performed on the organosilicon compound film formed on the substrate under the same conditions as described above, and then fine powder such as SiO ₂ is selectively applied to the exposed portion of this film. Impregnate.

Next, an organic silicon compound film is applied to 50-150.
Heat treatment is performed at 5 ° C. for about 5 to 30 minutes in the same manner as in the case of forming the negative pattern in the second invention. Before the heat treatment step, the heat resistance and the like of the insulating film can be further improved by immersing the organosilicon compound film in the sol solution of the metal alkoxide as described above.

After this, the portion not impregnated with the fine powder was
It can be dissolved and removed using either an organic solvent or an alkaline aqueous solution. That is, since silanol-containing hydroxyl groups are not generated in the unexposed portion not impregnated with the fine powder, the siloxane bond (Si—O—Si) having a crosslink density insoluble in the solvent is not formed even by the heat treatment. Therefore, it can be dissolved and removed with an aromatic solvent such as xylene; a ketone solvent such as methyl ethyl ketone; an alcohol solvent such as ethanol. On the other hand, in order to dissolve and remove the unimpregnated portion of the fine powder with the alkaline aqueous solution, the organosilicon compound film is previously exposed to ultraviolet rays for exposure.
The exposure here can be performed under the same conditions as described above,
The wavelength is 150 to 400 nm, more preferably 200 to 3
It is preferable 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 ~ 3J. Since this exposure forms silanol hydroxyl groups, it can be easily dissolved and removed using the alkaline aqueous solution as described above. However, in this case, in the polysilane used, R ¹ in the general formula (2) needs to be a substituted or unsubstituted aryl group. Note that an aqueous solution of hydrofluoric acid can also be used here.

According to the method of the third invention, Si--O--Si
An insulating film comprising a vitrified silicon-based matrix having a three-dimensional structure of bonds and impregnated with at least one of SiO ₂ fine powder and SiN fine powder can be produced. The obtained insulating film has a high film density due to the impregnated fine powder, high resistance, and high strength, as in the case of using the silicon polymer composition of the second invention. When SiO ₂ fine powder is used, the dielectric breakdown resistance can be further enhanced. Further, when SiN fine powder is used, ion trapping property and H ₂ O barrier property can be imparted.

[0172]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

(Example I) (Example I-1) An average molecular weight of 4 represented by the following chemical formula:
15 g of polysilane of 000 t-butyl lactate 1
After dissolving in 100 g, the obtained resist solution was spin-coated on a silicon substrate and then prebaked at 100 ° C. for 5 minutes to form a resist film having a thickness of 0.5 μm. Then, 500 mJ / cm ² of ultraviolet ray having a wavelength of 254 nm is irradiated from a low pressure mercury lamp through a mask pattern, and a 2.38 wt% tetramethylammonium hydroxide aqueous solution is used at 25 ° C.
When development was performed for 40 seconds, a positive pattern having a good pattern shape was accurately formed.

[0174]

Embedded image

In the formula, n represents the degree of polymerization.

Comparative Example I-1 15 g of polysilane having an average molecular weight of 4,000 represented by the following chemical formula was dissolved in 100 g of t-butyl lactic acid ester, and the obtained resist solution was spin-coated on a silicon substrate. Pre-baking was performed at 5 ° C. for 5 minutes to form a resist film having a thickness of 0.8 μm. Then, 500 mJ / cm ² of ultraviolet ray having a wavelength of 254 nm is irradiated from a low pressure mercury lamp through the mask pattern,
When immersed in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 0 ° C., no pattern was formed.

[0177]

Embedded image

In the formula, n represents the degree of polymerization.

(Example I-2) The average molecular weight is 9,000.
100 g of the polysilane having the same structure as in Example (I-1) except that the above is used, 4 g of benzoyl peroxide as a radical generator serving as a cross-linking agent of this polysilane, and 6 g of phenylenedialdehyde which is an unsaturated compound are added to 50 parts of toluene.
After being dissolved in g, the obtained resist solution was spin-coated on a silicon substrate and then prebaked at 100 ° C. for 5 minutes to form a resist film having a thickness of 0.5 μm. Next, ultraviolet rays having a wavelength of 254 nm are irradiated at 500 mJ / cm ² from a low-pressure mercury lamp through a mask pattern, and the solution is made into a 2.48 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C.
As a result of development for 0 seconds, a positive pattern having a good pattern shape was accurately formed.

