JP2003055556A - Method for forming silicon film or silicon oxide film and composition for them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silane composition capable of forming a silicon film or a silicon oxide film on a substrate by using a liquid raw material with a simple operation and device different from a method requiring a complex vacuum system device such as a CVD method of sputtering method, efficiently e.g. in a high yield and forming speed, and to provide a method for forming the silicon film or the silicon oxide film by using the composition. SOLUTION: The silane composition contains a polysilane compound and at least 1 kind of a silane compound selected from the group consisting of cyclopentasilane, cyclohexasilane and silylcyclopentasilane. The method for forming the silicone film or the silicon oxide film comprises applying the silane composition on the base substrate and treating the formed coated film under a non-oxidizing atmosphere or an oxidizing atmosphere, respectively.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silane composition and a method for forming a silicon film or a silicon oxide film. More specifically, it relates to a silane composition suitable for forming a silicon film and a silicon oxide film on a substrate, and a method for forming a silicon film and a silicon oxide film using the same.

[0002]

2. Description of the Related Art Conventionally, as a method for forming an amorphous silicon film or a polysilicon film used for manufacturing a solar cell, thermal CVD (Che of a monosilane gas or a disilane gas is used.
The metallic vapor deposition method, plasma CVD, photo-CVD and the like are used. Generally, thermal CVD (J. Vac.
Sci. Technology. , Vol. 14, p. 1082 (1977)), and for forming an amorphous silicon film, plasma CVD (Solid StateC).
om. , 17: 1193 (1975)) is widely used.

However, since the vapor phase reaction is used in the formation of the silicon film by these CVD methods, the production yield is low due to the generation of silicon particles in the vapor phase to contaminate the equipment and the generation of foreign matters. It is difficult to obtain a film having a uniform film thickness on a substrate having irregularities on the surface, productivity is low due to the slow film formation rate, and a complicated and expensive high-frequency generator or vacuum device in the plasma CVD method There was a problem such as the need for etc., and further improvement was awaited.

In terms of materials, since gaseous silicon hydride, which is highly toxic and reactive, is used, it is not only difficult to handle, but a gaseous vacuum requires a closed vacuum device. Generally, these devices are large-scaled and not only expensive, but they also consume a lot of energy in a vacuum system or a plasma system, which leads to high product cost.

On the other hand, the silicon oxide film has been frequently used as an electric insulating film, a dielectric film and a protective film for silicon devices such as semiconductors. Usually, these silicon oxide films are formed by a method of thermally oxidizing silicon in air, a method of forming silane gas or disilane gas by plasma CVD method in an oxidizing gas such as oxygen or nitric oxide, or a direct sputtering method from quartz. In addition to a dry process such as a method of forming by a method, a wet process in which an alkoxysilane or the like such as tetraethoxysilane is applied to a substrate in a partially hydrolyzed sol state and then thermally decomposed by heat is known.

However, among these methods, there are the following problems when the silicon oxide film is formed by the dry process. Since this is a gas phase reaction, particles of impurities are generated in the gas phase, so the production yield is low due to contamination of the equipment and generation of foreign matter. Since the raw material is gaseous, it is difficult to obtain a film having a uniform film thickness on a substrate having irregularities on the surface. Productivity is low due to the slow film formation rate. The plasma CVD method requires a complicated and expensive high-frequency generator, vacuum device, and the like. It is difficult to apply to large area substrates.

Furthermore, these dry processes are difficult to handle because they use gaseous silicon hydride, which is highly toxic and reactive in terms of materials, and requires a closed vacuum device because they are gaseous. Becomes In general, these devices are not only expensive and expensive,
Since a large amount of energy is consumed in the vacuum system and the plasma system, the cost of the product is high.

The system using the sol-gel reaction of the wet process is a method in which a partial hydrolyzate such as an alkoxysilane is heated to cause a dehydration condensation reaction of the hydrolyzate. Therefore, water is generated as the reaction progresses, so that it is difficult to obtain a dense silicon oxide film, and
Cracks are likely to occur due to the generation of internal stress in the film. Since it is heated at a higher temperature, it cannot be applied to a plastic substrate having low heat resistance.

