JP2001348219A - Spiro [4, 4] nonasilane and composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new spiro silane compound, the application and a utilizing method of its application. SOLUTION: The method of forming spiro [4, 4] nonasilane, which is a new compound, is performed by reacting hexadeca phenyl spiro [4, 4] nonasilane with gaseous hydrogen chloride in the presence of Lewis acid to form hexadeca chloro spiro [4, 4] nonasilane and hydrogenating. The application, the composition containing the same and the method of forming a silicon film on a supporting body using a silicon hydride compound as a starting silicon source by utilizing the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound, spiro [4.4] nonasilane, its use and a composition containing it, and the use of this composition. More specifically, the present invention relates to spiro [4.4] nonasilane, its use, a composition containing the same, and a method of forming a silicon film on a support using a silicon hydride compound as a starting silicon source.

[0002]

2. Description of the Related Art Conventionally, as a method of forming an amorphous silicon film or a polysilicon film, thermal CVD (Chemical Vapor D) of monosilane gas or disilane gas is used.
An evaporation method, a plasma CVD method, an optical CVD method, or the like is employed. In general, a thermal CVD method (J.Vac.Sci.Technolo) is applied to polysilicon.
gy., vol. 14, p. 1082 (1977)), and the amorphous silicon is formed by a plasma CVD method (Soli).
d State Com., vol. 17, p. 1193 (1975)
Is widely used, and is used for manufacturing a liquid crystal display device having a thin film transistor, a solar cell, and the like.

However, in the formation of a silicon film by the CVD method, the following further improvements have been awaited in terms of process. Since a gas phase reaction is used, silicon particles are generated in the gas phase, so that the production yield due to contamination of the apparatus and generation of foreign matter is low. Since the raw material is gaseous, it is difficult to obtain a substrate with a uniform thickness on a substrate having an uneven surface. Low productivity due to slow film formation rate. The plasma CVD method requires a complicated and expensive high-frequency generator or vacuum device. Further, in terms of material, gaseous silicon hydride having high toxicity and reactivity is used, so that there is not only a difficulty in handling but also a gaseous silicon requires a closed vacuum device. In general, these devices are large-scale and expensive, and also consume a large amount of energy in a vacuum system or a plasma system, which leads to an increase in product cost.

In recent years, a method of applying liquid silicon hydride without using a vacuum system has been proposed. JP-A-1-29661 discloses a method of forming a silicon-based thin film by liquefying and adsorbing a gaseous raw material on a cooled substrate and reacting it with chemically active atomic hydrogen. I have. However, in this method, since the vaporization and cooling of the silicon hydride as the raw material are continuously performed, not only a complicated apparatus is required, but also it is difficult to control the film thickness.

Further, Japanese Patent Application Laid-Open No. Hei 7-267621 discloses a method of applying a liquid silicon hydride having a low molecular weight to a substrate. However, this method is difficult to handle because the system is unstable. In addition, since the raw material is liquid, it is difficult to obtain a uniform film thickness when applied to a large-area substrate. On the other hand, examples of solid silicon hydride polymers are reported in British Patent GB-2077710A, but cannot be formed into a film by coating because they are insoluble in a solvent.

Further, Japanese Patent Application Laid-Open No. Hei 9-237927 discloses a method of applying a polysilane solution to a substrate and thermally decomposing the silicon film to release a silicon film for the purpose of manufacturing a solar cell. However, in the case of a silicon compound containing carbon, a large amount of carbon remains as an impurity in thermal decomposition or photolysis by ultraviolet irradiation, so that it is difficult to obtain an amorphous or polycrystalline silicon film having excellent electric characteristics. Further, JP-A-60-24261 discloses the following formula:

[0007]

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(Where n is 3, 4 or 5;
Is a H or SiH ₃ ) gaseous atmosphere of a cyclic silane compound and a halogen compound, which is formed in a deposition chamber in which the support is disposed, and heat energy is applied to these compounds to form silicon on the support. A method for forming a silicon deposited film by thermal CVD for forming a deposited film containing atoms is disclosed. In the above publication, the cyclic silane compound represented by the above formula is specifically disclosed by five kinds of chemical structural formulas. However, with respect to these cyclic compounds, not only the identification data of the compounds but also their production methods are not described in the publication.