Further, this pattern is gradually heated to 1
After a step bake at 00 ° C to 200 ° C for about 30 minutes, it was confirmed that the pattern shape was not impaired, and the surface hardness of the pattern after heat treatment was 3H in pencil hardness. Was done.

(Example I-3) 5 g of the same polysilane as in Example (I-1) and 10 g of polyvinylphenol having an average molecular weight of 12,000 which is an alkali-soluble organic compound.
Was dissolved in 100 g of t-butyl lactate, and the obtained resist solution was spin-coated on a silicon substrate and then 10
Prebaking was performed at 0 ° C. for 5 minutes to form a resist film having a thickness of 0.6 μm. Then, ultraviolet rays with a wavelength of 254 nm are emitted from the low-pressure mercury lamp through the mask pattern to 500 mJ / cm.
^Two irradiations were performed, and development was performed with a 1.19 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 40 seconds. As a result, a positive pattern having a good pattern shape was accurately formed.

(Comparative Example I-2) 5 g of polysilane having an average molecular weight of 5,000 represented by the following chemical formula and 10 g of polyvinylphenol having an average molecular weight of 12,000, which is an alkali-soluble organic compound, and 100 g of t-butyl lactic acid ester.
The obtained resist solution was spin-coated on a silicon substrate and then prebaked at 100 ° C. for 5 minutes to a thickness of 0.
A 6 μm resist film was formed. Next, 500 mJ / cm ² of ultraviolet light having a wavelength of 254 nm was irradiated from a low pressure mercury lamp through a mask pattern, and an attempt was made to develop it with a 1.19 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 40 seconds, but the pattern did not appear at all. Not formed.

[0183]

Embedded image

Example I-4 5 g of polysilane having an average molecular weight of 7,000 represented by the following chemical formula and polyamic acid which is an alkali-soluble organic compound (concentration of 0.5 g / dl N-methyl-measured at 30 ° C.) were used. Intrinsic viscosity of 2-pyrrolidone solution: 0.54 dl / g) 10 g was dissolved in 100 g of γ-butyrolactone, and the obtained resist solution was spin-coated on a silicon substrate and then prebaked at 100 ° C. for 5 minutes to give a thickness of 1 A resist film having a thickness of 0.2 μm was formed. Then, from the low-pressure mercury lamp through the mask pattern, the wavelength 2
After irradiation with 54 nm ultraviolet light and development with a 0.56 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 10 seconds, a positive pattern having a good pattern shape was accurately formed. Furthermore, when this pattern was subjected to heat treatment at 150 ° C. for 1 hour, 250 ° C. for 1 hour, and 400 ° C. for 1 hour, the polyamic acid in the pattern was sufficiently imidized and a film pattern mainly composed of a polyimide resin was formed. I was able to get

[0185]

Embedded image

In the formula, PS is a polysilane skeleton.

Example I-5 2 g of polysilane having an average molecular weight of 12,000 represented by the following chemical formula was added to 10 parts of toluene.
It was dissolved in g to prepare a 20 wt% solution. After spin coating the obtained resist solution on a silicon substrate, 100
Prebaking was performed at 5 ° C. for 5 minutes to form a 0.7 μm thick resist film. Then, 1 J / cm ² of ultraviolet ray having a wavelength of 254 nm was irradiated from a low-pressure mercury lamp through a mask pattern, and developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 90 seconds, and a line width of 1.0 μm was obtained. A pattern was formed. Furthermore, when this pattern was gradually heated from room temperature to 400 ° C., an insulating film having a dielectric constant of 2.8% and a volume resistivity of 1 × 10 ¹³ Ω · cm was obtained.

[0188]

Embedded image

In the formula, n represents the degree of polymerization.