Further, Japanese Patent Publication No. 7-29769 discloses that a film made of amic acid containing a hydrolyzable silicon atom is irradiated with ultraviolet rays in the presence of ozone to form a silicon oxide film. . In this method, since a silicon compound containing a highly heat-resistant amic acid as an organic component is used as a precursor of a silicon oxide film, a thick film can be obtained, but a large amount of ultraviolet rays are irradiated to oxidize and decompose the organic component. Therefore, there is a point to be improved that productivity is poor.

[0010]

SUMMARY OF THE INVENTION The object of the present invention is to provide a CV
Unlike methods that require complicated vacuum equipment such as D method and sputtering method, liquid raw materials can be operated with simple operations and equipment.
It is an object of the present invention to provide a silane composition capable of efficiently forming a silicon film and a silicon oxide film on a substrate, for example, with a high yield and a high formation rate.

Another object of the present invention is to provide a method for forming a silicon film as described above using the silane composition of the present invention. Still another object of the present invention is to
It is another object of the present invention to provide a method for forming a silicon oxide film as described above using the silane composition of the present invention. Other objects and advantages of the present invention will be apparent from the following description.

[0012]

According to the present invention, the above objects and advantages of the present invention are as follows: (A) Formula Si _n R _m, where n is an integer of 3 or more, and m is n- (2n +
2) is an integer and m R are independently of each other a hydrogen atom, an alkyl group, a phenyl group or a halogen atom, provided that all of the m R are hydrogen atoms and m = 2n.
And n is an integer of 7 or more, and at least one silane selected from the group consisting of (B) cyclopentasilane, cyclohexasilane, and silylcyclopentasilane. This is achieved by a silane composition containing a compound.

According to the present invention, secondly, the above objects and advantages of the present invention are represented by the formula (A ') Si _i H _{2i + 2,} where i is an integer of 2-8. Hydrogenated chain silane compound, formula Si _j H _2j, where j is an integer of 3 to 10, and a hydrogenated cyclic silane compound represented by the formula Si _k H _k, where k is an integer of 6 to 10. A product produced by the irradiation of at least one silane compound selected from the group consisting of hydrogenated cage silane compounds represented by
And (B) a silane composition containing at least one silane compound selected from the group consisting of cyclopentasilane, cyclohexasilane, and silylcyclopentasilane.

According to the present invention, thirdly, the above objects and advantages of the present invention are obtained by forming a coating film comprising the silane composition of the present invention on a support, and then applying heat and / or heat in a non-oxidizing atmosphere.
Alternatively, it is achieved by a method of forming a silicon film on a substrate, which is characterized by performing light treatment.

Finally, according to the present invention, the above objects and advantages of the present invention are obtained by forming a coating film comprising the silane composition of the present invention on a support and then in an atmosphere containing oxygen and / or ozone. It is achieved by a method of forming a silicon oxide film on a substrate, which is characterized by heat treatment and / or light treatment at Hereinafter, the silane composition of the present invention will be described in detail.

The polysilane compound used in the present invention is
It is represented by the above formula. Examples of the alkyl group represented by R include, for example, methyl group, ethyl group, n-propyl group, i-
Propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, neopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n Preferable ones are alkyl groups having 1 to 10 carbon atoms such as -nonyl group and n-decyl group.

Preferred examples of the halogen atom include fluorine, chlorine and bromine. The polysilane compound may have a chain shape, a ring shape, or a cage shape.

Of the above polysilane compounds, hydrogenated polysilane compounds in which all R are hydrogen atoms are preferably used. Such hydrogenated polysilane compound, hydrogenated chain polysilane represented by the formula Si _n H _{2n + 2,}
Hydrogenated cyclic polysilane represented by the formula Si _n H _2n, and hydrogenated cage-like polysilane compound represented by the formula Si _n H _n is preferably used. In addition, "cage-like" means a thing including a Prisman skeleton, a Cuban skeleton, a pentagonal prism skeleton, and the like.