On the other hand, with respect to a method for producing polysilane, generally, a monomer having each structural unit is used as a raw material.
For example, it can be manufactured by the following method.
(A) A method of dehalogenating polycondensation of halosilanes in the presence of an alkali metal in an amount equivalent to a halogen atom (so-called “Kipping method”, J. Am. Chem. Soc., 1
10, 124 (1988), Macromole
cures, 23, 3423 (1990)); (b)
A method of subjecting halosilanes to dehalogen condensation polymerization by electrode reduction (J. Chem. Soc., Chem. Commun.,
1161 (1990), J. Chem. Soc., Ch.
em. Commun., 897 (1992));
(C) A method of subjecting hydrosilanes to dehydrocondensation polymerization in the presence of a metal catalyst (JP-A-4-334551):
(D) A method by anionic polymerization of disilene cross-linked with biphenyl or the like (Macromolecules, 23
Volume, 4494 (1990)). (E) After synthesizing a cyclic silicon compound substituted with a phenyl group or an alkyl group by the above method, a known method (for example, Z. anorg.a
Chem., 459, p. 123 (1979)) to obtain a hydro-substituted or halogen-substituted product. These halogenated cyclosilane compounds can be prepared by known methods (for example, Mh. Chem. Vol. 106,
503, 1975), (Z. Anorg. All)
g. Chem. Vol. 621, p. 1517, 1995), (J. Chem. Soc., Chem. Commu).
n., p. 777, 1984). As described above, polysilane is generally synthesized by a polycondensation reaction, but a step of purifying the synthesized polymer is necessary because polycondensation produces a salt or the like as a by-product. Recently, Macromolecules (Macromole)
cules, 27, 2360, 1994)
It is disclosed that phenylnonamethylcyclopentasilane 1 undergoes anionic ring-opening polymerization to produce poly (phenylnonamethylpentasilanylene) 2. Unlike the above-mentioned polycondensation reaction, this ring-opening polyaddition reaction of a cyclic monomer has no by-product, and is an excellent method for synthesizing high-purity polysilane. Such ring-opening addition polymerization is particularly preferable in applications requiring high purity such as electronic materials. However, in the above-mentioned monomers, carbon atoms such as methyl group and phenyl group are bonded to silicon atoms, and even if such polysilane is thermally decomposed, only polycarbosilane with carbon incorporated is generated, and silicon for semiconductor Can not get. Also, regarding a method for synthesizing a spiro [4.4] nonasilane skeleton, J. Organomet. Chem., 19
In 1975, vol. 100, p. 127, when bi (nonamethylcyclopentasilanyl) or octadecamethylbicyclo [4.4.0] decasilane was treated with an aluminum chloride catalyst, skeletal rearrangement proceeded and monosilyl spiro [4 .4]
It has been reported that a methyl-substituted product having a nonasilane skeleton and a spiro [4.5] decasilane skeleton can be obtained at a ratio of 7: 3, and that the spiro [4.4] nonasilane skeleton is thermodynamically stable. I know. However, the monosilylspiro [4.4] nonasilane skeleton has all substituents of a methyl group, and no hydrogen-substituted form has been reported. Cannot be converted.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel compound spiro [4.4] nonasilane composed of only a silicon atom and a hydrogen atom. Another object of the present invention is to provide a method for producing spiro [4.4] nonasilane and its use. Still another object of the present invention is to provide a composition for realizing the above-mentioned use of spiro [4.4] nonasilane. Yet another object of the present invention is to provide a method for producing polysilane from the composition of the present invention. Still another object of the present invention is to provide a method for converting a polysilane film to a silicon film. Still other objects and advantages of the present invention will become apparent from the following description.

[0011]

According to the present invention, the above objects and advantages of the present invention are firstly achieved by the following formula:

[0012]

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This is achieved by a spiro [4.4] nonasilane represented by the formula:

The above objects and advantages of the present invention are:
Hexadecaphenyl spiro [4.4] nonasilane is reacted with hydrogen chloride gas in the presence of a Lewis acid to produce hexadecachlorospiro [4.4] nonasilane, which is then hydrogenated. 4.4] This is achieved by a method for producing nonasilane. Thirdly, the above objects and advantages of the present invention are achieved by the use of spiro [4.4] nonasilane as an initiator for radical polymerization of cyclic silicon hydride compounds. Fourth, the above objects and advantages of the present invention are attained by a ring-opening polymerizable composition containing spiro [4.4] nonasilane and a cyclic silicon hydride compound.

Fifth, the above objects and advantages of the present invention are attained by a method for producing polysilane, which comprises subjecting a cyclic silicon hydride compound to ring-opening polymerization in the presence of spiro [4.4] nonasilane. Sixth, the above objects and advantages of the present invention are achieved by a method for forming a silicon film on a support, which comprises thermally or photolyzing a polysilane film formed on the support.

The spiro [4.4] nonasilane of the present invention is
For example, a known method of converting a phenyl group bonded to a silicon atom from hexadecaphenylspiro [4.4] nonasilane to a chlorine atom and then further converting to a hydrogen atom (for example, Mh. Chem. 106: 503, 1975
Year), (Z. Anorg. Allg. Chem. No. 62)
1, 1517 (1995)), (J. Chem.
Soc., Chem. Commun., 777, 1984). For example, hexadecaphenyl spiro [4.4] nonasilane is chlorinated by introducing hydrogen chloride gas in the presence of a Lewis acid catalyst such as aluminum chloride and then hydrogenated with lithium aluminum hydride to obtain hexadecaphenyl. Spiro [4.
[4] By converting all phenyl substituents of nonasilane to hydrogen atoms, spiro [4.4] nonasilane consisting of only silicon and hydrogen atoms can be produced.

The chlorination reaction can be carried out, for example, at a temperature of 0 to 80 ° C. for 1 to 12 hours. The Lewis acid catalyst can be used, for example, in a ratio of 0.1 to 20% by weight based on hexadecaphenylspiro [4.4] nonasilane. As a reaction solvent, for example, an organic solvent such as toluene is used. The reduction reaction is performed, for example, at a temperature of 0 to 50 ° C for 1 to 24 hours.

Hexadecaphenylspiro [4.4] nonasilane as a raw material is obtained, for example, by dehalogenating and condensing diphenyldichlorosilane and tetrachlorosilane with lithium metal or the like.