In the above-mentioned step, the film after pattern exposure was heated at 150 ° C. for 10 minutes and developed with toluene for 90 seconds. As a result, an inverted pattern having a line width of 1.0 μm was formed. This pattern from room temperature to 400
When the temperature was gradually raised to 0 ° C., an insulating film having a dielectric constant of 2.8% and a volume resistivity of 1 × 10 ¹³ Ω · cm was obtained.

Example I-6 A solution similar to the above Example (I-5) was prepared except that polysilane having an average molecular weight of 12,000 represented by the following chemical formula was used, and this solution was prepared in the same manner as above. When the solution was applied onto the substrate, exposed and developed, a pattern having a line width of 1.0 μm was formed. Furthermore, when this pattern was gradually heated from room temperature to 400 ° C., the dielectric constant was 3.2% and the volume resistivity was 1 × 10 ¹³ Ω.
An insulating film of cm was obtained.

[0192]

Embedded image

In the formula, n represents the degree of polymerization.

From the above results, it is understood that by using the resist of the present invention, it is possible to obtain a resist containing polysilane which can be developed with an alkali and can form a fine pattern with high accuracy.

Example II First, the polysilane used in this example was synthesized as follows.

(Synthesis of Polysilane AZr) 60 ml of diethyl ether and 5.34 g of zirconocene dichlore which had been dried at −20 ° C. under an argon atmosphere were stirred, and 1.
5M Methyllithium was added little by little and stirred for 70 minutes. After further stirring at 0 ° C. for 30 minutes, diethyl ether was removed, and the produced white solid was sublimated to prepare zirconocene dimethyl.

Next, this zirconocene dimethyl was added to phenylsilane at a molar ratio of 50: 1, and phenylsilane was polymerized at room temperature for 5 hours. Next, the obtained crude polymer was dissolved in toluene and poured into methanol with stirring to reprecipitate the polymer. Further, the polymer was similarly reprecipitated twice in methanol and then dried under reduced pressure at 80 to 90 ° C. to obtain polysilane AZr represented by the following chemical formula and having a weight average molecular weight of about 6,000.

[0198]

Embedded image

In the formula, n represents the degree of polymerization.

(Synthesis of polysilane BZr) 10 g of the polysilane AZr and 15.5 g of azobis (isobutyronitrile) synthesized as described above were dissolved in 50 g of acetone and refluxed for 3 days to remove hydrogen atoms bonded to silicon atoms. Polysilane B represented by the following chemical formula having a weight average molecular weight of about 6,000, in which 50% is replaced with an isopropyl group.
Zr was obtained.

[0201]

Embedded image

(Synthesis of polysilane CNa) 10 g of methyldichlorosilane and 1 of methylphenyldichlorosilane
6.6 g was dissolved in toluene to prepare a 50 wt% toluene solution. On the other hand, in a 1 L flask, shredded metal Na
8.4 g was dispersed in 100 ml of toluene, and the above 50 wt% toluene solution was added dropwise thereto little by little at 110 ° C. After stirring for 2 hours, the temperature was lowered to room temperature and the filtrate filtered under an argon atmosphere was concentrated, and the filtrate was added dropwise to isopropyl alcohol to precipitate a polymer.

Next, the obtained polymer was dried under reduced pressure, dissolved in toluene again, washed with water, and similarly dropped into isopropyl alcohol to prepare a polymer. further,
After repeating this operation 5 times, the polymer was dried under reduced pressure to obtain polysilane CNa represented by the following chemical formula and having a weight average molecular weight of about 12,000.

[0204]

Embedded image

(Synthesis of Polysilane ENa) 10 g of methyldichlorosilane and 10 g of methylphenyldichlorosilane.
And phenyltrichlorosilane (7.4 g) were dissolved in toluene to prepare a 50 wt% toluene solution, and polysilane ENa represented by the following chemical formula having a weight average molecular weight of about 15,000 was prepared in exactly the same manner as when polysilane CNa was synthesized. Got

[0206]

Embedded image

In the formula, PS is a polysilane skeleton.

