JP2019156689A - Polysilane composition, and manufacturing method of hetero element-introduced polysilane composition - Google Patents

Abstract

To provide a polysilane composition, etc., having reduced amounts of metal impurities such as aluminum content and to which a hetero element can be introduced without using a metal halide for halogenation of a hydrogenated silane.SOLUTION: The polysilane composition is characterized by containing a halosilane represented by a general formula of SiX(m=3-8, X is a halogen) and a hydrogenated silane represented by a general formula of SiH(n=3-8) and having an aluminum content of, on a mass basis, 0.01 ppb-1000 ppm.SELECTED DRAWING: None

Description

  The present invention relates to a polysilane composition and a method for producing a heteroelement-introduced polysilane composition.

Thin film silicon is used for applications such as solar cells and semiconductors, and this thin film silicon is conventionally produced by a vapor deposition method (CVD method) using monosilane as a raw material. As another method for producing a silicon film, a CVD method using a hydrogenated silane compound represented by the general formula (SiH ₂ ) _n (n = 4, 5, or 6) as a raw material (Patent Document 1), cyclohexasilane A method of producing polysilane by photopolymerization by forming a solution layer using cyclopentasilane or cyclohexasilane as a solute on a substrate (Patent Document 2) has been reported. Yes.

  As a method of producing a hydrogenated silane compound, a halosilane cyclization reaction is performed in the presence of a specific coordination compound to obtain a halogenated silane neutral complex, and then this is reduced to reduce the hydrogenated silane compound. Has disclosed a method for producing a lipase (Patent Document 4).

On the other hand, when manufacturing solar cells, semiconductors, etc. at a low temperature and in a large area, liquid silane introduced with a heteroelement of group 13 or 15 is used as a dopant. There is also a need for halogen-containing polysilanes that can be substituted with elements.
As a method for preparing a halogen-containing polysilane that can be substituted with a heteroelement, for example, a method in which a silane hydride is halogenated with a halogenating reagent and reacted with a heteroelement-containing nucleophile is disclosed (Patent Document 5).

JP 60-26664 A Special table 2013-537705 gazette JP 2013-187261 A JP2015-134755A Special table 2011-521953 gazette

However, in the technique of Patent Document 5, the corresponding hydrogenated silane is halogenated in order to obtain a halogenated silane, and a metal halide is used as a halogenating reagent for halogenation at this time. This reaction is light sensitive, produces harmful substances, and has many unreacted substances, making it difficult to control the reaction, and the metal halide is added as a solid in an excessive amount. There is a problem that metal impurities derived from metal halides are contained, and as a result, purification of the product becomes difficult.
On the other hand, the metal impurities include, for example, aluminum-containing materials derived from reaction raw materials, aluminum-containing materials derived from hydrogenated silane compounds obtained by using free halosilanes and reducing agents, and have a high aluminum content. If it becomes, there exists a possibility that a hydrogenated silane compound may superpose | polymerize and there exists a tendency which becomes a problem in terms of the long-term storage property of hydrogenated silane.
Therefore, the present invention provides a polysilane composition in which the amount of metal impurities such as aluminum content can be reduced without using a metal halide for halogenating silane hydride, and a heteroelement can be introduced. An object of the present invention is to provide a method for producing an introduceable polysilane composition.

  The gist of the present invention is as follows.