Utilizing the above reaction, spiro [4.4] nonasilane can be prepared as a composition with cyclopentasilane containing the same as follows. For example, a mixture of diphenyldichlorosilane and tetrachlorosilane is cyclized with lithium metal in tetrahydrofuran to form a mixture containing decaphenylcyclopentasilane and hexadecaphenylspiro [4.4] nonasilane, and then the mixture is dissolved in toluene. By treating with hydrogen chloride gas in the presence of an aluminum chloride catalyst and then with a hydrogenating agent such as lithium aluminum hydride, cyclopentasilane is converted from decaphenylcyclopentasilane and hexadecaphenylspiro [4.4]
Spiro [4.4] nonasilane is produced from nonasilane. After the treatment with the hydrogenating agent, desalting treatment can be performed using silica gel, activated carbon, or the like, if necessary.

A mixture containing spiro [4.4] nonasilane and cyclopentasilane can also be produced by aging a solution of a mixture of cyclopentasilane and silylcyclopentasilane in an inert atmosphere. A mixture of cyclopentasilane and silylcyclopentasilane can be obtained, for example, by cyclizing diphenyldichlorosilane with lithium metal in tetrahydrofuran to form a mixture of decaphenylcyclopentasilane and dodecaphenylcyclohexasilane, and then chloride in the presence of aluminum chloride. It can be produced by treating with hydrogen and further treating with a hydrogenating agent such as lithium aluminum hydride. Thereafter, if necessary, desalting treatment can be performed using silica gel, activated carbon, or the like. If the solution of this mixture is allowed to stand for 2 weeks or more in an inert atmosphere, spiro [4.4] nonasilane, which was not detected immediately after the production, is produced, and a mixture containing spiro [4.4] nonasilane and cyclopentasilane A solution is formed.

Spiro [4.4] nonasilane can also be obtained as a single compound instead of as a mixture with cyclopentasilane. For example, from the mixture of decaphenylcyclopentasilane and hexadecaphenylspiro [4.4] nonasilane obtained above, only hexadecaphenylspiro [4.4] nonasilane is isolated by fractional crystallization or the like. Spiro [4.4] nonasilane can be produced according to the method described above. The spiro [4.4] nonasilane of the present invention is obtained by radical ring-opening addition polymerization of a silicon hydride compound consisting of only silicon atoms and hydrogen atoms, for example, a cyclic silicon hydride compound such as cyclopentasilane, to give a solvent-soluble polysilane. It has the chemical property that it can be converted. That is, even if cyclopentasilane alone is dissolved in a hydrocarbon solvent such as toluene, and the solution is heated to about the boiling point of the solvent, the polymerization reaction does not proceed. Similarly, when about 1% by weight of spiro [4.4] nonasilane is dissolved in a hydrocarbon solvent such as toluene and heated, the polymerization reaction of cyclopentasilane proceeds smoothly. This is Spiro [4.4]
Nonasilane is radically cleaved at its spiro site to generate a silicon radical, which acts as an initiator to cause a radical ring-opening reaction of a silicon hydride compound, for example, a cyclic silicon hydride compound such as cyclopentasilane. Inferred.

The polysilane solution thus obtained has good coating properties and can form a good polysilane film on a substrate. The polysilane film is further decomposed by thermal decomposition or photodecomposition. It was also found that it could be converted to a silicon film.

Therefore, the spiro [4.4] nonasilane of the present invention obtained as described above is mixed with various silicon hydride compounds, and these silicon hydride compounds are mixed with the above-mentioned cyclopentasilane. It can be polymerized similarly. Examples of the silicon hydride compound used here include hydrogenated cyclic silane compounds such as cyclotrisilane, cyclotetrasilane, cyclopentasilane, cyclohexasilane, cycloheptasilane, and cyclooctasilane; n-pentasilane, i-pentasilane , Neo-
Pentasilane, n-hexasilane, n-heptasilane,
Chain silane compounds such as n-octasilane and n-nonasilane; 1,1′-bicyclobutasilane, 1,1′-bicyclopentasilane, 1,1′-bicyclohexasilane,
1'-bicycloheptasilane, 1,1'-cyclobutasilylcyclopentasilane, 1,1'-cyclobutasilylcyclohexasilane, 1,1'-cyclobutasilylcycloheptasilane, 1,1'-cyclopenta Silylcyclohexasilane, 1,1′-cyclopentasilylcycloheptasilane, 1,1′-cyclohexasilylcycloheptasilane, spiro [2.2] pentasilane, spiro [3.
3] Spiro structure silane compounds such as heptatasilane, spiro [4.5] decasilane, spiro [4.6] undecasilane, spiro [5.5] undecasilane, spiro [5.6] undecasilane, spiro [6.6] tridecasilane And the like. Of these, cyclopentasilane, cyclohexasilane, cycloheptasilane, and the like are preferable in terms of ease of synthesis and purification, stability, and the like.

The ring-opening polymerizable solution composition of the present invention containing spiro [4.4] nonasilane and a silicon hydride compound can be prepared by dissolving these compounds in a suitable solvent. Such a solvent is not particularly limited as long as it dissolves spiro [4.4] nonasilane and a silicon hydride compound and does not react with them. Hydrocarbon solvents such as n-heptane, n-octane, decane, toluene, xylene, cymene, durene, indene, dipentene, tetrahydronaphthalene, decahydronaphthalene, cyclohexylbenzene; ethylene glycol dimethyl ether, ethylene glycol diethyl ether; Ether solvents such as ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether and p-dioxane: propylene carbonate, γ-butyrolactone , N-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide, cyclohexanone, etc. It can be exemplified ton polar solvent. Of these, hydrocarbon solvents and ether solvents are preferred, and hydrocarbon solvents are more preferred, in view of the solubility of spiro [4.4] nonasilane and the silicon hydride compound and the stability of the solution. These solvents can be used alone or as a mixture of two or more.