(Preparation of Silicon Polymer Composition) Polysilane AZr (15 g) was dissolved in toluene (85 g) to obtain a toluene solution, and the solution was added with S having an average particle size of about 0.2 μm.
2.5 g of iO ₂ fine powder was dispersed with a dispersant to obtain a silicon polymer composition (P-1).

Further, 15 g of polysilane AZr was dissolved in 85 g of toluene to obtain a toluene solution, and 5 g of SiN fine powder having an average particle diameter of about 0.2 μm was dispersed in the solution with a dispersant to obtain a silicon polymer composition (P- 2) was obtained.

Example II-1 The silicon polymer composition (P-1) was spin-coated on a silicon substrate, and then 100
Prebaking was performed at 5 ° C. for 5 minutes to form an organosilicon compound film having a thickness of 2 μm. Then, the organic silicon compound film was exposed to 1 J / c of ultraviolet rays from a low pressure mercury lamp through a mask pattern.
After irradiation with m ² and development with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 1 minute, a positive pattern was formed.

When this pattern was heated at 400 ° C. for 1 hour, a dense insulating film having a pencil hardness of 5H was obtained. When the adhesion of the obtained film with a silicon substrate was evaluated by a cross-cut test, 100/100 remained on the substrate, and no peeling of the film was observed. Furthermore, the volume resistivity of this film was as good as 1 × 10 ¹⁴ Ω · cm, and it did not soften even when heated to 300 ° C.

Example II-2 A silicon polymer composition (P-1) was spin-coated on a silicon substrate, and then 100
Prebaking was performed at 5 ° C. for 5 minutes to form an organosilicon compound film having a thickness of 2 μm. Then, the organic silicon compound film was exposed to 1 J / c of ultraviolet rays from a low pressure mercury lamp through a mask pattern.
After irradiation with m ² , the substrate was heated at 150 ° C. for 10 minutes. Then, as a result of developing with toluene for 1 minute, a negative pattern was formed.

When this pattern was heated at 400 ° C. for 1 hour, a dense insulating film having a pencil hardness of 5H was obtained. When the adhesion of the obtained film with a silicon substrate was evaluated by a cross-cut test, 100/100 remained on the substrate, and no peeling of the film was observed. Furthermore, the volume resistivity of this film was as good as 1 × 10 ¹⁴ Ω · cm, and it did not soften even when heated to 300 ° C.

(Example II-3) The silicon polymer composition (P-2) was spin-coated on a silicon substrate, and then 100
Prebaking was performed at 5 ° C. for 5 minutes to form an organosilicon compound film having a thickness of 2 μm. Then, the organic silicon compound film was exposed to 1 J / c of ultraviolet rays from a low pressure mercury lamp through a mask pattern.
After irradiation with m ² and development with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 1 minute, a positive pattern was formed.

This pattern was irradiated with 1 J / cm ^{2 of} ultraviolet rays from a low-pressure mercury lamp and then heated at 300 ° C. for 1 hour, whereby a dense insulating film having a pencil hardness of 5H was obtained.
When the adhesion of the obtained film with a silicon substrate was evaluated by a cross-cut test, 100/100 remained on the substrate, and no peeling of the film was observed. Furthermore, the volume resistivity of this film is as good as 1 × 10 ¹⁴ Ω · cm,
Moreover, it did not soften even when heated to 300 ° C.

Further, the Na trapping property and the H ₂ O barrier property were examined as follows. First, a SiO ₂ film was formed on the surface of a silicon substrate by a CVD method, and then an insulating film was formed on the surface of this SiO ₂ film in the same manner as described above except that a positive pattern was not formed to obtain a sample. .

After this sample was immersed in a 1 wt% NaOH aqueous solution for 1 hour, SIMS was used to remove N in the substrate and the insulating film.
An attempt was made to detect a ion. As a result, Na ions were adsorbed in the vicinity of the surface of the insulating film, and their existence was not recognized in the SiO ₂ film.

