NOVEL POLYSILANE COMPOSITION

Abstract: A novel polysilane composition useful as an organic semiconductor, which comprises a specified nonchlorinated polysilane compound having a weight-average molecular weight of 6,000 to 200,000, wherein all of the substituents and terminal groups are substituted by specified oxygen-free organic groups, and an acceptor level forming substance or/and a donor level forming substance.

Description: FIELD OF THE INVENTION The present invention relates to a new composition containing a specific polysilane compound and a dopant. More particularly, the present invention relates to a new composition containing a new polysilane compound of 6000 to 200000 in a weight average molecular weight in which all the substitutional groups and end groups being substituted by specific organic groups not containing oxygen atoms and an acceptor level forming material or a donor level forming material. The present invention includes a process of producing said composition. The composition of the present invention is useful as an organic semiconductor. BACKGROUND OF THE INVENTION Polysilane compounds were reported to be insoluble in solventsIn ( The Journal of American Chemical Society, 125, pp. 2291 (1924) ). Thereafter, it was reported that polysilanes are soluble in solvents and films can be made of them ( The Journal of American Ceramic Society, 61, pp. 504 (1978) ). Since then, the public attention has been focussed on polysilane compounds. Further, as for polysilane compounds, it was reported that they can be dissociated with ultraviolet rays, and research was made on utilization of them in resists ( Japanese Unexamined Patent Publications Sho.60(1985)-98431 and Sho.60(1985)-119550 ). Further, it was reported that polysilane compounds have photosemiconductor characteristics in which carriers are mobile due to σ-bonds of their principal chains ( Physical Review B, 35 , pp. 2818 (1987) ). And these polysilane compounds have been expected to be usable also in electrophotographic photosensitive members. However, in order that polysilane compounds be applicable in electronic materials, those polysilane compounds are required to be soluble in solvents and capable of providing films which are free of minute defects and excel in homogeneity. As for the electronic materials, any minute defect is not allowed and because of this, polysilane compounds to be used in the preparation of such electronic materials are required to be high quality polysilane compounds, which can be structurally defined also with respect to substituents and do not cause any abnormality upon film formation. There have been made various reports for synthesis of polysilane compounds. Those polysilane compounds reported are still problematic in using them in electronic materials. There are reported low-molecular weight polysilane compounds in which all the Si radicals being substituted by organic groups ( The Journal of American Chemical Society, 94, (11), pp.3806 (1972) and Japanese Patent Publication Sho.63(1988)-38033 ). Those described in the former literature are of the structure in which the end group of dimethylsilane being substituted by a methyl group. Those described in the latter literature are of the structure in which the end group of dimethylsilane being substituted by an alcoxy group. Any of them is 2 to 6 in polymerization degree and does not exhibit characteristics as the polymer. Particularly in this respect, any of them does not have an ability of forming a film as it is and is not industrially applicable. High-molecular weight polysilane compounds of the structure in which all the Si radicals being substituted by organic groups have been recently reported ( Nikkei New Material, pp. 46, August 15 of 1988 ). These compounds are synthesized through specific intermediates to cause reduction in their yield and it is difficult to mass-produce them on the industrial scale. In addition, methods of synthesizing polysilane compounds are reported ( The Journal of Organometallic Chemistry, pp. 198 C27 (1980) and The Journal of Polymer Science, Polymer Chemistry Edition vol. 22, pp.159-170 (1984) ) ). USP 4 546 163, is directed to a vinyl-containing polysilane capable of being converted to silicon-carbid-containing ceramics by pyrrolysis (abstract). According to column 8, lines 12 to 17, it is preferred to replace the chlorine or bromine endblocking groups with less reactive endblocking groups in case that a low oxygen containing ceramic material should be prepared. However, any of these synthetic methods is directed only to condensation reaction of the polysilane principal chain but does not touch about the end groups. And, in any of these synthetic methods, unreacted chlorine radicals and by-products due to side reactions are caused and it is difficult to stably obtain polysilane compounds as desired. DE-A-3 634 281 is directed to an electrically conductive polysilane composition comprising a polysilane being chemically or electrochemically doped. The polysilane according to D1 comprises halogen atoms as endgroups. Use of polysilane compounds as a photoconductive material is reported ( U.S. Patent No. 4,618,551, U.S. Patent No. 4,772,525 and Japanese Unexamined Patent Publication Sho.62(1987)-269964 ). However, in any of these cases, occurrence of undesirable negative effects due to unreacted chlorine radicals and by-products caused by side reactions are considered. Particularly, in U.S. Patent No. 4,618,551, polysilane compounds are used in electrophotographic photosensitive members and an extremely high voltage of 1000 V is applied upon use of those photosensitive members, although a voltage of 500 to 800 V is applied in an ordinary electrophotographic copying machine. It is considered that this is done in order to prevent occurrence of spotted abnormal phenomena on images reproduced since defects due to the structural defects of the polysilane compound will cause in the electrophotographic photosensitive member at an ordinary potential. In Japanese Unexamined Patent Publication Sho.62(1987)-269964, it is described that electrophotographic photosensitive members are prepared by using polysilane compounds and a photosensitivity is observed for each of them. However, any of those electrophotographic photosensitive members is not sufficient in photosensitivity and is inferior to the known selenium photosensitive member or the known organic photosensitive member in any respect. As above described, there are a number of unsolved problems for any of the known polysilane compounds to be utilized in the electronic materials. Thus, any polysilane compound which can be desirably used for industrial purposes has not yet realized. Summary of The Invention An object of the present invention relates is to provide a new polysilane composition usable as an organic semiconductor which contains a new polysilane compound having a weight average molecular weight of 6000 to 200000 and not containing chlorine atom in which all the substitutional groups and end groups being substituted by specific oxygen-free organic groups and an acceptor level forming material or/and a donor level forming material. Other object of the present invention is to provide said polysilane composition which has a good solubility in solvents and which makes it possible to form a semiconductor film having excellent characteristics. A further object of the present invention is to provide said polysilane composition which is usable in the preparation of various electronic devices and the like. A still further object of the present invention is to provide a method for producing said polysilane composition. The present invention attains the above objects, and the polysilane composition to be provided by the present invention is of the constitution which will be under described. That is, it is a polysilane composition containing a polysilane compound having a weight average molecular weight of 6000 to 200000 free from chlorine- and oxygen-containing groups, soluble in organic solvents and capable of forming films and which is represented by the following general formula (I) and either an acceptor level forming material or a donor level forming material, in which the content of said acceptor level forming material or said donor level forming material is 1 x 10⁻⁴ to 10 parts by weight versus 100 parts by weight of said polysilane compound. [Wherein, R₁ stands for an alkyl group of 1 to 2 carbon atoms; R₂ stands for an alkyl group, cycloalkyl group, aryl group or aralkyl group of 3 to 8 carbon atoms; R₃ stands for an alkyl group of 1 to 4 carbon atoms; R₄ stands for an alkyl group of 1 to 4 carbon atoms; A and A' respectively stands for an alkyl group, cycloalkyl group, aryl group or aralkyl group of 4 to 12 carbon atoms wherein the two substituents may be the same or different one from the other; and each of n and m is a mole ratio showing the proportion of the number of respective monomers versus the total of the monomers in the polymer wherein n + m = 1, 0 < n ≦ 1 and 0 ≦ m < 1.] In the polysilane compound represented by the general formula (I), A and A' are respectively an alkyl group or a cycloalkyl group of 5 to 12 carbon atoms. The acceptor level forming material comprises a halogen compound represented by the general formula : MXa ( wherein, M is an element belonging to the group VA of the periodic table, X is a halogen element, and a is an integer which is decided depending upon the valence number of the element M. ). The donor level forming material comprises an amine