[1] A halosilane represented by the general formula Si _m X _2m (m = 3 to 8, X is a halogen element) and a hydrogenated silane represented by the general formula Si _n H _2n (n = 3 to 8). A polysilane composition comprising an aluminum content of 0.01 ppb to 1000 ppm on a mass basis.
[2] The polysilane composition according to [1], wherein the hydrogenated silane is a reaction product of a halosilane for preparing a hydrogenated silane and a reducing agent, and the halosilane is a halosilane for external addition.
[3] The polysilane composition according to [1] or [2], wherein the purity of the hydrogenated silane is 90% by mass or more.
[4] The polysilane composition according to any one of [1] to [3], wherein the content (mass basis) of the halosilane is 0.01 to 10 mol with respect to 1 mol of the hydrogenated silane.
[5] The polysilane composition according to any one of [1] to [4], wherein at least a part of the halogen element contained in the halosilane is substituted with at least one element selected from Group 13 and Group 15. .
[6] The polysilane composition according to any one of [1] to [5], wherein the halosilane is a cyclic halosilane represented by the general formula Si _m X _2m (m = 5 to 6, X is a halogen element).
[7] The polysilane composition according to [6], wherein the cyclic halosilane is cyclic chlorosilane.
[8] The polysilane composition according to [7], wherein the cyclic chlorosilane is dodecachlorocyclohexasilane.
[9] The polysilane composition according to any one of [1] to [8], wherein the hydrogenated silane is a cyclic hydrogenated silane (n = 5 to 6) represented by a general formula Si _n H _2n .
[10] The polysilane composition according to [9], wherein the cyclic hydrogenated silane is cyclohexasilane.
[11] A method for producing a polysilane composition into which a hetero element is introduced,
Mixing and / or mixing a halosilane represented by the general formula Si _m X _2m (m = 3 to 8, X is a halogen element) and a hydrogenated silane represented by the general formula Si _n H _2n (n = 3 to 8) Or the process made to contact is mentioned, The aluminum content is 0.01 ppb-1000 ppm by mass reference | standard, The manufacturing method characterized by the above-mentioned.
[12] The production method according to [11], wherein the mixture of the halosilane and the hydrogenated silane is a solution.
[13] The production method according to [11] or [12], further comprising a step of mixing and / or contacting a compound having at least one element selected from Group 13 and Group 15.

  According to the present invention, a polysilane composition capable of introducing a heteroelement in which the amount of metal impurities such as aluminum content is reduced without using a metal halide for halogenating a silane hydride, and a heteroelement is provided. It is possible to provide a method for producing a polysilane composition that can be introduced. Moreover, the polysilane composition (for dope) containing various functional groups in arbitrary ratios can be provided.

1. Polysilane Composition The polysilane composition of the present invention comprises a halosilane represented by the general formula Si _m X _2m (m = 3 to 8, X is a halogen element) and a hydrogenated silane represented by the general formula Si _n H _2n ( n = 3 to 8), and the aluminum content is 0.01 ppb to 1000 ppm on a mass basis.
The polysilane composition of the present invention can contain a hetero element at an arbitrary ratio by adjusting the number of halogen elements contained in the halosilane and the amount of halosilane with respect to the amount of hydrogenated silane, and halogenates the hydrogenated silane. Therefore, it is possible to reduce the amount of metal impurities because the reaction can proceed in a liquid without using a metal halide.

The halosilane is a cyclic halosilane represented by the general formula Si _m X _2m (m = 3 to 8, X is a halogen element).
The halogen element is preferably a chlorine element, a fluorine element, a bromine element, or an iodine element. m is preferably 4 to 7, and more preferably 5 to 6.

  A halosilane is a cyclic halosilane, that is, a compound having a structure (cyclic halosilane structure) in which silicon atoms are linked to form a monocyclic ring, and a halogen atom is bonded to at least one silicon atom constituting the monocyclic ring. Preferably there is.

  The cyclic halosilane may contain a silicon atom that does not constitute a simple ring, for example, a silicon atom that constitutes a simple ring may have a substituent (for example, a silyl group) containing a silicon atom bonded thereto. Good. It is sufficient that at least one halogen atom is bonded to a monocyclic ring formed from silicon atoms, and preferably, one or two halogen atoms (preferably, each silicon atom constituting the monocyclic ring). 2) It is connected.

  Among them, the cyclic halosilane is more preferably a cyclic chlorosilane, further preferably a cyclic chlorosilane having 5 or 6 silicon, and even more preferably dodecachlorocyclohexasilane.

  The content (mass basis) of the halosilane is preferably 0.01 to 10 mol, more preferably 0.05 to 9 mol, still more preferably 0.1 to 7 mol, and even more based on 1 mol of the hydrogenated silane. Preferably it is 0.2-5 mol.