In evaluating the H ₂ O barrier property, first, the same sample as described above was left for 1 day in a Petri dish containing D ₂ O. At this time, the coated surface of the substrate was placed so as to be exposed to the D ₂ O atmosphere. After that, as a result of attempting to detect D ₂ O in the substrate and the insulating film by SIMS, the presence of D ₂ O was not found in the insulating film and the SiO ₂ film.

(Example II-4) After the silicon polymer composition (P-2) was spin-coated on a silicon substrate, 100
Prebaking was performed at 5 ° C. for 5 minutes to form an organosilicon compound film having a thickness of 2 μm. Then, the organic silicon compound film was exposed to 1 J / c of ultraviolet rays from a low pressure mercury lamp through a mask pattern.
After irradiation with m ² , the substrate was heated at 150 ° C. for 10 minutes. Then, as a result of developing with toluene for 1 minute, a negative pattern was formed.

When this pattern was heated at 400 ° C. for 1 hour, a dense insulating film having a pencil hardness of 5H was obtained. When the adhesion of the obtained film with a silicon substrate was evaluated by a cross-cut test, 100/100 remained on the substrate, and no peeling of the film was observed. Furthermore, the volume resistivity of this film was as good as 1 × 10 ¹⁴ Ω · cm, and it did not soften even when heated to 300 ° C.

Further, in the same manner as in the above-mentioned Example (II-3), the Na-trapping property and H _{2 of the} organosilicon compound film were
When the O barrier property was examined, it was confirmed that it had Na trapping ability and H ₂ O barrier property.

(Comparative Example II-1) In the same manner as in Example (II-1) except that a silicon polymer composition containing polymethylphenylsilane having an average molecular weight of 8,000 was used in place of polysilane AZr. , An organosilicon compound film was formed. Then, the organic silicon compound film is heated to 400 ° C.
However, a sufficiently dense film was not obtained, and the film was damaged by the pencil hardness B and peeled from the substrate.

Example II-5 Polysilane AZr 15
A wt% toluene solution was spin-coated on a silicon wafer substrate and then prebaked at 100 ° C. for 5 minutes to form an organosilicon compound film having a thickness of 2 μm. The obtained organic silicon compound film was irradiated with ultraviolet rays from a low pressure mercury lamp at 1 J / cm ² . Then, SiO ₂ fine powder (average particle size of about 0.1 μm)
The wafer was immersed in an isopropyl alcohol solution in which m) was dispersed at a concentration of 10 wt%, washed with water, and then at 150 ° C. for 3 minutes.
By heating and drying for 0 minutes at 400 ° C. for 1 hour, S
An insulating film composed of a silicon-based matrix impregnated with iO ₂ fine powder could be formed.

The obtained film was sufficiently dense with a pencil hardness of 5H, and the adhesiveness to a silicon wafer substrate was evaluated by a cross-cut test. As a result, 100/100 remained on the substrate and No peeling was observed at all. Furthermore, the volume resistivity of this film was as good as 1 × 10 ¹⁴ Ω · cm, and it did not soften even when heated to 300 ° C.

Example II-6 Polysilane BZr 15
A wt% toluene solution was spin-coated on a silicon wafer substrate and then prebaked at 100 ° C. for 5 minutes to form an organosilicon compound film having a thickness of 2 μm. The obtained organic silicon compound film was irradiated with ultraviolet rays from a low pressure mercury lamp at 1 J / cm ² . Subsequently, SiN fine powder (average particle size of about 0.1 μm)
The above wafer is immersed in an isopropyl alcohol solution in which is dispersed at a concentration of 10 wt%, washed with water, and then heated at 150 ° C.
By drying for 1 minute at 400 ° C., an insulating film composed of a silicon-based matrix impregnated with SiN fine powder could be formed.

The obtained film was sufficiently dense with a pencil hardness of 5H, and the adhesiveness to a silicon wafer substrate was evaluated by a cross-cut test. As a result, 100/100 remained on the substrate and No peeling was observed at all. Furthermore, the volume resistivity of this film was as good as 1 × 10 ¹⁴ Ω · cm, and it did not soften even when heated to 300 ° C.