However, n in each of the above formulas is an integer of 3 to 100,000, preferably 5 to 50,000 in the hydrogenated chain polysilane, and 7 to 100,000, preferably 8 in the hydrogenated cyclic polysilane. ~ 50,0
Is an integer of 0, and in hydrogenated cage polysilanes 6 to 100,000, preferably 7 to 50,000.
Is an integer.

In this case, if n is smaller than the above-mentioned minimum value, the film-forming property of the polysilane compound may be difficult, and if n is larger than the above-mentioned maximum value, the cohesive force of the polysilane compound may be caused. A decrease in solubility may be observed.

Such a polysilane compound alone is
Further, two or more kinds can be mixed and used.

The polysilane compound used in the present invention can be produced, for example, by the following method using a monomer having a desired structural unit as a raw material. (A) A method of dehalogenating polycondensation of halosilanes in the presence of an alkali metal (so-called "kipping method", J. Am. Che
m. Soc. , 110 , 2342 (1988) and M.
acromolecules, 23 , 3423 (199
0)); (b) Method of dehalogenating polycondensation of halosilanes by electrode reduction (J. Chem. Soc., C.
hem. Commun. 1161 (1990) and J. Chem. Soc. Chem. Commun. ，
896 (1992)); (c) A method for dehydrogenative condensation polymerization of hydrosilanes in the presence of a metal catalyst (JP-A-4-26
No. 334551): (d) Method by anionic polymerization of disilene crosslinked with biphenyl or the like (Macr
o molecules, 23, 4494 (1990)
reference). (E) After synthesizing the cyclic silicon compound substituted with a phenyl group or an alkyl group by the above method, a known method (for example, Z. Anorg. Allg. Chem., 4
59 , 123-130 (1979), E.I. Henggg
e et al Mh. Chem. Volume 106, Pages 503, 197
It can be converted to a hydro-substituted product, a halogen-substituted product or the like after 5 years), and (f) the silane compound synthesized by the above method can be irradiated with light to obtain a higher molecular weight polysilane compound.

When a polysilane compound is synthesized by irradiating a silane compound with light, the silane compound as a raw material is represented by the formula Si _i H _{2i + 2} (where i is an integer of 2 to 8,
It is preferably an integer of 2 to 4. ) A hydrogenated chain silane compound represented by the formula: Si _j H _{2 j} (where j is an integer of 3 to 10, preferably an integer of 3 to 6) A compound and a hydrogenated cage silane compound represented by the formula Si _k H _k (k is an integer of 6 to 10) are preferable. Of these, the hydrogenated cyclic silane compounds are more preferable, and at least one compound selected from the group consisting of cyclopentasilane, cyclohexasilane, and silylcyclopentasilane is particularly preferable. These are respectively represented by the following formulas (1) to
It is represented by (3).

[0024]

[Chemical 1]

These silane compounds can be produced through decaphenylcyclopentasilane and dodecaphenylcyclopentasilane produced from diphenyldichlorosilane. These silane compounds can be used alone or as a mixture of two or more kinds.

When irradiating light, in addition to visible light, ultraviolet light, far ultraviolet light, low-pressure or high-pressure mercury lamp, deuterium lamp, discharge light of rare gas such as argon, krypton, xenon, YAG laser, argon. laser,
Carbon dioxide laser, XeF, XeCl, XeBr, Kr
An excimer laser such as F, KrCl, ArF, or ArCl can be used as a light source. As these light sources, those having an output of 10 to 5,000 W are preferably used. Usually 100 to 1,000 W is sufficient. The wavelength of these light sources is not particularly limited as long as it is absorbed by the silane compound as a raw material, but 170n
m-600 nm is preferable.

The temperature for the light irradiation treatment is preferably room temperature to 300 ° C. or lower. The processing time is about 0.1 to 30 minutes. The light irradiation treatment is preferably performed in a non-oxidizing atmosphere. Further, the light irradiation treatment may be carried out in the presence of a suitable solvent. As such a solvent, those similar to the solvent described below as an optional addition component of the composition of the present invention can be used.