compound. Preferably the polysilane compound of the polysilan composition has a weight average molecular weight of 8000 to 120 000. Further, preferably in the polysilane composition the element belonging to the group VA is an element selected from the group consisting of N, P, As and Sb. Examples of the halogen compound represented by the general formula: MX a include NF₃, NF₅, NCl₃, NCl₅, NBr₃, NB₅, NI₃, PF₃, PF₅, PCl₃, PCl₅, PBr₃, PBr₅, PI₃, AsF₃, AsF₅, AsCl₃, AsBr₃, AsI₃, SbF₃, SbF₅, SbCl₃, SbCl₅, SbBr₃ and SbI₃. Detailed Explanation of the Preferred Embodiments The polysilane compound to be used in the present invention which is expressed by the foregoing general formula (I) and has a weight average molecular weight of 6000 to 200000 does have neither chlorine-containing group nor side reaction-causing group, and all the Si radicals thereof are substituted by specific organic groups not containing any oxygen atom. The polysilane compound is innoxious, easily soluble in aromatic solvents such as toluene, benzene, xylene, etc., halogenated solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, etc., and other solvents such as tetrahydrofuran (THF), dioxane, etc., and has an excellent film-forming ability. And, the film formed of the polysilane compound is homogenous, uniform in thickness, has an excellent heat-resistance and excels in hardness and toughness. Thus, the polysilane compound to be used in the present invention can be employed in the preparation of various electronic devices, medical devices, and it is a high molecular compound of high industrial value in use. Said electronic device includes organic photoconductive members, electric conductive members, photoresists, light information memory elements, etc. As described above, the polysilane compound to be used in the present invention is represented by the foregoing general formula (I) and has a weight average molecular weight of 6000 to 200000. In the viewpoints of desirable solubility in solvents and desirable film-forming ability, the polysilane compound is desired to be one that has a weight average molecular weight preferably of 8000 to 120000, most preferably of 10000 to 80000. As for the weight average molecular weight, polysilane compounds of less than 6000 in weight average molecular weight do not exhibit polymer characteristics and do not have a film-forming ability. On the other hand, polysilane compounds exceeding 200000 in weight average molecular weight are poor with respect to solubility in solvents, and it is difficult to form films therefrom. In the case where a film especially excelling in toughness is desired to be formed, it is desired to selectively use a polysilane compound of the foregoing formula (I) wherein the end groups A and A' are groups selected from the group consisting of alkyl groups having 5 to 12 carbon atoms, cycloalkyl groups, aryl groups and aralkyl groups respectively having 5 to 12 carbon atoms. The most desirable polysilane compounds in this case are those in which the end groups A and A' are groups selected from the group consisting of alkyl groups having 5 to 12 carbon atoms and cycloalkyl groups having 5 to 12 carbon atoms. The foregoing polysilane compound to be used in the present invention can be synthesized in the following manner. That is, under high purity inactive atmosphere containing neither oxygen nor water, dichlorosilane monomer in a solvent is contacted with a condensation catalyst comprising an alkaline metal to conduct dehalogenation and condensation polymerization, to thereby synthesize an intermediate polymer. The intermediate polymer thus obtained is separated from unreacted monomer and is reacted with a selected halogenating organic reagent in the presence of a condensation catalyst comprising an alkaline metal to condense an organic group to the terminals of the intermediate polymer, whereby obtaining the polysilane compound. And, the polysilane composition of the present invention can be obtained by adding to the polysilane compound thus obtained a halogen compound represented by the foregoing general formula : MXa as the acceptor level forming material or/and an amine compound as the donor level forming material. In the above synthesizing process, as any of the foregoing dichlorosilane monomer, intermediate polymer, halogenating organic reagent and alkaline metal condensation catalyst is highly reactive with oxygen and water, the foregoing polysilane compound to be used in the present invention cannot be obtained under such atmosphere wherein oxygen and/or water are present. Therefore, the foregoing procedures of obtaining the polysilane compound to be used in the present invention is necessary to be carried out under the atmosphere containing neither oxygen nor water. Thus, due regards are to be made such that all the reagents to be used and the reaction vessel to be used contain neither oxygen nor water and the reaction system is not incorporated with oxygen or/and water during the synthesizing process. Specifically, with respect to the reaction vessel to be used, it is subjected to vacuum suction and argon gas substitution in a blow box, whereby eliminating adsorption of water or/and oxygen in the inside of said vessel. As for the argon gas used in any case, it is necessary that the argon gas is dehydrated by passing it through a silica gel column, oxygen is then removed therefrom by passing the dehydrated through a column charged with copper power which is maintained at 100°C and the argon gas thus treated is used. As for the dichlorosilane monomer as the starting material, prior to introducing it into the reaction system, oxygen is removed therefrom by subjecting it to vacuum distillation with the use of said treated argon gas free of oxygen, and thereafter it is introduced into the reaction system. Likewise, as for the for halogenating organic reagent to be used for introducing a specific organic group and the solvent to be used, they are also treated to be free of oxygen in the same manner as in the above case of treating the dichlorosilane monomer and are introduced into the reaction system. As for the dehydrogenation of the solvent, it is desired to be treated such that after being subjected to vacuum distillation with the use of the foregoing argon gas, the solvent is further treated with metallic sodium to be completely free of water. As the foregoing condensation catalyst, it is desired to use a wire-like shaped alkaline metal or chipped alkaline metals is preferred in view of enlarging the surface area of the catalyst. In order to obtain said wired alkaline metal or chipped alkaline metals, the starting alkaline metal is wired or chipped in a paraffinic solvent free of oxygen, and the resultant is used while having due regard not to case oxidation thereof. As the starting dichlorosilane monomer to be used for producing the polysilane compound of the foregoing formula (I) to be used in the present invention, there is selectively used a silane compound represented by the general formula: R₁R₂SiCl₂ which will be later detailed or in addition, also selectively used a silane compound represented by the general formula: R₃R₄SiCl₂ which will be later detailed. As the foregoing condensation catalyst, an alkaline metal capable of causing dehalogenation and providing condensation reaction is desirably used. Specific examples of such alkaline metal are lithium, sodium and potassium, among these, lithium and sodium being the most preferred. The foregoing halogenating organic reagent is used for the introduction of a substituent represented by the A and a substituent represented by the A'. As such halogenating organic reagent, there is used a relevant compound selected from the group consisting of halogenated-alkyl compounds, halogenated-cycloalkyl compounds, halogenated-aryl compounds and halogenated-aralkyl compounds, that is, a relevant compound selected from the compounds represented by the general formula: A-X and/or a compound selected from the compounds represented by the general formula: A'-X (wherein X is Cl or Br) which will be later exampled. As for the foregoing dichlorosilane monomer represented by the general formula: R₁R₂SiCl₂ or the dichlorosilane monomer represented by the general formula: R₃R₄SiCl₂ which is used at the time of synthesizing the foregoing intermediate polymer, they are dissolved in predetermined solvents and introduced into the reaction system. As such solvent, nonpolar paraffinic hydrocarbon solvents are desirably used. Specific examples of such nonpolar solvent are n-hexane, n-octane, n-nonane, n-dodecane, cyclohexane, cyclooctane. The intermediate polymer synthesized is insoluble in any of these solvents and thus, it can be effectively separated from the unreacted dichlorosilane monomer. At the time of reacting the intermediate polymer separated from the unreacted dichlorosilane monomer with the halogenating organic reagent, they are dissolved in the same solvent and they are reacted. In this case, there is desirably used an aromatic solvent such as benzene, toluene, xylene, etc. as said solvent. In order to obtain a desired intermediate by condensating the foregoing dichlorosilane monomer with the use of the foregoing alkaline metal catalyst, the polymerization degree of the resulting intermediate polymer can be controlled as desired by properly adjusting the reaction temperature and the reaction period of time. However, as for the reaction temperature, it is desired to be regulated in the range of from 60°C to 130°C. A preferred embodiment of the method for