The hydrogenated silane is a cyclic hydrogenated silane represented by the general formula Si _n H _2n (n = 3 to 8).
The halogen element is preferably a chlorine element, a fluorine element, a bromine element, or an iodine element. n is preferably 4 to 7, and more preferably 5 to 6.

  The hydrogenated silane is a cyclic hydrogenated silane, that is, a compound having a monocyclic ring composed of continuous silicon atoms and composed of a silicon atom and a hydrogen atom. Cyclic hydrogenated silanes are those in which hydrogen atoms may be bonded to all substitution positions of silicon atoms constituting the monocyclic ring, and unsubstituted silyl groups are bonded to silicon atoms constituting the monocyclic ring. There may be. However, from the viewpoint of storage stability, it is preferable that no silicon atoms other than silicon atoms constituting the monocyclic ring are contained.

  Among them, the cyclic hydrogenated silane is more preferably a cyclic hydrogenated silane having 5 or 6 silicon, and further preferably cyclohexasilane.

  The purity of the hydrogenated silane may be based on, for example, gas chromatography, preferably 90% by mass or more, more preferably 93% by mass or more, and further preferably 95% by mass or more. Preferably, it is still more preferably 97% by mass or more, and particularly preferably 98% by mass or more. The upper limit of the purity of the hydrogenated silane is better as it is closer to 100% by mass, for example, 99.99% by mass.

Such purity can be determined, for example, using the following gas chromatography conditions.
Detection: FID
Column: Capillary column of poly (5% diphenyl / 95% dimethyl) siloxane phase, 0.25 μm × 0.25 mm × 30 m
Vaporization chamber temperature: 250 ° C
Detector temperature: 280 ° C
Temperature rising conditions: 1) Holding at 50 ° C. for 5 minutes, 2) Heating up to 250 ° C. at a heating rate of 20 ° C./min, 3) Heating up to 280 ° C. at a heating rate of 10 ° C./min, 4) Minute hold

  The hydrogenated silane of the present invention may be, for example, one prepared from cyclohexasilane as a cyclic hydrogenated silane, one obtained by solid-liquid separation of cyclohexasilane, or one obtained by distilling cyclohexasilane. It may be.

  The hydrogenated silane of the present invention may have undergone, for example, cyclization of a halogenated monosilane, preparation of a cyclic halosilane salt, liberation of a cyclic halosilane salt, reduction of a cyclic halosilane compound, It is preferable to be obtained.

As the reducing agent, it is preferable to use one or more selected from the group consisting of an aluminum-based reducing agent and a boron-based reducing agent. Examples of the aluminum reducing agent include lithium aluminum hydride (LiAlH ₄ ; LAH), diisobutylaluminum hydride (DIBAL), sodium bis (2-methoxyethoxy) aluminum hydride [“Red-Al” (manufactured by Sigma-Aldrich). (Registered trademark)] and the like. Examples of the boron-based reducing agent include metal hydrides such as sodium borohydride and lithium triethylborohydride, and diborane. It is preferable to use a metal hydride.

The aluminum content in the polysilane composition is 0.01 ppb to 1000 ppm on a mass basis, preferably 100 ppm or less, more preferably 1000 ppb or less, and even more preferably 500 ppb or less.
When hydrogenated silane is obtained through a reduction process, a metal element derived from a reducing agent is contained in the order of several thousand ppm to several percent. Further, when a mixture of hydrogenated silane and unreacted halosilane is obtained in the reduction step, it is difficult to purify while maintaining the mixed state, so it is difficult to obtain the aluminum content.

  The aluminum content can be determined by, for example, ICP mass spectrometry, ICP emission spectrometry, atomic absorption spectrometry, or the like, and Agilent 7700S (manufactured by Agilent Technologies) may be used.

The polysilane composition may not contain the solvent and may contain the solvent.
The solvent may be any solvent that does not react with halosilane or hydrogenated silane; aliphatic hydrocarbon solvents such as hexane, heptane, octane; aromatic hydrocarbon solvents such as benzene, toluene, xylene; diethyl ether, tetrahydrofuran, cyclopentylmethyl An ether solvent such as ether may be used.