The appropriate concentration of the solid content in the above solution composition varies depending on the thickness of the silicon film to be formed, but is preferably, for example, 0.01 to 30% by weight, and preferably 0.1 to 20% by weight. % Is more preferable, and
Particularly preferred is 10% by weight. The ratio of spiro [4.4] nonasilane to the silicon hydride compound is 0.01 to 100 parts by weight of the silicon hydride compound.
It is preferably 20 parts by weight, more preferably 0.1 to 15 parts by weight, particularly preferably 0.5 to 10 parts by weight.

The above solution composition does not impair the purpose or function.
Fluorine, silicone, non-ionic as required within the range
A small amount of a surface tension adjusting material such as a system can be contained.
This non-ionic surface tension adjusting material is applied to the solution
Improved wettability and improved leveling of the applied film.
Good, prevention of bumping of coating film, generation of citron skin, etc.
Help. Examples of such nonionic surfactants include fluorine.
Having an alkylated or perfluoroalkyl group
Has a fluorine-based surfactant or an oxyalkyl group
And polyether alkyl surfactants.
You. Examples of the fluorine-based surfactant include C₉F₁₉CON
HC₁₂H_{twenty five}, C₈F₁₇SO_TwoNH- (C_TwoH _FourO)₆H, C₉
F₁₇O (Pluronic L-35) C₉F₁₇, C₉F₁₇O
(Pluronic P-84) C₉F₁₇, C₉F₇O (Tetro
Nick-704) (C₉F₁₇)_TwoAnd so on.
You. Here, Pluronic L-35: Asahi Denka Kogyo Co., Ltd.
Manufactured by Polyoxypropylene-Polyoxyethylene Block
Copolymer, average molecular weight 1,900; Pluronic P-
84: Polyoxypropylene-Po available from Asahi Denka Kogyo Co., Ltd.
Lioxyethylene block copolymer, average molecular weight 4,2
00; Tetronic-704: manufactured by Asahi Denka Kogyo Co., Ltd.
N, N, N ', N'-tetrakis (polyoxypropylene
-Polyoxyethylene block copolymer), average molecular weight
5,000. Commercialization of these fluorinated surfactants
Specific examples of products include F-top EF301 and EF3
03, EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), Megapha
F171 and F173 (Dainippon Ink Co., Ltd.),
Asahi Guard AG710 (made by Asahi Glass Co., Ltd.), Florer
FC-170C, FC430, FC431 (Sumitomo
3M Co., Ltd.), Surflon S-382, SC
101, SC102, SC103, SC104,
SC105 and SC106 (made by Asahi Glass Co., Ltd.), BM
-1000, 1100 (BM Chemie)
Scheggo-Fluor (Schwegma)
nn company). Also polyether
Examples of the alkyl-based surfactant include polyoxyethylene.
Lenalkyl ether, polyoxyethylene allylate
Ter, polyoxyethylene alkylphenol ether
, Polyoxyethylene fatty acid ester, sorbitan fat
Fatty acid ester, polyoxyethylene sorbitan fatty acid
Stele, oxyethylene oxypropylene block poly
And the like. These polyethers
Specific examples of commercially available alkyl surfactants include emma
Rugen 105, 430, 810, 920, Leod
SP-40S, TW-L120, Emanol 31
99, 4110, Exel P-40S, Bridge 3
0, 52, 72, 92, Arussel 20, Emazo
320, Tween 20, 60, Merge 45 (Izu
Remo (made by Kao Corporation), Noni Ball 55 (Sanyo Chemical Co., Ltd.)
Manufactured). Non-ionic other than the above
As the surfactant, for example, polyoxyethylene fatty acid
Ester, polyoxyethylene sorbitan fatty acid ester
And polyalkylene oxide block copolymers
Yes, specifically Chemistat 2500 (Sanyo Chemical Industries, Ltd.)
Co., Ltd.), SN-EX9228 (San Nopco Co., Ltd.)
Nonal 530 (manufactured by Toho Chemical Industry Co., Ltd.)
Can be mentioned.

In forming a coating film with the above solution composition, the solution composition can be used after filtering the solution composition with a membrane filter made of Teflon or regenerated cellulose to remove solid foreign matter.

Next, there is no particular limitation on the material, shape, etc. of the support on which the solution composition is applied to form a coating film, but the material is preferably one that can withstand the heat treatment in the next step. Is preferably flat. Specific examples of the material of these supports include glass, metal,
Plastics, ceramics, etc. can be mentioned. As the glass, for example, quartz glass, borosilicate glass, soda glass, and lead glass can be used. As the metal, for example, gold, silver, copper, nickel, aluminum, iron,
Stainless steel can be used. As the plastic, for example, polyimide, polyether sulfone, or the like can be used. Further, the shape of these materials is not particularly limited in a bulk shape, a plate shape, a film shape and the like.

The coating method is not particularly limited, and for example, it can be performed by spin coating, dip coating, curtain coating, roll coating, spray coating, ink jet method, or the like. Coating is generally performed at a temperature of room temperature (20 ° C.) or higher. If the temperature is lower than room temperature, the solubility of the silicon compound may be reduced and the silicon compound may be partially deposited. The atmosphere for the application is preferably an inert gas such as nitrogen, helium, or argon. Further, if necessary, a reducing gas such as hydrogen may be mixed. When the spin coating method is used, the rotation speed of the spinner is determined by the thickness of the thin film to be formed, the composition of the coating solution, and the like.
5000 rpm, preferably 300 to 3000 rpm is used. The application can be repeated once or a plurality of times. The thickness of a suitable coating film varies as appropriate depending on the solid content concentration, but is 0.01 to 100 μm as the solid content.
m is preferred, and more preferably 0.1 to 10 μm. After the application, a heat treatment is performed to remove the solvent. The heating temperature varies depending on the type and boiling point of the solvent used, but is usually from 100 ° C to 200 ° C. The atmosphere is preferably performed in the same inert gas as nitrogen, helium, argon or the like used in the above-mentioned coating step.