producing the foregoing polysilane compound represented by the formula (I) to be used in the present invention will be explained in the following. That is, the method for producing the foregoing polysilane compound to be desirably used in the present invention comprises the steps of (a) producing the intermediate polymer and (b) introducing the substituents A and A' to the terminals of said intermediate polymer. The step (a) can be carried out as follows. That is, the inside of the reaction system of a reaction vessel is made substantially free of oxygen and water, charged with argon gas and the gas pressure thereof is maintained at a predetermined value. A paraffinic solvent free of oxygen and a condensation catalyst free of oxygen are introduced into the reaction system, and dichlorosilane monomer(s) free of oxygen is introduced thereinto. The reactants thus introduced are heated to a predetermined temperature while mixing them to cause condensation of said monomer. In this case, the condensation degree of said dichlorosilane monomer is controlled as desired by properly regulating the reaction temperature and the reaction period of time, to thereby obtain an intermediate polymer having a desired polymerization degree. The reaction in this case is performed in the way as shown in the following reaction formula (i), wherein the chlorine radicals of the dichlorosilane monomers and the condensation catalyst are reacted to cause dechlorination reaction wherein the Si radicals are repeatedly condensated and polymerized, whereby affording an intermediate polymer. The reaction procedures in the above are made such that the condensation catalyst (alkaline metal) is firstly placed in the paraffinic solvent, into which the dichlorosilane monomers are dropwise introduced while strirring the reaction mixture and maintaining it at an elevated temperature. The polymerization degree of the resultant is confirmed by sampling the reaction liquid. The confirmation of the polymerization degree can be simply conducted by observing the state of the sampled reaction liquid if a film can be formed or not therefrom. When condensation proceeds to form a polymer, said polymer becomes precipitated in the form of white solid in the reaction liquid. When such white solid is precipitated as desired, the reaction liquid containing the white solid is cooled and decanted to separate the precipitate from the solvent. Thus, there is afforded an intermediate polymer. Then, the foregoing step (b) is carried out. Specifically, the intermediate polymer thus obtained is subjected to dechlorination condensation with the use of the halogenating organic reagent and the condensation catalyst (alkaline metal) to thereby substitute the end groups of said intermediate polymer by predetermined organic groups. The reaction in this case is performed in the way as shown in the following reaction formula (ii). Specifically in this respect, the intermediate polymer obtained by condensation of the dichlorosilane monomers is dissolved in the aromatic solvent. Then, the foregoing condensation catalyst (alkaline metal) is added to the solution, and the foregoing halogenating organic reagent is dropwise added at room temperature. Wherein said halogenating organic reagent is added in an excessive amount of 0.01 to 0.1 holds over the amount of the starting monomer in order to compete condensation reaction between the end groups of the polymer. The reaction mixture is gradually heated, and it is stirred for an hour while maintaining at a temperature of 80°C to 100°C to thereby perform the reaction as desired. After the reaction being completed, methanol is added in order to remove the alkaline metal as the catalyst. Then, the polysilane compound resulted is extracted with toluene and purified by using a silica gel column. Thus, there is obtained an objective polysilane compound to be used in the present invention. Specific Examples of the R₁R₂ SiCl₂ and R₃R₄ SiCl₂ Note : Among the following compounds, compounds of a-2 to 16, 18, 20, 21,23 and 24 are used as the dichlorosilane monomer of the general formula: R₁R₂SiCl₂, and compounds of a-1, 2, 11, 17, 19, 22, 23 and 25 as the dichlorosilane monomer of the general formula: R₃R₄SiCl₂. (CH₃)₂SiCℓ₂ a-1 ((CH₃)₂CH)₂SiCℓ₂ a-22 ((CH₃)₃C)₂SiCℓ₂ a-25 Specific Examples of the A-X and the A'-X (CH₃)₂CHCH₂Cℓ b-1 CH₃(CH₂)₄Cℓ b-2 CH₃(CH₂)₅Cℓ b-3 CH₃(CH₂)₁₀Cℓ b-4 CH₃(CH₂)₅Br b-14 CH₃(CH₂)₁₀Br b-15 Specific Examples of the polysilane compound to be used in the present invention Note : X and Y in the above structural formulas respectively stands for a polymeric unit of the monomer. n is obtained by the calculation equation: X/(X+Y) , and m is obtained by the calculation equation: Y/(X+Y) . ( Examples of Synthesis ) In the following, detailed explanation will be made about synthesis of the polysilane compound to be used in the present invention with reference of examples of synthesis. Example of Synthesis 1 A three-necked flask was placed in a blow box which had been vacuum-aspirated and charged with argon gas. A reflux condenser, a temperature gage and a dropping funnel were attached to the device. And argon gas was passed through a by-pass pipe of the dropping funnel. 100 g of dehydrated dodecane and 0.3 moles of wire-like shaped metallic sodium were introduced into the three-necked flask and heated to 100°C while stirring. Then, a solution prepared by dissolving 0.1 mole of dichlorosilane monomer (product by Chisso Kabushiki Kaisha)(a-7) in 30 g of dehydrated dodecane was dropwise and slowly added to the reaction system. After its addition being completed, the reactants were subjected to condensation polymerization at 100°C for an hour, wherein white solids were precipitated. Thereafter the resultant was cooled, and the dodecane was removed by way of decantation. 100 g of dehydrated toluene was added to dissolve the white solids, to which 0.01 mole of mettalic sodium was added. Then, a solution prepared by dissolving 0.01 mole of n-hexylchloride (product by Tokyokasei Kabushiki Kaisha)(b-3) in 10 ml of toluene was dropwise and slowly added to the reaction system while stirring, followed by heating at 100°C for an hour while continuing the stirring. After cooling, 50 ml of methanol was dropwise and slowly added to treat excessive mettalic sodium. As a result, there were formed a suspended phase and a toluene phase. The toluene phase was separated, subjected to vacuum concentration, and purified by way of chromatography development using a silica gel column to obtain a product corresponding to a polysilane compound No. 1 ( C-1 ). The yield was 65%. This polysilane compound was subjected to THF development by a known GPC method to examine the weight average molecular weight thereof. As a result, it was 75,000 (wherein polystyrene was made to be the reference standard). A KBr pellet of the product was prepared and it was set to a Nicolet FT-IR 750 (product by Nicolet Japan Co., Ltd.) to examine its IR spectrum. Further, a specimen of the product was dissolved in CDCl₃ and the resultant was set to a FT-NMR FX-90Q (product by JEOL, Ltd.) to examine its NMR spectrum, whereby performing the identification of the polysilane compound. The results obtained are shown in Table 4. For the polysilane compound synthesized in this example of synthesis, there was not found any IR absorption belonging to unreacted Si-Cl bond, Si-O-Si bond or Si-O-R bond of by-products. Example of Synthesis 2 A three-necked flask was placed in a blow box which had been vacuum-aspirated and charged with argon gas. A reflux condenser, a temperature gage and a dropping funnel were attached to the device. Argon gas was passed through a by-pass pipe of the dropping funnel. 100 g of dehydrated dodecane and 0.3 moles of metallic lithium of 1 mm in size were introduced into the three-necked flask and heated to 100°C while stirring. Then, a solution prepared by dissolving 0.1 mole of dichlorosilane monomer (product by Chisso Kabushiki Kaisha)(a-7) in 30g of dehydrated dodecane was dropwise and slowly added to the reaction system. After its addition being completed, the reactants were subjected to condensation polymerization at 100°C for two hours, wherein white solids were precipitated. The resultant was cooled, and the dodecane was removed by way of decantation. 100 g of dehydrated toluene was added to dissolve the white solids, to which 0.02 moles of metallic lithium was added. Then, a solution prepared by dissolving 0.02 moles of chlorobenzene (product by Tokyo Kasei Kabushiki Kaisha)(b-7) in 10 ml of toluene was dropwise and slowly added to the reaction system while stirring, followed by heating at 80°C for an hour while continuing the stirring. After cooling, 50 ml of methanol was dropwise and slowly added to treat excessive metallic lithium. As a result, there were formed a suspended phase and a toluene phase. The toluene phase was separated, subjected to vacuum concentration, and purified by chromatography development using a silica gel column to obtain a product corresponding to a polysilane compound No. 2 (C-3). The yield was 72%. Its weight average molecular weight was examined in the same manner as in Example of Synthesis 1. As a result, it was 92,000. Further, the product was identified in the same manner as in Example of Synthesis 1. The results obtained are shown in Table 4. For this polysilane compound, there was not found any IR absorption belonging to unreacted Si-Cl bond, Si-O-Si bond or Si-O-R bond of by-products. Example of Synthesis 3 A three-necked flask was placed in a blow box which had been vacuum-aspirated and charged with argon gas. A reflux condenser, a temperature gage and a dropping funnel were attached to the device. Argon gas was passed through a by-pass pipe of the dropping funnel. 