The above polysilane compound is a high molecular weight compound having a degree of polymerization n in the formula Si _n R _m of about 10 or more,
Solubility in general-purpose solvents such as hydrocarbon-based solvents and ether-based solvents becomes extremely low, making it substantially insoluble,
It was substantially impossible to form such a polysilane compound on a substrate and convert it into a silicon film or a silicon oxide film.

In the present invention, it was found that a specific liquid silane compound exhibits good solubility in such an originally solvent-insoluble polysilane compound, and the polysilane compound is used as a raw material for a silicon film or a silicon oxide film. It became possible to do. By using such a relatively high molecular weight polysilane compound as a raw material for a silicon film or a silicon oxide film, there is an advantage that the formed film is dense and excellent in uniformity and of high quality.

The specific silane compound used in the present invention is at least one silane compound selected from the group consisting of cyclopentasilane, cyclohexasilane and silylcyclopentasilane. In the present invention,
These silane compounds can be used alone or as a mixture of two or more kinds.

The ratio of the polysilane compound to the silane compound constituting the solution composition of the present invention is preferably 0.01 to 1,000% by weight, more preferably 0.0.
It is 5 to 500% by weight, particularly preferably 0.1 to 100% by weight. If this value is less than 0.01% by weight, the coating film may be too thin after application to finally form a continuous silicon film or silicon oxide film. On the other hand, when this value exceeds 1,000% by weight, the polysilane compound may not be completely dissolved. The composition of the present invention may further contain a solvent.

The solvent used here is not particularly limited as long as it does not react with each component of the composition of the present invention. For example, n-pentane, n-hexane, n
-Heptane, n-octane, decane, dicyclopentane, benzene, toluene, xylene, durene, indene, tetrahydronaphthalene, decahydronaphthalene,
Hydrocarbon solvents such as squalane; diethyl ether,
Dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether,
Tetrahydrofuran tetrahydropyran, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether,
Examples thereof include ether solvents such as p-dioxane and tetrahydrofuran; and polar solvents such as propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone, dimethylformamide, acetonitrile, dimethylsulfoxide, methylene chloride and chloroform. Of these, hydrocarbon solvents are preferable from the viewpoint of stability of the solution. These solvents may be used alone or in 2
It can also be used as a mixture of two or more species.

When the above solvent is used, the amount used can be appropriately adjusted according to the desired film thickness of the silicon film and the silicon oxide film. It is preferably 10,000% by weight or less, and particularly preferably 5,000% by weight or less, based on the above silane compound. If it exceeds 10,000% by weight, a polysilane compound may be precipitated, which is not preferable.

If desired, a surfactant may be added to the composition of the present invention as long as the purpose and function of the present invention are not impaired. Such surfactants can be cationic, anionic, zwitterionic, or nonionic. Among these, nonionic surfactants improve the wettability of the composition to the object to be coated, improve the leveling property of the coated film, and prevent the occurrence of crushing of the coating film and the occurrence of orange peel skin. It can be preferably used because of its usefulness.

Examples of such nonionic surfactants include fluorine-based surfactants having a fluorinated alkyl group or perfluoroalkyl group, and polyether alkyl-based surfactants having an oxyalkyl group.