Before the solution composition is coated on a support to form a coating film, the solution composition can be subjected to ultraviolet irradiation, if necessary. Irradiation with ultraviolet light improves the coating performance of the solution composition, although the reason is not necessarily clear, and makes it possible to easily form a coating film having a uniform thickness. Irradiation with ultraviolet light is sufficient at, for example, an amount of 0.1 to 100 J / cm ^{2 at} 365 nm. Examples of the ultraviolet light source include a low-pressure or high-pressure mercury lamp, a deuterium lamp, or discharge light of a rare gas such as argon, krypton, or xenon; YA
G laser, argon laser, carbon dioxide laser, X
eF, XeCl, XeBr, KrF, KrCl, Ar
An excimer laser such as F or ArCl can be used as a light source. As these light sources, 10
A power of 5000 W is used, and usually 100 to
1000 W is sufficient.

The polysilane film thus obtained can be converted into a silicon film by a dehydrogenation reaction when it is subsequently subjected to heat treatment or light treatment. In the case of heat treatment, an amorphous silicon film is generally obtained at an ultimate temperature of about 550 ° C. or lower, and a polycrystalline silicon film is obtained at a higher temperature. When an amorphous silicon film is to be obtained, preferably 30
0 ° C to 550 ° C, more preferably 350 ° C to 500 ° C is used. If the ultimate temperature is lower than 300 ° C., thermal decomposition of the silicon compound does not sufficiently proceed, and a silicon film having a sufficient thickness may not be formed. The atmosphere in which the heat treatment is performed is preferably an atmosphere in which an inert gas such as nitrogen, helium, or argon, or a reducing gas such as hydrogen is mixed. It is surprising that the resulting silicon film has a uniform thickness and a mirror-like finish. This is presumably because the heated coating contained unreacted spiro [4.4] nonasilane. Because Spiro [4.
4] This is because a coating film containing no nonasilane often forms a silicon film having an uneven thickness or a partially broken silicon film in some cases. Although the details have not been determined yet, according to the study of the present inventors, the solvent first volatilizes by this heating, and spiro [4.4] nonasilane contained at the same time or before or after that is spiro at the spiro site. Radical cleavage generates silicon radicals, which act as an initiator to cause a radical ring-opening reaction of a silicon hydride compound, for example, a cyclic silicon hydride compound such as cyclopentasilane, to partially oligomerize, Thereafter, it is believed that the thermal decomposition of the oligomer and the cyclic silicon hydride compound generates hydrogen and simultaneously forms a silicon film. In the case of light treatment, the light source used is a low-pressure or high-pressure mercury lamp, deuterium lamp, or discharge light of a rare gas such as argon, krypton, xenon; YAG laser, argon laser, carbon dioxide laser, XeF , XeCl, XeB
An excimer laser such as r, KrF, KrCl, ArF, or ArCl can be used as a light source. As these light sources, those having an output of 10 to 5000 W are used, and usually 100 to 1000 W is sufficient. The wavelength of these light sources is not particularly limited as long as the silicon compound absorbs even a little, but preferably 170 nm
６００600 nm. The use of laser light is particularly preferable in terms of conversion efficiency to a silicon film. The temperature during these light treatments is usually about room temperature, and the atmosphere is preferably in the above-mentioned inert gas, but can be appropriately selected according to the purpose.

Thus, from the composition containing spiro [4.4] nonasilane and the silicon hydride compound of the present invention, a silicon film, particularly an amorphous silicon film, can be advantageously formed on a support. The thickness of the silicon film can be, for example, 0.001 μm to 10 μm. The amorphous silicon film formed according to the present invention is used for various electronic devices such as a solar cell, an optical sensor, a thin film transistor, a photosensitive drum, and a protective film.

[0033]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, gas chromatography uses C
A silicone-based OV-17 (5%) was used as a liquid phase in Chromosorb W (60-80 mesh), and 120
Evolved with helium gas at ℃. The high performance liquid chromatography is performed on a normal phase column YMC-PACK-SIL.
(A-011) (trade name, manufactured by YMC) and developed with cyclohexane.

Synthesis Example 1 A three-liter four-necked flask 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 20.3 g of lithium metal were charged, and the mixture was bubbled with argon gas. While stirring at 0 ° C., a mixture of 296 g of diphenyldichlorosilane and 24.8 g of tetrachlorosilane was added to the suspension from a dropping funnel. After completion of the dropwise addition, stirring was continued at 25 ° C. for 12 hours until lithium metal completely disappeared. The reaction mixture was poured into 5 L of ice water to precipitate a reaction product. This precipitate was separated by filtration, washed well with water, washed with cyclohexane, and dried under vacuum to obtain 180 g of a white solid. Each spectrum of IR, ¹ H-NMR and ²⁹ Si-NMR indicated that this white solid was a mixture of two components.
The mixture was separated by high performance liquid chromatography, and it was found that the ratio of the main product to the by-product was 6: 1. Further, each IR, ¹ H-NMR, ²⁹
Measure each spectrum of Si-NMR and TOF-MS,
It was confirmed that the main product was decaphenylcyclopentasilane and the by-product was hexadecaphenylspiro [4.4] nonasilane. FIG. 1 shows a high performance liquid chromatogram of the above mixture.