100 g of dehydrated n-hexane and 0.3 moles of metallic sodium of 1 mm in size were introduced into the three-necked flask and heated to 80°C while stirring. Then, a solution prepared by dissolving 0.1 mole of dichlorosilane monomer (product by Chisso Kabushiki Kaisha)(a-7) in dehydrated n-hexane was dropwise and slowly added to the reaction system. After its addition being completed, the reactants were subjected to condensation polymerization at 80°C for 3 hours, wherein white solids were precipitated. The resultant was cooled, and the n-hexane was removed by way of decantation. 100 g of dehydrated toluene was added to dissolve the white solids, to which 0.01 mole of metallic sodium was added. Then, a solution prepared by dissolving 0.01 mole of benzyl chloride (product by Tokyo Kasei Kabushiki Kaisha)(b-12) in 10 ml of toluene was dropwise and slowly added to the reaction system while stirring, followed by heating at 80°C for an hour white continuing the stirring. After cooling, 50 ml of methanol was dropwise and slowly added to treat excessive metallic sodium. As a result, there were formed a suspended phase and a toluene phase. The toluene phase was separated, subjected to vacuum concentration, and purified by chromatography development using a silica gel column to obtain a product corresponding to a polysilane compound No. 3 (C-4). The yield was 61%. Further, the product was identified in the same manner as in Example of Synthesis 1. The results obtained are shown in Table 4. For this polysilane compound, there was not found any IR absorption belonging to unreacted Si-Cl bond, Si-O-Si bond or Si-O-R bond of by-products. Examples of Synthesis 4 and 5 The procedures of Example of Synthesis 3 were repeated, except that the dichlorosilane monomer and each of the end group treating agents shown in Table 1 were used. The yield of each of the polysilanes synthesized, its weight average molecular weight, IR spectrum and NMR spectrum measured in the same manner as in Example of Synthesis 1 are shown in Table 4. For each of the polysilane compounds, there was not found any IR absorption belonging to unreacted Si-Cl bond, Si-O-Si bond or Si-O-R bond of by-products. Comparative Example of Synthesis 1 The procedures of Example of Synthesis 3 were repeated, except that neither the condensation using the dichlorosilane monomer (product by Chisso Kabushiki Kaisha)(a-7) nor the end group treatment of the polymer were performed, to obtain a polysilane compound No. D-1. The yield was 60%. As a result of measuring its weight average molecular weight in the same manner as in Example of Synthesis 1, it was 46,000. Further, its identification was performed in the same manner as in Example of Synthesis 1. The results obtained are shown in Table 4. As for this polysilane compound, there were observed IR spectra belonging to unreacted Si-Cl for the end group and belonging to Si-O-R of a by-product. Examples of Synthesis 6 to 10 The same condensation polymerization and purification as in Example of Synthesis 3 were performed, except for changing the dichlorosilane monomer, the reaction period of time and the end group-treating agent as shown in Table 2. There were obtained polysilane compounds Nos. 6 to 10. The yield of each of the polysilane compounds synthesized, its weight average molecular weight, IR spectrum and NMR spectrum measured in the same manner as in Example of Synthesis 1 are shown in Table 4. For each of the polysilane compounds, there was not found any IR absorption belonging to unreacted Si-Cl bond, Si-O-Si bond or Si-O-R bond of by-products. Comparative Example of Synthesis 2 The procedures of Example of Synthesis 6 were repeated, except that the reaction period of time was changed to 10 minutes, to thereby obtain a polysilane compound No. D-2. The yield of the polysilane synthesized, its weight average molecular weight, IR spectrum and NMR spectrum measured in the same manner as in Example of Synthesis 1 are shown in Table 4. For this polysilane compound, there was not found any IR absorption belonging to unreacted Si-Cl bond, Si-O-Si bond or Si-O-R bond of by-products. Examples of Synthesis 11 to 14 The procedures of Example of Synthesis 1 were repeated, except that dichlorosilane monomers and end group-treating agents were selectively used. The yield of each of the polysilanes synthesized, its weight average molecular weight, IR spectrum and NMR spectrum measured in the same manner as in Example of Synthesis 1 are shown in Table 4. The copolymerized ratio of the silane monomer in each case was obtained by the number of protons in the NMR. Comparative Example of Synthesis 3 A three-necked flask was placed in a blow box which had been vacuum-aspirated and charged with argon gas. A reflux condenser, a temperature gage and a dropping funnel were attached to the device. Argon gas was passed through a by-pass pipe of the dropping funnel. 100 g of dehydrated dodecane and 0.3 moles of wire-like shaped metallic sodium were introduced into the three-necked flask and heated to 100°C while stirring. Then, a solution prepared by dissolving 0.1 mole of dichlorosilane monomer (product by Chisso Kabushiki Kaisha) in 30 g of dehydrated dodecane was dropwise and slowly added to the reaction system. After its addition being completed, the reactants were subjected to condensation polymerization at 100°C for an hour, wherein white solids were precipitated. After cooling, 50 ml of methanol was dropwise and slowly added to treat excessive metallic sodium. Then, the resultant was subjected to filtration to thereby separate the white solids, which were repeatedly washed with n-hexane and methanol, to thereby obtain a polysilane compound No. D-3. This polysilane compound was insoluble in organic solvents such as toluene, chloroform, THF. Thus, its identification was performed by its IR spectrum. The results obtained are shown in Table 4. Comparative Example of Synthesis 4 A three-necked flask was placed in a blow box which had been vacuum-aspirated and charged with argon gas. A reflux condenser, a temperature gage and a dropping funnel were attached to the device. Argon gas was passed through a by-pass pipe of the dropping funnel. 100 g of dehydrated dodecane and 0.3 moles of wire-like shaped metallic sodium were introduced into the three-necked flask and heated to 100°C while stirring. Then, a solution prepared by dissolving 0.1 mole of dichlorosilane monomer (product by Chisso Kabushiki Kaisha) in 30 g of dehydrated dodecane was dropwise and slowly added to the reaction system. After its addition being completed, the reactants were subjected to condensation polymerization at 100°C for an hour, wherein white solids were precipitated. After cooling, 50 ml of methanol was dropwise and slowly added to treat excessive metallic sodium. Then, the resultant was subjected to filtration to obtain the white solids, which were repeatedly washed with n-hexane and methanol to obtain a polysilane compound No. D-4. This polysilane compound was insoluble in organic solvents such as toluene, chloroform, THF. Thus, its identification was performed by its IR spectrum. The results obtained are shown in Table 4. Any of the polysilane compounds synthesized in the above examples of synthesis has an excellent film-forming property and is capable of being formed into film, particle or fiber shapes. Further, the polysilane compound can be optionally controlled to be of a desired conduction type by a specific acceptor level forming material or a specific donor level forming material. As such acceptor level forming material (that is, an acceptor doping material), there can be illustrated halogen compounds represented by the the foregoing general formula : MXa (wherein, M is an element belonging to the group VA of the periodic table, X is a halogen element, and a is an integer which is decided depending upon the valence number of the M.). Specific examples of the element M include N, P, As and Sb. Likewise, specific examples of the element X include F, Cl, Br and I. Further, specific examples of the halogen compound include NF₃, NF₅, NCl₃, NCl₅, NBr₃, NBr₅, NI₃, PF₃, PF₅, PCl₃, PCl₅, PBr₃, PBr₅, PI₃, AsF₃, AsF₅, AsCl₃, AsBr₃, AsI₃, SbF₃, SbF₅, SbCl₃, SbCl₅, SbBr₃ and SbI₃. These halogen compounds may be used either singly or in combination of two or more of them. As such donor level forming material (that is, a donor doping material), there can be illustrated amine compounds. Specific examples include aliphatic primary amines represented by the general formula : C m H 2m+1 NH₂, aliphatic secondary amines represented by the general formula : (C m H 2m+1 )₂NH, aliphatic tertiary amines represented by the general formula : (C m H 2m+1 )₃N (wherein, m is an integer of more than 1 in any of the cases), aliphatic unsaturated amines such as allylamine, diallylamine, triallylamine, etc.; alicyclic amines such as cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, etc.; and aromatic amines such as aniline, methylaniline, dimethylaniline, ethylaniline, diethylaniline, o-, m- and p-toluidines, benzylamine, dibenzylamine, tribenzylamine, diphenylamine, triphenylamine, α-naphthylamine, β-naphthylamine, 0-, m- and p-phenylenediamines, tetramethyl-p-phenylenediamine (TMPD), etc. These amine compounds can be used either singly or in combination of two or more of