Examples of the above-mentioned fluorine-containing surfactants include F-top EF301, EF303, EF352.
(Manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F
173 (manufactured by Dainippon Ink and Chemicals, Inc.), Asahi Guard AG7
10 (manufactured by Asahi Glass Co., Ltd.), Florard FC-170C,
FC430 and FC431 (Sumitomo 3M Limited)
Manufactured), Surflon S-382, SC101, SC1
02, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), BM-1000, SC1
100 (manufactured by BM Chemie), Schsego
-Fluor (manufactured by Schwegmann), C ₉ F ₁₉
CONHC ₁₂ H ₂₅ , C ₈ F ₁₇ SO ₂ NH- (C ₂ H ₄ O) ₆
H, C ₉ F ₁₇ O (Pluronic L-35) C ₉ F ₁₇ , C ₉
F ₁₇ O (Pluronic P-84) C ₉ F ₁₇ , C ₉ F ₇ O
(Tetronic-704) (C ₉ F ₁₇ ) _{2 and the} like can be mentioned. (Here, Pluronic L-35: Asahi Denka Kogyo KK, polyoxypropylene-polyoxyethylene block copolymer, average molecular weight 1,900; Pluronic P-84: Asahi Denka Kogyo KK, polyoxy Propylene-polyoxyethylene block copolymer, average molecular weight 4,200; Tetronic-704: Asahi Denka Co., Ltd., N, N, N ', N'-tetrakis (polyoxypropylene-polyoxyethylene block copolymer Polymer),
The average molecular weight is 5,000. ) Further, as the polyether alkyl-based surfactant, for example, polyoxyethylene alkyl ether, polyoxyethylene allyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, oxyethylene An oxypropylene block polymer etc. can be mentioned.

Specific examples of these polyether alkyl-based surfactants include Emulgen 105, 430, 810, 920, Rhodol SP-40S and TW-.
L120, Emanol 3199, Same 4110, Exel P-40S, Bridge 30, Same 52, Same 72, Same 92,
Examples include Arassel 20, Emazol 320, Tween 20, 60, Merge 45 (all manufactured by Kao Corporation), Noniball 55 (manufactured by Sanyo Kasei Co., Ltd.) and the like. Examples of nonionic surfactants other than the above include polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyalkylene oxide block copolymer, and the like. Specifically, Chemistat 2500 (Sanyo Chemical Co., Ltd.) Manufactured), SN-EX92
28 (manufactured by San Nopco Co., Ltd.) and Nonal 530 (manufactured by Toho Chemical Industry Co., Ltd.).

The amount of such a surfactant used is preferably 1 with respect to 100 parts by weight in total of the polysilane compound, the silane compound, and the solvent optionally added.
The amount is 0 parts by weight or less, particularly preferably 0.1 to 5 parts by weight. Here, if the amount exceeds 10 parts by weight, the composition obtained is likely to foam, and thermal discoloration may occur, which is not preferable.

Further, colloidal silica dispersed in a suitable dispersion medium may be added to the composition of the present invention.
This colloidal silica is used to increase the silicon concentration of the composition of the present invention, and the amount of this component used can also control the thickness of the resulting coating film. When colloidal silica is used, it is preferable to select and use a dispersion medium in consideration of compatibility with the silane compound used in the present invention and an organic solvent which is an optional additional component. As such a dispersion medium, the compounds exemplified as the solvent which is an optional addition component of the present invention can be used.

In addition, the composition of the present invention has the properties of preventing gelation and thickening of the composition, improving the heat resistance, chemical resistance, hardness and adhesion of the resulting silicon oxide film, and further preventing static electricity. For the purpose, fine powders of metal oxides such as aluminum oxide, zirconium oxide, and titanium oxide can be appropriately mixed.

In the present invention, the composition of the present invention is applied onto a substrate by a suitable method such as a spray method, a roll coating method, a curtain coating method, a spin coating method, a screen printing method, an offset printing method or an ink jet method. Thus, the coating is applied so that the film thickness is preferably 0.005 to 10 μm, particularly preferably 0.01 to 5 μm. When the composition contains a solvent, the above film thickness should be understood as the film thickness after removal of the solvent.

The film forming process is performed in a non-oxidizing atmosphere. In order to realize such an atmosphere, an atmosphere that does not substantially contain an oxidizing substance such as oxygen or carbon dioxide may be used. Specifically, nitrogen, hydrogen, a rare gas, or a mixed gas thereof may be used. Atmosphere can be preferably used. Also,
In order to form a coating film of the composition of the present invention on a substrate with good adhesion and high density, it is preferable to perform light irradiation treatment at least once before and after coating.