Synthesis Example 2 After replacing the inside of a three-liter four-necked flask equipped with a thermometer, a cooling condenser, a dropping funnel and a stirrer with argon gas, 160 g of octaphenylcyclobutasilane which had been thoroughly dried and lithium metal were removed. 15.1 g was charged, and 1.5 L of dried tetrahydrofuran was added thereto from a dropping funnel while stirring. 25 ° C after dropping
For 3 hours. The suspension was filtered under a stream of argon to remove excess lithium metal,
While stirring with, 18.6 g of tetrachlorosilane was added from a dropping funnel. After completion of the dropwise addition, stirring was continued at 25 ° C. for further 12 hours. The reaction mixture was poured into 5 L of ice water to precipitate a reaction product. This precipitate was separated by filtration, washed well with water, washed with cyclohexane, and dried under vacuum to obtain 150 g of a white solid. This white solid was subjected to gel permeation chromatography, IR, ¹ H-NM
When each spectrum of R, ²⁹ Si-NMR and TOF-MS was measured, it was found that a mixture of 90% of octaphenylcyclobutasilane used as a raw material and 10% of the above hexadecaphenyl spiro [4.4] nonasilane was used. I understand.

Synthesis Example 3 50 g of a 9: 1 mixture of decaphenylcyclopentasilane and hexadecaphenylspiro [4.4] nonasilane of Synthesis Example 1 and 500 ml of dry toluene were charged into a 1 L flask, and 2 g of aluminum chloride was added. Hydrogen chloride was introduced at 25 ° C., and the reaction was continued for 5 hours under an argon atmosphere. Here, separately, 20 g of lithium aluminum hydride
And 200 ml of diethyl ether were charged into a 2 L flask, and the above reaction mixture was added thereto while stirring at 0 ° C. under an argon atmosphere. After stirring at the same temperature for 1 hour, stirring was further continued at 25 ° C. for 12 hours. When the aluminum compound was removed from the reaction mixture and the solvent was distilled off, 5 g of a viscous oil was obtained. This is IR, ¹ H-NMR,
^From each spectrum of ²⁹ Si-NMR and GC-MS, it was found that the mixture was a mixture containing cyclopentasilane and spiro [4.4] nonasilane at a ratio of 9: 1.

Synthesis Example 4 A three-liter four-necked flask equipped with a thermometer, a cooling condenser, a dropping funnel, and a stirrer was replaced with argon gas, and dried with tetrahydrofuran.
5 L and 21 g of lithium metal were charged and bubbled with argon gas. To this suspension, 380 g of diphenyldichlorosilane was added from a dropping funnel while stirring at 0 ° C. After completion of the dropwise addition, stirring was continued at 25 ° C. for 12 hours until lithium metal completely disappeared. 1 reaction mixture
The reaction product was precipitated by pouring into 0 L of ice water. The precipitate was separated by filtration, washed well with water, washed with cyclohexane, and dried under vacuum to obtain 230 g of a white solid.
Each spectrum of IR, ¹ H-NMR and ²⁹ Si-NMR indicated that this white solid was a mixture of two components. When this mixture was separated by high performance liquid chromatography, the ratio of the main product to the by-product was found to be 9: 1. In addition, each IR,
¹ H-NMR, ²⁹ Si-NMR, and TOF-MS spectra were measured, and it was confirmed that the main product was decaphenylcyclopentasilane and the by-product was dodecaphenylcyclohexasilane.

Synthesis Example 5 50 g of a 9: 1 mixture of decaphenylcyclopentasilane and dodecaphenylcyclohexasilane of Synthesis Example 4 was subjected to the same process as in Synthesis Example 3 to obtain 5 g of a viscous oil. These are IR, ¹ H-NMR, ²⁹ Si-NMR, GC-M
From each spectrum of S, it was found that the mixture was a mixture containing cyclopentasilane and silylcyclopentasilane at a ratio of 10: 1. 3 g of the mixture thus obtained was dissolved in 27 g of toluene under a nitrogen atmosphere. The gas chromatogram of this is shown in FIG. After leaving this toluene solution at 25 ° C. in a nitrogen atmosphere for 2 weeks, it was analyzed by gas chromatography. As a result, a new high-boiling component was detected in addition to cyclopentasilane and silylcyclopentasilane. The gas chromatogram of this is shown in FIG. When the GC-MS spectrum of this high boiling point component was measured, it was confirmed that the high boiling point component completely matched spiro [4.4] nonasilane. For reference, FIG. 4 shows a gas chromatogram of a toluene solution of a mixture of cyclopentasilane and spiro [4.4] nonasilane obtained in Synthesis Example 3.

Synthesis Example 6 85 g of a 9: 1 mixture of decaphenylcyclopentasilane and hexadecaphenylspiro [4.4] nonasilane of Synthesis Example 1 was recrystallized with 4 L of ethyl acetate to obtain 55 g of pure decaphenylcyclopentasilane. Obtained. When 50 g of decaphenylcyclopentasilane thus obtained was subjected to the process according to Synthesis Example 3, 5 g of pure cyclopentasilane was obtained. This was confirmed to have a purity of 99% or more by gas chromatography.