them. The polysilane composition of the present invention can be obtained by adding a predetermined amount of the above doping material to the foregoing polysilane compound. Any of the following three methods can be employed in order to obtain the polysilane composition of the present invention. Method (1) : in the case where the doping material is solid or liquid, the following method can be employed. That is, firstly, the foregoing polysilane compound is dissolved in a dehydrated organic solvent of benzene, toluene or THF to prepare a solution (hereinafter referred to as "polysilane solution"). The concentration of the polysilane compound in the polysilane solution at this time is desired to be preferably 1 x 10⁻³ g/l to 2 x 10³ g/l, more preferably 1 x 10⁻² g/l to 1 x 10³ g/l, or most preferably 1 x 10⁻¹ g/l to 5 x 10² g/l. As for the doping material to be used, when it is liquid, it can be used as it is. However, in the case where the doping material to be used is either liquid or solid, it is desired that the doping material has a compatibility with the above solvent and that the doping material is dissolved in a sufficiently dehydrated solvent to be a solution (this solution will be hereinafter referred to as "dopant liquid"). The concentration of the doping material in the dopant liquid at this time is desired to be preferably 1 x 10⁻⁶ g/l to 2 x 10² g/l, more preferably 2 x 10⁻⁵ g/l to 1 x 10² g/l, or most preferably, 1 x 10⁻⁵ g/l to 5 x 10¹ g/l. Then, the dopant liquid is dropwise added to the foregoing polysilane solution and sufficiently stirred, if necessary while heating (the solution thus treated will be hereinafter referred to as "treated liquid"). The temperature of heating the contents at this time is desired to be set at a temperature of more than the glass-transition temperature of the polysilane compound. Thereafter, the treated liquid is transferred into a relevant making apparatus, wherein film-like, particle-like or fiber-like material is formed from the treated liquid, whereby obtaining the polysilane composition of the present invention. Method (2) : in the case where the doping material is solid or liquid and can be sublimated or gasified, the following method can be employed. That is, firstly, the foregoing polysilane compound is dissolved in a dehydrated organic solvent of benzene, toluene or THF to prepare a polysilane solution. The concentration of the polysilane compound in the polysilane solution at this time is desired to be preferably 1 x 10⁻³ g/l to 2 x 10³ g/l, more preferably 1 x 10⁻² g/l to 1 x 10³ g/l, or most preferably 1 x 10⁻¹ g/l to 5 x 10² g/l. Then, the polysilane solution is transferred into a relevant making apparatus, wherein film-like, particle-like or fiber-like material is formed from the polysilane solution. The formed material is transferred into a relevant doping treating apparatus capable of being vacuum-sealed, wherein the formed material is exposed to an atmosphere comprising gas of the doping material, if necessary, while heating, to thereby absorb or impregnate the doping material in the formed material, whereby obtaining a desired polysilane composition. The atmosphere comprising gas of the doping material may be in the state of pressure, normal pressure or reduced pressure. And, the temperature of heat-treating the polysilane composition at this time is desired to be set a temperature of more than the glass-transition temperature of the polysilane compound. Method (3) : the polysilane composition of the present invention be obtained by subjecting the foregoing polysilane compound to doping treatment by an electrochemical method. Specifically, a desired polysilane composition may be obtained by placing a polysilane moulding formed in the same manner as that described in the above method (2) in a relevant electrolytic solution as an electrode, placing an opposite metal electrode therein, and applying an electric voltage between these electrodes, to thereby make the polysilane moulding applied with doping treatment. The above electrolytic solution is one that is obtained by dissolving in an organic solvent the doping material as an electrolyte. Specific examples of the organic solvent include acetonitrile, propylene carbonate, -butyrolactone, chlorobenzene, etc. The concentration of the electrolyte at this time is desired to be preferably 5 x 10⁻⁶ g/l to 5 x 10² g/l, more preferably 5 x 10⁻⁵ g/l to 5 x 10² g/l, or most preferably, 1 x 10⁻⁴ g/l to 1 x 10² g/l. And, specific examples of the above metal electrode include Pt, Au, Ag, Cu and Pd. In this method (3), an acceptor level or/and a donor level can be formed by making the foregoing polysilane moulding to be an anode. ( Examples ) In the following, the present invention will be explained in more detail with reference to examples, but the present invention is not restricted to these examples. Example 1 - 1 In this example, there was prepared a polysilane composition of the present invention by the foregoing doping treatment method (1). 10g of the polysilane compound (No.1) obtained in Example of Synthesis 1 was introduced into a three-necked flask which had been sufficiently dried and charged with nitrogen, wherein 100 ml of tetrahydrofuran, which had been subjected to distillation drying twice, was dropwise added while stirring within nitrogen stream to thereby prepare a polysilane solution. Then, 0.02 µl of SbF₅ in liquid form as a doping material was dropwise added through a microcylinder to the polysilane solution within nitrogen stream in the three-necked flask, followed by stirring at room temperature for 30 minutes. After the stirring being terminated, the polysilane solution was transferred into a spin coating device placed in a glove box charged with nitrogen, wherein a 1.0 µm thick film comprising the polysilane composition was formed on a No. 7059 glass (25,4 mm x 76,2 mm i.e. 1 inch x 3 inches in size) manufactured by Corning Glass Works Company as a substrate. The film was subjected to vacuum drying treatment to obtain a specimen as Film Sample No. 1. The above operations and procedures were repeated, except for changing the amount of the dopant liquid to be dropwise added to 0.5 µl, 5 µl, 500 µl, 3 ml and 5 ml respectively, there were prepared film specimens to be Film Samples Nos. 2 to 6 respectively comprising the polysilane composition. Each of the specimens was set to a vacuum evaporation apparatus, wherein a 1000Å thick comb-shaped electrode of 150 µm in gap width and 3 cm in length for measuring a conductivity and a 1000Å thick parallel gap electrode of 100 µm in gap width and 5 mm in length for measuring a thermoelectric power were formed by an electron beam evaporation method, using Pt as an evaporation metal for forming such gap electrode at a vacuum of about 1 x 10⁻⁵ x 133,3 Pa (1 x 10⁻⁵ Torr). At the time of evaporation, the specimen was not particularly heated. The resultant was taken out, and a dark current was measured at an applied voltage of 30 V by using a pA METER HP 4140B to obtain a conductivity in dark σ d (S/cm). Further, a conduction type was observed by using a thermoelectric power measuring equipment. The measured results and the evaluated results were as shown in Table 5. From these results, it has bee found that others than Samples Nos. 1 and 6 all exhibit good electric properties. Further, there was performed a test to observe the adhesion of the film formed with the substrate by sticking a cellophane tape of 5 mm in width and 1 cm in length on the film comprising the polysilane composition, and 5 minutes after, removing the cellophane tape. As a result, any of the samples exhibited a good adhesion. Further in addition, there was performed a scratching test by using a diamond needle. As a result, no scratch was observed until 2g in stylus pressure. Example 1 - 2 There were prepared six polysilane composition film samples with different amounts of the doping material in the same operations and procedures as in Example 1 - 1, except for using the polysilane compound (No.13) synthesized in Example of Synthesis 13 instead of the polysilane compound (No.1). For each of the samples obtained, measurement and evaluation were performed in the same manner as in Example 1 - 1. The results obtained were as shown in Table 5. From the results obtained, it has been found that others than the film samples prepared with 0.02 µl and 5 ml in the amount of the dopant liquid to be dropwise added exhibit good electric properties. And, the adhesion and the scratch resisting property were good as well as those obtained in Example 1 - 1. Example 1 - 3 There were prepared six polysilane composition film samples with different amounts of the doping material in the same operations and procedures in Example 1 - 1, except for using the polysilane compound (No.9) synthesized in Example of Synthesis 9 instead of the polysilane compound (No.1) and a dopant liquid prepared by dissolving 0.5 g of SbCl₃ as a doping material in 1000 l of dehydrated benzene instead of the SbF₅ as the doping material. Wherein, the amount of the dopant liquid to be dropwise added was made to be 5 µl, 10 µl, 100 µl, 1 ml, 10 ml and 50 ml respectively. For each of the samples obtained, measurement and evaluation were performed in the same manner as in Example 1 - 1. The results obtained were as shown in Table 5. From the results obtained, it has been found that others than the film samples prepared with 5 µl and 50 ml in the amount of the dopant liquid to be dropwise added exhibit good electric properties. And, the adhesion and the scratch resisting property were good as well as those obtained in Example 1 - 1. Example 1 - 4 In this example, there was prepared a polysilane composition of the present invention by the foregoing doping treatment method (2). 