In such light irradiation treatment, in addition to visible light, ultraviolet light, far ultraviolet light, low-pressure or high-pressure mercury lamp, deuterium lamp, discharge light of rare gas such as argon, krypton, xenon, YAG laser, etc. , Argon laser, carbon dioxide laser, XeF, XeCl,
An excimer laser such as XeBr, KrF, KrCl, ArF, or ArCl can be used as a light source. These light sources are preferably 10 to 5,000.
An output of 0 W is used. Usually 100 to 100
0 W is sufficient. The wavelength of these light sources is not particularly limited as long as the polysilane compound in the composition or the coating film absorbs even a little, but 170 nm to 600 nm is preferable.

The temperature during the light irradiation treatment is preferably room temperature to 300 ° C. The processing time is about 0.1 to 30 minutes. It is preferable that these light irradiation treatments are performed in a non-oxidizing atmosphere similar to the film forming step of the polysilane compound. It is presumed that such light irradiation treatment causes the cleavage of the silicon-silicon bond and the recombination reaction of the polysilane compound in the coating film, thereby improving the film physical properties such as adhesion to the substrate. It Furthermore, the silane compound in the coating film undergoes ring-opening polymerization by light irradiation to become polysilane,
It is considered that a denser film is formed.

The coating film of the composition of the present invention formed as described above is converted into a silicon film or a silicon oxide film by heat and / or light treatment in a suitable atmosphere. The treatment method at this time preferably includes a heat treatment step.

When forming a silicon film, the coating film of the composition of the present invention formed as described above is treated in a non-oxidizing atmosphere.
The heat treatment is preferably performed in an argon atmosphere or argon containing hydrogen, preferably at about 100 to 1,000 ° C, more preferably at about 200 to 850 ° C, and further preferably at about 300 ° C to 500 ° C. Generally, an amorphous silicon film is obtained at a temperature of about 550 ° C. or lower, and a polycrystalline silicon film is obtained at a temperature of 550 ° C. or higher. When the ultimate temperature is lower than 300 ° C., the thermal decomposition of the polysilane compound does not proceed sufficiently and the silicon film having a sufficient thickness may not be formed. When a polycrystalline silicon film is to be obtained, the amorphous silicon film obtained above can be irradiated with laser to be converted into a polycrystalline silicon film. It is preferable to use an inert gas such as helium or argon, or an atmosphere in which a reducing gas such as hydrogen is mixed, as the atmosphere for irradiating the laser.

The light irradiation treatment at this time can be carried out in the same manner as the light irradiation treatment at the time of forming the film of the composition of the present invention. When a silicon oxide film is to be formed, the coating film of the composition of the present invention formed as described above is heat-treated and / or irradiated with light in the presence of oxygen and / or ozone, for example, in the air. It is done by processing.

The heat treatment is carried out by using a heating means such as a hot plate or an oven, preferably 100 to 800.
C., more preferably 200 to 600.degree. C., further preferably 300.degree. C. to 500.degree. C., preferably 1 to 300.
Minutes, more preferably 5 to 120 minutes, still more preferably 1
It is performed for 0 to 60 minutes. When the treatment temperature is lower than 100 ° C, the oxidation reaction may be insufficient, while the treatment temperature is 80
If the temperature is higher than 0 ° C, cracks may occur in the film after oxidation, which is not preferable. If the treatment time is shorter than 1 minute, the oxidation reaction may be insufficient, while it is not necessary to perform the heat treatment for a long time exceeding 300 minutes.

The silicon film and the silicon oxide film formed in the present invention may contain impurities such as carbon in addition to silicon oxide, as long as the object of the present invention is not impaired. The film thickness of the silicon film and the silicon oxide film obtained in the present invention is preferably 0.005 to 20 μm.
m, more preferably about 0.01 to 10 μm.

The film thickness of the obtained silicon film and silicon oxide film can be further increased by forming the film a plurality of times by the method of the present invention. For example, the thickness is 1 m.
It is also possible to form a silicon oxide film of about m.