Synthesis Example 7 Mixture 200 of Decaphenylcyclopentasilane and Hexadecaphenyl Spiro [4.4] nonasilane of Synthesis Example 1
g was dissolved in 4 L of hot toluene and filtered while hot to obtain 20 g of a white solid in a toluene-insoluble portion. IR, ¹ H-NMR, ²⁹ Si-NMR, TOF-M of this white solid
When each spectrum of S and the retention time in high performance liquid chromatography were measured, it completely coincided with the above hexadecaphenylspiro [4.4] nonasilane. When the hexadecaphenyl spiro [4.4] nonasilane thus obtained was subjected to a process according to Synthesis Example 3, 2 g of pure spiro [4.4] nonasilane was obtained. This was confirmed to have a purity of 99% or more by gas chromatography. FIG. 5 shows a gas chromatogram of the toluene solution.

Spiro [4.4] nonasilane is oily at 25 ° C. FIG. 6 shows the infrared absorption spectrum. It is composed solely of silicon and hydrogen atoms, and the infrared spectrum is relatively simple, with a sharp peak at 2125 cm ^-1 attributed to the stretching vibration of silicon-hydrogen bonds, and at 985 cm ^-1 and 863 cm ^-1 . Silicon
A peak attributed to silicon stretching vibration is observed. FIG. 7 shows a mass spectrum. A molecular ion peak is observed at m / e = 268, which indicates that the molecular weight is 268. Further, a peak at m / e = 236 is strongly detected,
This is attributed to a fragment in which one monosilane (SiH ₄ ) was eliminated from the spiro [4.4] nonasilane molecule, and the peak at m / e = 206 was assigned to the spiro [4.4] nonasilane molecule.
4] It is attributed to a fragment from which disilane (Si ₂ H ₆ ) is eliminated from a nonasilane molecule.

The chemical properties of spiro [4.4] nonasilane include benzene, toluene, xylene, hexane,
Hydrocarbon solvents such as cyclohexane, indane and decahydronaphthalene; ether solvents such as diethyl ether, tetrahydrofuran, monoglyme and diglyme;
It is easily soluble in ordinary organic solvents such as ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone, and can be dissolved at any ratio. Spiro [4.4] nonasilane is a colorless and transparent oil at 25 ° C. It is very stable in an inert atmosphere such as argon or nitrogen, but is gradually oxidized when left in the air and easily converted to a siloxane structure. Is done. When spiro [4.4] nonasilane is exposed to heat of 300 ° C. or more in an inert atmosphere, a dehydrogenation reaction occurs and is converted into amorphous silicon. Further, this spiro [4.4] nonasilane generates a radical by heat treatment at about 100 ° C., and can be converted into a solvent-soluble polysilane by radical ring-opening polymerization of the cyclopentasilane.

Synthesis Example 8 Mixture 100 of octaphenylcyclobutasilane and hexadecaphenylspiro [4.4] nonasilane of Synthesis Example 2
g was dissolved in 2 L of hot toluene and filtered while hot to obtain 10 g of a white solid in a toluene-insoluble portion. IR, ¹ H-NMR, ²⁹ Si-NMR, TOF-M of this white solid
The spectrum of S and the retention time measured by gel permeation chromatography were completely consistent with the above hexadecaphenylspiro [4.4] nonasilane. When the hexadecaphenyl spiro [4.4] nonasilane thus obtained was subjected to the process according to Synthesis Example 3, 1 g of pure spiro [4.4] nonasilane was obtained. It has a purity of 9 by gas chromatography.
It was confirmed that it was 9% or more.

Example 1 10 g of a 10% toluene solution of spiro [4.4] nonasilane obtained in Synthesis Example 7 and 90 g of a 10% toluene solution of cyclopentasilane obtained in Synthesis Example 6 were mixed.
After the mixed solution was stirred at 50 ° C. for 12 hours in an argon atmosphere, the gas chromatogram was measured again.
No peak of spiro [4.4] nonasilane was observed for cyclopentasilane, indicating that it was converted to ring-opening-polymerized high-boiling polysilane. This solution was spin-coated at 2,000 rpm on a glass substrate in an argon atmosphere to obtain a colorless and transparent polysilane film. When this polysilane film was fired at 500 ° C., a silicon film having a metallic luster was obtained. The thickness of the silicon film measured by the alpha step was 1500 °. Further, when the ESCA of this silicon film was measured, only a peak derived from Si _2p was observed at 99 eV, and no other peak was observed. The Raman spectrum of the silicon film was measured, and the waveform was separated and analyzed. As a result, a Raman line attributed to TO phonon was observed at around 480 cm ⁻¹ ,
A Raman line attributed to LO phonon was observed at around m ^-1 and a Raman line attributed to LA phonon at around 320 cm ^-1 , indicating a 100% amorphous silicon film. When this amorphous silicon was irradiated with a XeCl excimer laser (308 nm), the silicon was polycrystallized and the crystallization ratio was 77%. When the 2P orbital energy of the silicon atom of the polycrystallized silicon film was measured by an ESCA spectrum (a spectrum diagram of which is shown in FIG. 8), it was found to be 99.0 eV, indicating that the film was silicon.