Further, in the same manner as in the above-mentioned Example (II-3), the Na-trapping property and H _{2 of the} organic silicon compound film were
When the O barrier property was examined, it was confirmed that it had Na trapping ability and H ₂ O barrier property.

Example II-7 Polysilane ENa 15
A wt% toluene solution was spin-coated on a silicon wafer substrate and then prebaked at 100 ° C. for 10 minutes to form an organosilicon compound film having a thickness of 2 μm. The obtained organic silicon compound film was irradiated with ultraviolet rays from a low pressure mercury lamp at 1 J / cm ² . Then, SiN fine powder (average particle size of about 0.1μ
The wafer was immersed in an isopropyl alcohol solution in which m) was dispersed at a concentration of 10 wt%, washed with water, and then at 150 ° C. for 3 minutes.
By drying for 0 minutes at 400 ° C for 1 hour, SiN
An insulating film composed of a silicon-based matrix impregnated with fine powder could be formed.

The obtained film was sufficiently dense with a pencil hardness of 5H, and the adhesiveness to a silicon wafer substrate was evaluated by a cross-cut test. As a result, 100/100 remained on the substrate. No peeling was observed at all. Furthermore, the volume resistivity of this film was as good as 1 × 10 ¹⁴ Ω · cm, and it did not soften even when heated to 300 ° C.

Further, in the same manner as in the above-mentioned Example (II-3), the Na-trapping property of the organosilicon compound film and H ₂
When the O barrier property was examined, it was confirmed that it had Na trapping ability and H ₂ O barrier property.

Example II-8 15 Polysilane CNa
A wt% toluene solution was spin-coated on a silicon wafer substrate and then prebaked at 100 ° C. for 5 minutes to form an organosilicon compound film having a thickness of 2 μm. The obtained organic silicon compound film was irradiated with ultraviolet rays from a low pressure mercury lamp at 1 J / cm ² through a mask pattern. Subsequently, the above wafer is immersed in an isopropyl alcohol solution in which SiN fine powder (average particle size: about 0.1 μm) is dispersed at a concentration of 10 wt%, washed with water, and dried at 150 ° C. for 30 minutes to select an exposed portion. As a result, an insulating film made of a silicon-based matrix impregnated with SiN fine powder could be formed.

Example II-9 Polysilane BZr 15
A wt% toluene solution was spin-coated on a silicon wafer substrate and then prebaked at 100 ° C. for 5 minutes to form an organosilicon compound film having a thickness of 2 μm. The obtained organic silicon compound film was irradiated with ultraviolet rays from a low pressure mercury lamp at 1 J / cm ² through a mask pattern. Subsequently, the above wafer is immersed in an isopropyl alcohol solution in which SiN fine powder (average particle size: about 0.1 μm) is dispersed at a concentration of 10 wt%, washed with water, and dried at 150 ° C. for 30 minutes to select an exposed portion. As a result, an insulating film made of a silicon-based matrix impregnated with SiN fine powder could be formed.

Further, the entire surface of this film was irradiated with a low pressure mercury lamp and then developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 1 minute.
The portion not impregnated with the fine powder was dissolved and removed, and a patterned insulating film was formed. 400 this pattern
By heating at 0 ° C. for 1 hour, a dense insulating film pattern could be formed.

Comparative Example II-2 Except that polymethylphenylsilane having an average molecular weight of 8,000 was used instead of polysilane AZr, S was carried out in the same manner as in Example (II-5).
An insulating film impregnated with fine powder of iO ₂ was formed. However, with the film obtained here, the pencil hardness was B and the film was damaged and peeled off from the substrate, resulting in insufficient adhesion to the substrate.

From the above results, according to the method for producing a silicon polymer composition or an insulating film of the present invention, Si--O--S
A silicon-based matrix having an i-bonded three-dimensional structure may be impregnated with fine powder such as SiO ₂ to form an insulating film having excellent adhesion to a substrate and heat resistance, and high resistance and strength. Recognize.