  The amount of the solvent is preferably 1 to 10000 parts by mass, more preferably 10 to 8000 parts by mass, and further preferably 100 to 6000 parts by mass with respect to 100 parts by mass in total of the halosilane and the hydrogenated silane.

The polysilane composition containing hydrogenated silane and halosilane may be subsequently doped as needed.
In the present invention, it is preferable that at least a part of the halogen element contained in the halosilane is substituted with at least one element selected from Group 13 and Group 15 (also referred to as a hetero element) and a substituent containing the element. More preferably, all of the halogen elements contained in the halosilane are substituted with at least one element selected from Group 13 and Group 15 and a substituent containing the element.

  Examples of the Group 13 element include B, Al, Ga, In, and Tl. Examples of the Group 15 element include N, P, As, Sb, and Bi.

These elements can be introduced into the halosilane by using a nucleophile.
Examples of the nucleophile include BR ₃ , B ₂ H ₆ , NR ₃ , PR ₃ , AsR ₃ (R = H or an alkyl group having 1 to 6 carbon atoms), alkali metal salt XMR ₃ (X = Na, Li Alkali metal such as M = 13 or 15 group element, R = H, or an alkyl group having 1 to 6 carbon atoms).

  An element selected from Groups 13 and 15 as a hetero atom is substituted with a halogen element bonded to halosilane. By appropriately adjusting the number of halogen elements contained in the halosilane and the amount of the halosilane relative to the hydrogenated silane, a polysilane composition into which various amounts of various heteroelements are introduced can be prepared.

  In the polysilane composition into which the hetero element is introduced, the ratio between the hydrogenated silane and the silane in which the halogen element is substituted with the hetero element is the same as the ratio between the hydrogenated silane and the halosilane before the hetero element is introduced. May be.

2. Manufacturing method of polysilane composition capable of introducing heteroelements The manufacturing method of a polysilane composition into which heteroelements of the present invention are introduced is a halosilane represented by the general formula Si _m X _2m (m = 3 to 8, X is a halogen element) ) And a hydrogenated silane represented by the general formula Si _n H _2n (n = 3 to 8) are mixed and / or contacted, and the aluminum content is 0.01 ppb to 1000 ppm on a mass basis It is characterized by that.

The production method of halosilane is not particularly limited, and various known production methods can be adopted, and a method of liberating a cyclic halosilane salt prepared by cyclization of a halogenated monosilane is preferable.
The production method of the hydrogenated silane is not particularly limited, and various known production methods can be adopted, and a method of reducing the released cyclic halosilane is preferable.

<Cyclization reaction of halogenated monosilane>
Examples of the halogenated monosilane include dihalosilanes such as dichlorosilane, dibromosilane, diiodosilane, and difluorosilane; trihalosilanes such as trichlorosilane, tribromosilane, triiodosilane, and trifluorosilane; tetrachlorosilane, tetrabromosilane, and tetra Tetrahalosilanes such as iodosilane and tetrafluorosilane; etc. can be used. Among these, trihalosilane is preferable, and trichlorosilane is particularly preferable.

The method for cyclizing the halogenated monosilane is not particularly limited. For example, the following method (A) or (B) is preferable.
(A) A method of obtaining a salt of a cyclic halosilane, which comprises a step of bringing a halogenated monosilane into contact with a phosphonium salt and / or an ammonium salt [hereinafter sometimes referred to as Method A].
(B) a method of obtaining a cyclic halosilane neutral complex, comprising a step of contacting a halogenated monosilane with at least one compound selected from the group consisting of the following (I) and (II) [hereinafter referred to as Method B] May be.]

(I) compounds represented by the XR _n [hereinafter sometimes referred to as the compound I]. When X is P or P═O, n = 3, and R is the same or different and represents a substituted or unsubstituted alkyl group or aryl group. When X is S, S═O or O, n = 2, and R is the same or different and represents a substituted or unsubstituted alkyl group or aryl group. When X is CN, n = 1, and R represents a substituted or unsubstituted alkyl group or aryl group. However, the number of amino groups in the XR _n is 0 or 1.