The substrate used for forming the silicon oxide film of the present invention is not particularly limited. The substrate on which the coating film is formed may be flat or non-planar with steps, and the form thereof is not particularly limited. When the oxidation treatment of the coating film of the polysilane compound is performed by heat treatment, the material of the substrate is preferably one that can withstand the treatment temperature.

As a concrete example of the material of such a substrate,
Examples thereof include glass, metal, plastic, ceramics and the like. Examples of the glass include quartz glass,
Borosilicate glass, soda glass, lead glass, lanthanum glass, etc. can be used. Examples of metals include gold, silver,
Copper, nickel, silicon, aluminum, iron and stainless steel can be used. As the plastic, for example, polyimide, polyether sulfone, norbornene ring-opening polymer and hydrogenated product thereof can be used. Furthermore, the shape of these substrates is not particularly limited to a lump shape, a plate shape, a film shape, or the like.

In the present invention, the silicon film or silicon oxide film is formed as described above. INDUSTRIAL APPLICABILITY The method of the present invention can form a dense silicon film or silicon oxide film regardless of the area or shape of the substrate, and can be suitably used for manufacturing a device that requires high reliability. . Further, the method of the present invention is low in cost because an expensive device such as a vacuum device is unnecessary.

In the case where the treatment for converting the coating film into a silicon film or a silicon oxide film is performed by light treatment, a part of the coating film can be selectively removed by using a photomask having a desired pattern. By irradiating with light, it is possible to form a silicon film and a silicon oxide film having an arbitrary pattern.

[0055]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 (Synthesis of Silane Compound) A 4-liter flask having a capacity of 3 L equipped with a thermometer, a cooling condenser, a dropping funnel and a stirrer was replaced with argon gas, and then dried with 1 L of tetrahydrofuran.
And 18.3 g of lithium metal were charged, and argon gas was bubbled. While stirring this suspension at 0 ° C., 333 g of diphenyldichlorosilane was added from a dropping funnel,
After the dropwise addition was completed, stirring was continued for 12 hours at room temperature until the lithium metal completely disappeared. The reaction mixture was poured into 5 L of ice water to precipitate the reaction product. This precipitate was separated by filtration, washed well with water, washed with cyclohexane, and vacuum dried to obtain 140 g of a white solid. 100 g of this white solid and 1,000 ml of dried cyclohexane
Was charged into a 2 L flask, 4 g of aluminum chloride was added, hydrogen chloride was introduced at room temperature, and the mixture was cooled to 5 under argon atmosphere.
The reaction continued for an hour. Here, separately, 40 g of lithium aluminum hydride and 400 ml of diethyl ether were charged into a 3 L flask, and the above reaction mixture was added with stirring at 0 ° C. under an argon atmosphere, followed by stirring at the same temperature for 1 hour and further at room temperature for 12 hours. Stirring was continued. After removing the aluminum compound from the reaction mixture, vacuum distillation was performed at 70 ° C. and 10 mmHg to obtain 10 g of a colorless liquid. This is IR, ¹ H-NMR, ²⁹ Si-NMR, GC-MS
From each spectrum of, it was found to be cyclopentasilane.

Synthesis Example 2 (Synthesis of Polysilane Compound) 10 g of the cyclopentasilane obtained in Synthesis Example 1 was added to a 100 mL flask under an argon atmosphere and irradiated with a 500 W high pressure mercury lamp for 30 minutes while stirring. A solid formed. The obtained white solid was insoluble in toluene, cyclohexane and THF. Moreover, when a part of this white solid was taken and exposed to air, it ignited and quickly burned.

Example 1 When 100 g of the cyclopentasilane obtained in Synthesis Example 1 was added to the white solid obtained in Synthesis Example 2, a colorless transparent solution was obtained. This solution was placed under a nitrogen gas atmosphere for 2,
After spin coating on a glass substrate at a rotation speed of 000 rpm, the glass substrate was set on a hot plate in a nitrogen gas atmosphere, heat-treated at 200 ° C. for 10 minutes, and further heat-treated at 500 ° C. for 15 minutes. The resulting coating film had a metallic luster. When the ESCA spectrum of this thin film having a metallic luster was measured, only a peak attributed to Si at 99 eV was observed, and other elements such as carbon due to the solvent were not detected at all. This ESCA spectrum is shown in FIG. The film thickness of this silicon film was 80 nm. Further, when the XRD of this Si film was measured, no crystal peak was confirmed and it was found to be amorphous silicon.