Example 2 A solution was prepared by dissolving 5 g of a mixture of cyclopentasilane and spiro [4.4] nonasilane obtained in Synthesis Example 3 in 95 g of toluene under an argon atmosphere. This solution was spin-coated on a quartz substrate under an argon atmosphere to form a film of a mixture of cyclopentasilane and spiro [4.4] nonasilane. The coated substrate is placed in an argon atmosphere at 500 ° C.
After heating for 5 minutes, a silicon film remained on the substrate. This silicon film was found to have 10
It was in a 0% amorphous state. XeCl excimer laser (308 nm) is applied to this amorphous silicon.
Irradiation, silicon is polycrystallized and the crystallization rate is 7
5%. When the 2P orbital energy of the silicon atom of the polycrystallized silicon film was measured by an ESCA spectrum, it was found to be 99.0 eV, which proved to be silicon.

Example 3 In an argon atmosphere, the spiro [4.
4] 1 g of nonasilane was dissolved in 9 g of toluene to prepare a solution. This solution was spin-coated on a quartz substrate under an argon atmosphere to form a spiro [4.4] nonasilane film. The coated substrate is placed in an argon atmosphere at 500 ° C. for 5 minutes.
After heating for a minute, a silicon film remained on the substrate. The silicon film was found to be 100% amorphous from the Raman scattering spectrum. When this amorphous silicon was irradiated with a XeCl excimer laser (308 nm), the silicon was polycrystallized and the crystallization ratio was 78%. When the 2P orbital energy of the silicon atom of the polycrystallized silicon film is measured by ESCA spectrum, 99.
It turned out to be 0 eV and it turned out to be silicon.

Comparative Example 1 In an argon atmosphere, a solution was prepared by dissolving 5 g of the cyclopentasilane obtained in Synthesis Example 6 in 95 g of toluene.
This solution was spin-coated on a quartz substrate in an argon atmosphere, but no repellent and uniform film was obtained.

Example 4 Under an argon atmosphere, 5 g of a mixture of cyclopentasilane and spiro [4.4] nonasilane obtained in Synthesis Example 3 was dissolved in 95 g of toluene to prepare a solution. This solution was spin-coated on a quartz substrate under an argon atmosphere to form a film of a mixture of cyclopentasilane and spiro [4.4] nonasilane. When the coated substrate was irradiated with UV under an argon atmosphere and then heated at 500 ° C. for 5 minutes, a silicon film remained on the substrate. The silicon film was found to be 100% amorphous from the Raman scattering spectrum. When this amorphous silicon was irradiated with a XeCl excimer laser (308 nm), the silicon was polycrystallized and the crystallization ratio was 80%. When the 2P orbital energy of the silicon atom of the polycrystallized silicon film was measured by an ESCA spectrum, it was found to be 99.0 eV, which proved to be silicon.

Example 6 A mixture of cyclopentasilane and spiro [4.4] nonasilane obtained in Synthesis Example 5 under an argon atmosphere (Synthesis Example 5)
5 g) was dissolved in 95 g of toluene to prepare a solution. This solution was spin-coated on a quartz substrate under an argon atmosphere to form a film of a mixture of cyclopentasilane and spiro [4.4] nonasilane. When this coated substrate was heated at 500 ° C. for 5 minutes in an argon atmosphere, a silicon film remained on the substrate. The silicon film was found to be 100% amorphous from the Raman scattering spectrum. Xe is added to this amorphous silicon.
When irradiated with a Cl excimer laser (308 nm), silicon was polycrystallized and the crystallization ratio was 75%.
When the 2P orbital energy of a silicon atom of a polycrystallized silicon film is measured by an ESCA spectrum, it is 99.0 eV.
It turned out to be silicon.

[0050]

According to the present invention, there is provided a novel compound spiro [4.4] nonasilane, a use thereof, a composition containing the same, and a support comprising a silicon hydride compound as a starting silicon source using the composition. A silicon film can be formed thereover.

[Brief description of the drawings]

FIG. 1 is a high performance liquid chromatogram of the mixture obtained in Synthesis Example 1.

FIG. 2 is a gas chromatogram of a toluene solution of a mixture of cyclopentasilane and silylcyclopentasilane used in Synthesis Example 5.

FIG. 3 is a gas chromatogram after leaving the above mixture at room temperature under a nitrogen atmosphere for 2 weeks.

FIG. 4 is a gas chromatogram of a toluene solution of a mixture of cyclopentasilane and spiro [4.4] nonasilane.

FIG. 5 is a gas chromatogram of a toluene solution of spiro [4.4] nonasilane obtained in Synthesis Example 7.

FIG. 6 is an infrared absorption spectrum of spiro [4.4] nonasilane obtained in Synthesis Example 7.

FIG. 7 is a mass spectrum diagram of spiro [4.4] nonasilane obtained in Synthesis Example 7.

FIG. 8 shows the ESC of the polycrystalline silicon film obtained in Example 1.
It is an A spectrum figure.

Claims (6)

[Claims] (1) The following formula (A): Spiro [4.4] nonasilane represented by the formula: 2. Reaction of hexadecaphenylspiro [4.4] nonasilane with hydrogen chloride gas in the presence of a Lewis acid to produce hexadecachlorospiro [4.4] nonasilane, followed by hydrogenation thereof. A method for producing spiro [4.4] nonasilane, which is characterized by the following. 3. Use of spiro [4.4] nonasilane as an initiator for radical polymerization of a cyclic silicon hydride compound. 4. A ring-opening polymerizable composition containing spiro [4.4] nonasilane and a cyclic silicon hydride compound. 5. The method of claim 1, wherein the cyclic silicon hydride compound is spiro [4.
4] A process for producing polysilane, which comprises subjecting ring-opening polymerization in the presence of nonasilane. 6. A method for forming a silicon film on a support, comprising subjecting a polysilane film formed on the support to thermal decomposition or photolysis.