10g of the polysilane compound (No.2) obtained in Example of Synthesis 2 was introduced into a three-necked flask which had been sufficiently dried and charged with nitrogen, wherein 100 ml of toluene, which had been subjected to distillation drying twice, was dropwise added while stirring within nitrogen stream to thereby prepare a polysilane solution. Then, the polysilane solution was transferred into a spin coating device placed in a glove box charged with nitrogen, wherein a 1.0 µm thick film comprising the polysilane composition was formed on a No. 7059 glass (25,4 mm x 76,2 mm i.e. 1 inch x 3 inches in size) manufactured by Corning Glass Works Company as a substrate. The polysilane film was set to a film holder placed in a vacuum treating apparatus, wherein it was subjected to vacuum drying by heating the film holder to 40°C. Then, gaseous AsF₅ was introduced into the vacuum treating apparatus until the inner pressure thereof became 500·133,3 Pa (500 Torr), and while maintaining this inner pressure, the polysilane film was exposed to an atmosphere comprising the AsF₅ for two hours, to thereby subject the polysilane film to doping treatment. As for the remaining cases, the above procedures were repeated to conduct doping treatment, except for changing the inner pressure of the vacuum treatment apparatus to 300·133,3 Pa, 100·133,3 Pa, 50·133,3 Pa and 10·133,3 Pa (300 Torr, 100 Torr, 50 Torr and 10 Torr) respectively. For each of the polysilane composition film samples obtained, measurement and evaluation were performed in the same manner as in Example 1 - 1. The results obtained were as shown in Table 6. From the results obtained, it has been found that others than the film sample prepared with 10·133,3 Pa (10 Torr) for the inner pressure of the vacuum treating apparatus exhibit good electric properties. And, the adhesion and the scratch resisting property were good as well as those obtained in Example 1 - 1. Example 1 - 5 There were prepared six polysilane composition film samples with different amounts of the doping material in the same operations and procedures as in Example 1 - 1, except for using the polysilane compound (No.13) synthesized in Example of Synthesis 13 instead of the polysilane compound (No.1) and using PF₅ instead of the AsF₅ as the doping material. For each of the samples obtained, measurement and evaluation were performed in the same manner as in Example 1 - 1. The results obtained were as shown in Table 6. From the results obtained, it has been found that others than the film sample prepared with 10·133,3 Pa (10 Torr) for the inner pressure of the vacuum treating apparatus exhibit good electric properties. And, the adhesion and the scratch resisting property were good as well as those obtained in Example 1 - 1. Example 1 - 6 In this example, there was prepared a polysilane composition of the present invention by the foregoing doping treatment method (3). 10g of the polysilane compound (No.11) obtained in Example of Synthesis 11 was introduced into a three-necked flask which had been sufficiently dried and charged with nitrogen, wherein 100 ml of toluene, which had been subjected to distillation drying twice, was dropwise added while stirring within nitrogen stream to thereby prepare a polysilane solution. Then, the polysilane solution was transferred into a bar coating device placed in a glove box charged with nitrogen, wherein a 5.0 µm thick film comprising the polysilane composition was formed on a No. 7059 glass (25,4 mm x 76,2 mm i.e. 1 inch x 3 inches in size) manufactured by Corning Glass Works Company as a substrate. After being sufficiently dried within nitrogen stream while heating to 30°C, the film was set to a vacuum evaporation apparatus, wherein an Al circle electrode of 3 mm in diameter was formed thereon by a resistance heating evaporation method. Pt wire was connected to the Pt circle electrode by a wire bonder, followed by connecting to the (+) volage side of a regulated power supply with the use of a lead wire. The resultant was made to be a polysilane electrode. Separately, 5 g of SbF₅ was dissolved in one liter of propylene carbonate to obtain an electrolytic solution. In the electrolytic solution thus prepared, a Pt plate electrode (20mm x 50mm x 1 mm in size) being connected to the (-) voltage side of the regulated power supply and the polysilane electrode prepared in the above were immersed, and doping treatment was performed for two hours while applying a constant voltage of 0.5 V between the two electrodes. After termination of the doping treatment, the polysilane electrode was taken out, followed by subjecting to vacuum drying, to thereby prepare a polysilane composition film sample. Then, the above procedures were repeated, except that the applied voltage was made to be 1 V, 5 V, 10 V and 50 V, to thereby prepare a plurality of polysilane composition film samples. For each of the polysilane composition film samples obtained, measurement and evaluation were performed in the same manner as in Example 1 - 1. The results obtained were as shown in Table 7. From the results obtained, it has been found that others than the film samples prepared with 0.5 V and 50 V for the applied voltage exhibit good electric properties. And, the adhesion and the scratch resisting property were good as well as those obtained in Example 1 - 1. Example 1 - 7 There were prepared five polysilane composition film samples with different amounts of the doping material in the same operations and procedures as in Example 1 - 6, except for using the polysilane compound (No.3) synthesized in Example of Synthesis 3 instead of the polysilane compound (No.11) and using AsBr₃ instead of the SbF₅ as the doping material. For each of the samples obtained, measurement and evaluation were performed in the same manner as in Example 1 - 1. The results obtained were as shown in Table 7. From the results obtained, it has been found that others than the film samples prepared with 0.5 V and 50 V for the applied voltage exhibit good electric properties. And, the adhesion and the scratch resisting property were good as well as those obtained in Example 1 - 1. Example 1 - 8 There were prepared five polysilane composition film samples with different amounts of the doping material in the same operations and procedures as in Example 1 - 6, except for using the polysilane compound (No.7) synthesized in Example of Synthesis 7 instead of the polysilane compound (No.11) and using AsBr₃ instead of the SbF₅ as the doping material. For each of the samples obtained, measurement and evaluation were performed in the same manner as in Example 1 - 1. The results obtained were as shown in Table 7. From the results obtained, it has been found that others than the film samples prepared with 0.5 V and 50 V for the applied voltage exhibit good electric properties. And, the adhesion and the scratch resisting property were good as well as those obtained in Example 1 - 1. Example 1 - 9 There was prepared a polysilane composition film sample in the same operations and procedures as in Example 1 - 3, except for using the polysilane compound (No.4) synthesized in Example of Synthesis 4 instead of the polysilane compound (No.9), PCl₅ instead of the SbCl₃ as the doping material, and a substrate made of stainless steel deposited with a 1 µm thick Ag film (127 mm x 127 mm i.e. 5 inches x 5 inches in size, 1 mm in thickness) instead of the No. 7059 glass manufactured by Corning Glass Works Company as the substrate. Wherein, the amount of the dopant liquid to be dropwise added was made to be 500 µl. Successively, a 100 Å thick Au thin film of 5 mm in diameter was deposited on the polysilane composition film by an electron beam evaporation method. Then, current outputting lead wire was bonded to the Au thin film by a wire bonder. Diode characteristics of the resultant were evaluated by a pA METER HF 4140B. As a result, the diode factor was n = 1.40 ± 0.05, and good diode characteristics were provided. Example 1 - 10 There were prepared a plurality of polysilane composition film samples in the same operations and procedures as in Example 1 - 4, except for using the polysilane compound (No.14) synthesized in Example of Synthesis 14 instead of the polysilane compound (No.2), and a substrate made of stainless steel, which had been treated in the same way as in Example 1 - 9, as the substrate. Wherein, the inner pressure of the vacuum treating apparatus was controlled to be 100·133,3 Pa (100 Torr). Successively, a 100 Å thick Au thin film of 5 mm in diameter was deposited on each of the polysilane composition films by an electron beam evaporation method. Then, current outputting lead wire was bonded to the Au thin film by a wire bonder. Diode characteristics of each of the resultants were evaluated by a pA METER HP 4140B. As a result, the diode factor was n = 1.35 ± 0.05, and good diode characteristics were provided. Example 1 - 11 There were prepared a plurality of polysilane composition film samples in the same operations and procedures as in Example 1 - 6, except for using the polysilane compound (No.8) synthesized in Example of Synthesis 8 instead of the polysilane compound (No.11), and a substrate made of stainless steel, which had been treated in the same way as in Example 1 - 9, as the substrate. Wherein, the applied voltage was made to be 10 V. Successively, a 100 Å thick Au thin film of 5 mm in diameter was deposited on each of the polysilane composition films by an electron beam evaporation method. Then, current outputting lead wire was bonded to the Au thin film by a wire bonder. Diode characteristics of each of the resultants were evaluated by a pA METER HP 4140B. As a result, the diode factor was n = 1.40 ± 0.05, and good diode characteristics were provided. Example 2 - 1 In this example, there was prepared a polysilane composition of the present invention by the foregoing doping treatment method (1). 