[0236]

As described in detail above, according to the resist and the pattern forming method of the present invention, it is possible to form a fine pattern with high accuracy and high sensitivity by alkali development. Moreover, by vitrifying the obtained pattern,
It can also be used as an insulating film pattern having excellent strength and heat resistance. Further, according to the present invention, a method for producing an insulating film having excellent adhesion to a substrate and heat resistance, high resistance, and high strength, and a silicon polymer composition capable of easily producing such an insulating film are provided. It

The insulating film manufactured by using the present invention is useful as a passivation film or an interlayer insulating film of a semiconductor device, and its industrial value is great.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Rikako Kawada 1 Komukai Toshiba-cho, Sachi-ku, Kawasaki-shi, Kanagawa Toshiba Research and Development Center (72) Inventor Takeshi Okino Toshiba Komukai-shi, Kawasaki-shi, Kanagawa Town No. 1 Incorporated company Toshiba Research and Development Center (72) Inventor Sawako Fujioka Komukai Toshiba-cho, Kawasaki City, Kanagawa Prefecture No. 1 Inside Toshiba Research and Development Center

Claims (11)

[Claims] 1. A resist comprising a polysilane having a repeating unit represented by the following general formula (1). Embedded image (In the formula, Ar represents a substituted or unsubstituted aryl group having 6 to 24 carbon atoms.) 2. A resist comprising a polysilane having a repeating unit represented by the following general formula (1) and a crosslinking agent for the polysilane. Embedded image (In the formula, Ar represents a substituted or unsubstituted aryl group having 6 to 24 carbon atoms.) 3. The resist according to claim 1, which contains an alkali-soluble organic compound. 4. The resist according to claim 1, which is for alkaline development. 5. A step of forming a resist film containing polysilane having a repeating unit represented by the following general formula (1) on a substrate, and a step of exposing a desired region of the resist film on the substrate to light. A pattern forming method comprising a step of developing a resist film after exposure with an alkaline aqueous solution. Embedded image (In the formula, Ar represents a substituted or unsubstituted aryl group having 6 to 24 carbon atoms.) 6. A silicon polymer composition comprising a polysilane having a repeating unit represented by the following general formula (2) and at least one fine powder of SiO ₂ fine powder and SiN fine powder. Embedded image (In the formula, R ¹ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group.) 7. A film-forming step of forming an organosilicon compound film containing the silicon polymer composition according to claim 6 on a substrate, and three-dimensionalization by heating and drying the organosilicon compound film in an oxygen-containing atmosphere. A method for forming an insulating film, comprising: 8. The method for forming an insulating film according to claim 7, wherein prior to heating and drying the organic silicon compound film, the entire surface of the organic silicon compound film is exposed in an oxygen-containing atmosphere. 9. R ¹ in the general formula (2) is a substituted or unsubstituted aryl group, and a predetermined region of the organosilicon compound film is irradiated with ultraviolet light before heating and drying the organosilicon compound film. 8. The method for producing an insulating film according to claim 7, further comprising: an exposing step of: and a developing step of dissolving and removing an exposed portion of the organic silicon compound film after the exposing with an alkaline aqueous solution. 10. An exposure step of irradiating a predetermined region of the organosilicon compound film with ultraviolet rays before heating and drying the organosilicon compound film, a heat treatment step of heating the exposed organosilicon compound film, and the heat treatment. The method for producing an insulating film according to claim 7, further comprising a developing step of dissolving and removing an unexposed portion of the organic silicon compound film afterwards with an organic solvent. 11. A film forming step of forming an organosilicon compound film mainly containing polysilane having a repeating unit represented by the following general formula (2), and irradiating a predetermined region of the organosilicon compound film with ultraviolet rays. An exposure step; a step of impregnating the exposed portion of the organic silicon compound film with at least one of SiO ₂ fine powder and SiN fine powder; and three-dimensional heating and drying the organic silicon compound film impregnated with the fine powder. And a method of forming an insulating film provided with the step of forming. Embedded image (In the formula, R ¹ is a substituted or unsubstituted aryl group,
Or a substituted or unsubstituted alkyl group is shown. )