Example 2 A film was formed in the same manner as in Example 1 except that the heat treatment at 500 ° C. was performed in air. The resulting coating film was transparent and had no metallic luster. ES of this film
When the CA spectrum was measured, only silicon and oxygen atoms were detected, and it was found to be a silicon oxide film.
Furthermore, the energy of the 2p orbit of this silicon is 104 eV
Therefore, it was found that the film was a SiO ₂ film. This E
The SCA spectrum is shown in FIG.

Comparative Example 1 When toluene was used instead of cyclopentasilane in Example 1, a white solid was not dissolved at all, and polysilane could not be formed into a film.

[0061]

According to the present invention, unlike a method such as a CVD method or a sputtering method which uses a gaseous raw material which is highly toxic or reactive in a vacuum system, a simple operation or apparatus can be used.
Provided are compositions and methods capable of efficiently forming a silicon film and a silicon oxide film on a substrate, for example, with a high yield and a high formation rate. According to the present invention, a silicon film and an LSI used for a solar cell, a TFT, or the like,
It is possible to efficiently form a silicon oxide film useful as an electrical insulator film, a dielectric film, a protective film, or the like used in a thin film transistor, a photoelectric conversion device, a photoconductor, or the like.

[Brief description of drawings]

FIG. 1 is an ESCA spectrum diagram of the silicon film obtained in Example 1.

FIG. 2 ESCA of silicon oxide film obtained in Example 2
It is a spectrum figure.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 21/208 H01L 21/208 Z 21/316 21/316 C F term (reference) 4J002 CP211 EX006 GP00 GQ00 4J035 CA02N CA021 CA022 JA01 LB20 4J038 DL011 LA02 MA14 NA20 NA21 NA27 PA17 PA19 PB09 PC02 PC03 PC08 5F053 AA50 BB60 DD01 FF01 GG02 GG03 LL05 PP03 PP05 PP20 RR05 RR13 5F058 BA20 BC02 BD04 BF46 B10B17BH03 B02

Claims (5)

[Claims] 1. The formula (A) Si _n R _m wherein n is an integer of 3 or more, and m is n to (2n +).
2) is an integer and m R are independently of each other a hydrogen atom, an alkyl group, a phenyl group or a halogen atom, provided that all of the m R are hydrogen atoms and m = 2n.
And n is an integer of 7 or more, and at least one silane selected from the group consisting of (B) cyclopentasilane, cyclohexasilane, and silylcyclopentasilane. A silane composition containing a compound. 2. A hydrogenated chain silane compound represented by the formula (A ′) Si _i H _{2i + 2,} wherein i is an integer of 2 to 8, formula Si _j H _2j wherein j is A hydrogenated cyclic silane compound represented by, which is an integer of 3 to 10, and a formula Si _k H _k, wherein k is an integer of 6 to 10, from the group consisting of hydrogenated cage silane compounds represented by A product produced by irradiation of at least one selected silane compound,
And (B) a silane composition containing at least one silane compound selected from the group consisting of cyclopentasilane, cyclohexasilane and silylcyclopentasilane. 3. The silane composition according to claim 1, which is used for forming a silicon film or a silicon oxide film. 4. A coating film comprising the silane composition according to claim 1 or 2 is formed on a support, and then heat and / or light treatment is performed in a non-oxidizing atmosphere.
A method of forming a silicon film on a substrate. 5. A coating film comprising the composition according to claim 1 or 2 is formed on a support, and then heat and / or light treatment is performed in an atmosphere containing oxygen and / or ozone. A method of forming a silicon oxide film on a substrate.