10g of the polysilane compound (No.1) obtained in Example of Synthesis 1 was introduced into a three-necked flask which had been sufficiently dried and charged with nitrogen, wherein 100 ml of tetrahydrofuran, which had been subjected to distillation drying twice, was dropwise added while stirring within nitrogen stream to thereby prepare a polysilane solution. Separately, 5 g of N,N,N',N'-tetramethylphenylenediamine (TMPD) as a doping material was dissolved in 1000 ml of dehydrated benzene to prepare a dopant liquid (D-1). Then, 0.02 ml of the dopant liquid (D-1) was dropwise added to the polysilane solution within nitrogen stream in the three-necked flask, followed by stirring at room temperature for 30 minutes. After the stirring being terminated, the resultant polysilane solution was transferred into a spin coating device placed in a glove box charged with nitrogen, wherein a 1.0 µm thick film comprising the polysilane composition was formed on a No. 7059 glass (25,4 mm x 76,2 mm i.e. 1 inch x 3 inches in size) manufactured by Corning Glass Works Company as a substrate. The film was subjected to vacuum drying treatment to obtain a specimen as Film Sample No. 1. The above operations and procedures were repeated, except for changing the amount of the dopant liquid to be dropwise added to 0.2 ml, 2 ml, 20 ml, 200 ml and 500 ml respectively, there were prepared film specimens to be Film Samples Nos. 2 to 6 respectively comprising the polysilane composition. Each of the specimens was set to a vacuum evaporation apparatus, wherein a 1000Å thick comb-shaped electrode of 150 µm in gap width and 3 cm in length for measuring a conductivity and a 1000Å thick parallel gap electrode of 100 µm in gap width and 5 mm in length for measuring a thermoelectric power were formed by an electron beam evaporation method, using Pt as an evaporation metal for forming such gap electrode at a vacuum of about 1 x 10⁻⁵ x 133,3 Pa (1 x 10⁻⁵ Torr). At the time of evaporation, the specimen was not particularly heated. The resultant was taken out, and a dark current was measured at an applied voltage of 30 V by using a pA METER HP 4140B to obtain a conductivity in dark σ d (S/cm). Further, a conduction type was observed by using a thermoelectric power measuring equipment. The measured results and the evaluated results were as shown in Table 8. From these results, it has bee found that others than Samples Nos. 1 and 6 all exhibit good electric properties. Further, there was performed a test to observe the adhesion of the film formed with the substrate by sticking a cellophane tape of 5 mm in width and 1 cm in length on the film comprising the polysilane composition, and 5 minutes after, removing the cellophane tape. As a result, any of the samples exhibited a good adhesion. Further in addition, there was performed a scratching test by using a diamond needle. As a result, no scratch was observed until 2g in stylus pressure. Example 2 - 2 There were prepared six polysilane composition film samples with different amounts of the doping material in the same operations and procedures as in Example 2 - 1, except for using the polysilane compound (No.6) synthesized in Example of Synthesis 6 instead of the polysilane compound (No.1). For each of the samples obtained, measurement and evaluation were performed in the same manner as in Example 2 - 1. The results obtained were as shown in Table 8. From the results obtained, it has been found that others than the film samples prepared with 0.02 ml and 500 ml in the amount of the dopant liquid to be dropwise added exhibit good electric properties. And, the adhesion and the scratch resisting property were good as well as those obtained in Example 2 - 1. Example 2 - 3 There were prepared six polysilane composition film samples with different amounts of the doping material in the same operations and procedures in Example 2 - 1, except for using the polysilane compound (No.11) synthesized in Example of Synthesis 11 instead of the polysilane compound (No.1) and o-toluidine instead of the N,N,N',N'-tetramethylphenylenediamine as the doping material. For each of the samples obtained, measurement and evaluation were performed in the same manner as in Example 2 - 1. The results obtained were as shown in Table 8. From the results obtained, it has been found that others than the film samples prepared with 0.02 ml and 500 ml in the amount of the dopant liquid to be dropwise added exhibit good electric properties. And, the adhesion and the scratch resisting property were good as well as those obtained in Example 2 - 1. Example 2 - 4 In this example, there was prepared a polysilane composition of the present invention by the foregoing doping treatment method (2). 10g of the polysilane compound (No.2) obtained in Example of Synthesis 2 was introduced into a three-necked flask which had been sufficiently dried and charged with nitrogen, wherein 100 ml of toluene, which had been subjected to distillation drying twice, was dropwise added while stirring within nitrogen stream to thereby prepare a polysilane solution. Then, the polysilane solution was transferred into a spin coating device placed in a glove box charged with nitrogen, wherein a 1.0 µm thick film comprising the polysilane composition was formed on a No. 7059 glass (1 inch x 3 inches in size) manufactured by Corning Glass Works Company as a substrate. The polysilane film was set to a film holder placed in a vacuum treating apparatus, wherein it was subjected to vacuum drying by heating the film holder to 40°C. Then, dimethylamine was introduced while being gasified into the vacuum treating apparatus until the inner pressure thereof became 500·133,3 Pa (500 Torr), and while maintaining this inner pressure, the polysilane film was exposed to an atmosphere comprising gas of the dimethylamine for two hours, to thereby subject the polysilane film to doping treatment. As for the remaining cases, the above procedures were repeated to conduct the same doping treatment as in the above, except for changing the inner pressure of the vacuum treating apparatus to 300·133,3 Pa, 100·133,3 Pa, 50·133,3 Pa and 10·133,3 Pa (300 Torr, 100 Torr, 50 Torr and 10 Torr) respectively. For each of the polysilane composition film samples obtained, measurement and evaluation were performed in the same manner as in Example 2 - 1. The results obtained were as shown in Table 9. From the results obtained, it has been found that others than the film sample prepared with 10·133,3 Pa (10 Torr) for the inner pressure of the vacuum treating apparatus exhibit good electric properties. And, the adhesion and the scratch resisting property were good as well as those obtained in Example 2 - 1. Example 2 - 5 There were prepared six polysilane composition film samples with different amounts of the doping material in the same operations and procedures as in Example 2 - 4, except for using the polysilane compound (No.8) synthesized in Example of Synthesis 8 instead of the polysilane compound (No.2). For each of the samples obtained, measurement and evaluation were performed in the same manner as in Example 2 - 1. The results obtained were as shown in Table 9. From the results obtained, it has been found that others than the film sample prepared with 10·133,3 Pa (10 Torr) for the inner pressure of the vacuum treating apparatus exhibit good electric properties. And, the adhesion and the scratch resisting property were good as well as those obtained in Example 2 - 1. Example 2 - 6 In this example, there was prepared a polysilane composition of the present invention by the foregoing doping treatment method (3). 10g of the polysilane compound (No.12) obtained in Example of Synthesis 12 was introduced into a three-necked flask which had been sufficiently dried and charged with nitrogen, wherein 100 ml of toluene, which had been subjected to distillation drying twice, was dropwise added while stirring within nitrogen stream to thereby prepare a polysilane solution. Then, the polysilane solution was transferred into a bar coating device placed in a glove box charged with nitrogen, wherein a 5.0 µm thick film comprising the polysilane composition was formed on a No. 7059 glass (25,4 mm x 76,2 mm i.e. 1 inch x 3 inches in size) manufactured by Corning Glass Works Company as a substrate. After being sufficiently dried within nitrogen stream while heating to 30°C, the film was set to a vacuum evaporation apparatus, wherein an Al circle electrode of 3 mm in diameter was formed thereon by a resistance heating evaporation method. Pt wire was connected to the Pt circle electrode by a wire bonder, followed by connecting to the (-) volage side of a regulated power supply with the use of a lead wire. The resultant was made to be a polysilane electrode. Separately, 5 g of N,N,N',N'-tetramethylphenylenediamine was dissolved in one liter of propylene carbonate to obtain an electrolytic solution. In the electrolytic solution thus prepared, a Pt plate electrode (20mm x 50mm x 1 mm in size) being connected to the (+) voltage side of the regulated power supply and the polysilane electrode prepared in the above were immersed, and doping treatment was performed for two hours while applying a constant voltage of 0.5 V between the two electrodes. After termination of the doping treatment, the polysilane electrode was taken out, followed by subjecting to vacuum drying, to thereby prepare a polysilane composition film sample. Then, the above procedures were repeated, except that the applied voltage was made to be 1 V, 5 V, 10 V and 50 V, to thereby prepare a plurality of polysilane composition film samples. For each of the polysilane composition film samples obtained, measurement and evaluation were performed in the same manner as in Example 2 - 1. The results obtained were as shown in Table 10. From the results obtained, it has been found that others than the film samples prepared with 0.5 V and 50 V for the applied voltage exhibit good electric properties. And, the adhesion and the scratch resisting property were good as well as those obtained in Example 2 - 1. Example 2 - 7 There were prepared five polysilane composition film samples with different amounts of the doping material in the same operations and procedures as in Example 2 - 6, except for using the polysilane compound (No.4) synthesized in Example of Synthesis 4 instead of the polysilane compound (No.12) and triphenylamine instead of the N,N,N',N'-tetramethylphenylenediamine as the doping material. For each of the samples obtained, measurement and evaluation were performed in the same manner as in Example 2 - 1. The results obtained were as shown in Table 10. From the results obtained, it has been found that others than the film samples prepared with 0.5 V and 50 V for the applied voltage exhibit good electric properties. And, the adhesion and the scratch resisting property were good as well as those obtained in Example 2 - 1. Example 2 - 8 There were prepared five polysilane composition film samples with different amounts of the doping material in the same operations and procedures as in Example 2 - 6, except for using the polysilane compound (No.9) synthesized in Example of Synthesis 9 instead of the polysilane compound (No.12) and o-toluidine instead of the N,N,N',N'-tetramethylphenylenediamine as the doping material. For each of the samples obtained, measurement and evaluation were performed in the same manner as in Example 2 - 1. The results obtained were as shown in Table 10. From the results obtained, it has been found that others than the film samples prepared with 0.5 V and 50 V for the applied voltage exhibit good electric properties. And, the adhesion and the scratch resisting property were good as well as those obtained in Example 2 - 1. Example 2 - 9 There was prepared a polysilane composition film sample in the same operations and procedures as in Example 2 - 1, except for using the polysilane compound (No.7) synthesized in Example of Synthesis 7 instead of the polysilane compound (No.1), triphenylamine instead of the N,N,N',N'-tetramethylphenylenediamine as the doping material, and a substrate made of stainless steel deposited with a 1 µm thick Ag film (127 mm x 127 mm i.e. 5 inches x 5 inches in size, 1 mm in thickness) instead of the No. 7059 glass manufactured by Corning Glass Works Company as the substrate. Wherein, the amount of the dopant liquid to be dropwise added was made to be 200 ml. Successively, a 100 Å thick Au thin film of 5 mm in diameter was deposited on the polysilane composition film by an electron beam evaporation method. Then, current outputting lead wire was bonded to the Au thin film by a wire bonder. Diode characteristics of the resultant were evaluated by a pA METER HP 4140B. As a result, the diode factor was n = 1.35 ± 0.05, and good diode characteristics were provided. Example 2 - 10 There were prepared a plurality of polysilane composition film samples in the same operations and procedures as in Example 2 - 4, except for using the polysilane compound (No.10) synthesized in Example of Synthesis 10 instead of the polysilane compound (No.2), and a substrate made of stainless steel, which had been treated in the same way as in Example 2 - 9, as the substrate. Wherein, the inner pressure of the vacuum treating apparatus was controlled to be 100·133,3 Pa (100 Torr). Successively, a 100 Å thick Pt thin film of 5 mm in diameter was deposited on each of the polysilane composition films by an electron beam evaporation method. Then, current outputting lead wire was bonded to the Pt thin film by a wire bonder. Diode characteristics of each of the resultants were evaluated by a pA METER HP 4140B. As a result, the diode factor was n = 1.30 ± 0.05, and good diode characteristics were provided. Example 2 - 11 There were prepared a plurality of polysilane composition film samples in the same operations and procedures as in Example 2 - 6, except for using the polysilane compound (No.14) synthesized in Example of Synthesis 14 instead of the polysilane compound (No.12), and a substrate made of stainless steel, which had been treated in the same way as in Example 2 - 9, as the substrate. Wherein, the applied voltage was made to be 10 V. Successively, a 100 Å thick Pt thin film of 5 mm in diameter was deposited on each of the polysilane composition films by an electron beam evaporation method. Then, current outputting lead wire was bonded to the Pt thin film by a wire bonder. Diode characteristics of each of the resultants were evaluated by a pA METER HP 4140B. As a result, the diode factor was n = 1.30 ± 0.05, and good diode characteristics were provided.

Claims: A polysilane composition which is characterized by containing a polysilane compound having a weight average molecular weight of 6 000 to 200 000, free from chlorine- and oxygen-containing groups, soluble in organic solvents and capable of forming films and which is represented by the following general formula (I) and either an acceptor level forming material comprising a halogen compound represented by the general formula: MXa (wherein M stands for an element belonging to the group VA of the periodic table, X stands for an halogen element, and a stands for an integer which is decided depending upon the valence number of said element M) or a donor level forming material comprising an amine compound, in which the content of said acceptor level forming material or said donor level forming material is 1 x 10⁻⁴ to 10 parts by weight versus 100 parts by weight of said polysilane compound. [Wherein R₁ stands for an alkyl group of 1 to 2 carbon atoms; R₂ stands for an alkyl group, cycloalkyl group, aryl group or aralkyl group of 3 to 8 carbon atoms; R₃ stands for an alkyl group of 1 to 4 carbon atoms; R₄ stands for an alkyl group of 1 to 4 carbon atoms; A and A' respectively stands for an alkyl group, cycloalkyl group, aryl group or aralkyl group of 4 to 12 carbon atoms wherein the two substituents may be the same or different one from the other; and each of n and m is a mole ratio showing the proportion of the number of respective monomers versus the total of the monomers in the polymer wherein n + m = 1, 0 < n ≦ 1 and 0 ≦ m < 1.] A polysilane composition as defined in claim 1, wherein the weight average molecular weight of the polysilane compound is 8000 to 120000. A polysilane composition as defined in claim 1, wherein each of the A and A' in the polysilane compound represented by the general formula (I) is an alkyl group or a cycloalkyl group of 5 to 12 carbon atoms. A polysilane composition as defined in claim 1, wherein the element belonging to the group VA is an element selected from the group consisting of N, P, As and Sb. A polysilane composition as defined in claim 1, wherein the halogen element is F, Cl, Br or I. A polysilane composition as defined in claim 1, wherein the halogen compound represented by the general formula : MXa is a compound selected from the group consisting of NF₃, NF₅, NCl₃, NCl₅, NBr₃, NB₅, NI₃, PF₃, PF₅, PCl₃, PCl₅, PBr₃, PBr₅, PI₃, AsF₃, AsF₅, AsCl₃, AsBr₃, AsI₃, SbF₃, SbF₅, SbCl₃, SbCl₅, SbBr₃ and SbI₃. A polysilane composition as defined in claim 1, wherein the amine compound is a compound selected from the group consisting of aliphatic amines, aliphatic unsaturated amines, alicyclic amines, and aromatic amines. A polysilane composition as defined in claim 7, wherein the amine compound is a compound selected from the group consisting of allylamine, diallylamine, triallylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, aniline, methylaniline, dimethylaniline, ethylaniline, diethylaniline, o-, m-, and p-toluidines, benzylamine, dibenzylamine, tribenzylamine, diphenylamine, triphenylamine, -naphthylamine, β-naphthylamine, 0-, m-, and p-phenylenediamines, and tetramethyl-p-phenylenediamine (TMPD).

Inventors: AOIKE TATUYUKI CANON KABUSHIKI, KANAI MASAHIRO CANON KABUSHIKI, MATUDA KOUICHI CANON KABUSHIKI, NIWA MITUYUKI CANON KABUSHIKI, SAITOU KEISHI CANON KABUSHIKI, SAKOU HARUMI CANON KABUSHIKI K, SANO MASAFUMI CANON KABUSHIKI, TANAKA HISAMI CANON KABUSHIKI, AOIKE, TATUYUKI CANON KABUSHIKI KAISHA, KANAI, MASAHIRO CANON KABUSHIKI KAISHA, MATUDA, KOUICHI CANON KABUSHIKI KAISHA, NIWA, MITUYUKI CANON KABUSHIKI KAISHA, SAITOU, KEISHI CANON KABUSHIKI KAISHA, SAKOU, HARUMI CANON KABUSHIKI KAISHA, SANO, MASAFUMI CANON KABUSHIKI KAISHA, TANAKA, HISAMI CANON KABUSHIKI KAISHA
Applicants: CANON KK, CANON KABUSHIKI KAISHA
Application year: 1990
Main classification: C08L83
IPC codes: C08K5, G03F7, H01L51, C08G77, C08K3