  (II) At least one heterocyclic compound selected from the group consisting of substituted or unsubstituted heterocyclic compounds containing N, O, S or P having an unshared electron pair in the ring [hereinafter referred to as Compound II There are]. However, the number of tertiary amino groups as substituents of the heterocyclic compound is 0 or 1.

  First, the method (A) will be described.

The phosphonium salt is preferably a quaternary phosphonium salt, preferably a salt represented by the following formula (11). In the following formula (11), R ^{1 to} R ⁴ may be different from each other, but are preferably all the same group.

Moreover, it is preferable that the said ammonium salt is a quaternary ammonium salt, and the salt represented by following formula (12) is mentioned preferably. In the following formula (12), R ^{5 to} R ⁸ may be different from each other, but are preferably all the same group.

In the above formula (11) and the above formula (12), R ^{1 to} R ⁴ and R ^{5 to} R ⁸ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and A ⁻ represents a monovalent anion. .

Examples of the alkyl group for R ^{1 to} R ⁴ and R ^{5 to} R ⁸ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group. Linear alkyl groups such as a group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group; cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexyl group, etc. .
Carbon number of an alkyl group becomes like this. Preferably it is 1-16, More preferably, it is 1-8.

Preferred examples of the aryl groups of R ^{1 to} R ⁴ and R ^{5 to} R ⁸ include aryl groups having 6 to 18 carbon atoms such as phenyl groups and naphthyl groups, and aryl groups having 6 to 12 carbon atoms are more preferable.

R ^{1 to} R ⁴ and R ^{5 to} R ⁸ are preferably an alkyl group or an aryl group, and more preferably an aryl group. If R ^{1 to} R ⁴ and R ^{5 to} R ⁸ are aryl groups, the cyclic halosilane salt precipitates in the reaction solution when the cyclic halosilane salt is produced, as described later. It becomes easy to obtain a salt with high purity. For the same reason, it is preferable to use a phosphonium salt rather than an ammonium salt.

In the above formulas (11) and (12), examples of the monovalent anion represented by A ⁻ include halide ions (for example, Cl ⁻ , Br ⁻ , I ^{− and the} like), borate ions (for example, BF ₄ ⁻ ). And phosphorus anions (for example, PF ₆ ⁻ ) and the like. Among these, halide ions are preferable from the viewpoint of availability, more preferably Cl ⁻ , Br ⁻ , I ⁻ , and particularly preferably Cl ⁻ and Br ⁻ .

  Only one or both of the phosphonium salt and ammonium salt may be used. Only one type of phosphonium salt may be used, or two or more types may be used in combination. Only one ammonium salt may be used, or two or more ammonium salts may be used in combination.

  The amount of the phosphonium salt and / or ammonium salt used (when two or more are used, the total amount used) is preferably 0.01 mol or more, more preferably 0.05 mol or more, and still more preferably with respect to 1 mol of halosilane. It is 0.08 mol or more, preferably 1.0 mol or less, more preferably 0.7 mol or less, still more preferably 0.5 mol or less. When the amount of the phosphonium salt and / or ammonium salt is in the above range, the yield of the cyclic halosilane salt tends to be improved.

  The method (A) is preferably performed in the presence of a chelate ligand such as polyether, polythioether, and polydentate phosphine. By carrying out the cyclization coupling reaction in the presence of a chelate ligand, a salt of a cyclic halosilane can be produced efficiently. In addition, the number of hydrogens and the composition ratio in the obtained cyclic halosilane can be adjusted by appropriately selecting the type of chelate-type ligand to be used.

  Examples of the polyether include 1,1-dimethoxyethane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dipropoxyethane, 1,2-diisopropoxyethane, 1,2 -Dibutoxyethane, 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-dipropoxypropane, 1,3-diisopropoxypropane, 1,3-dibutoxypropane, 1,4-dimethoxy Dialkoxyalkanes such as butane, 1,4-diethoxybutane, 1,4-dipropoxybutane, 1,4-diisopropoxybutane, 1,4-dibutoxybutane, 1,2-diphenoxyethane, 1 , 3-diphenoxypropane, diaryloxyalkanes such as 1,4-diphenoxybutane, and the like. Among these, 1,2-dimethoxyethane is particularly preferable.

  As said polythioether, what substituted the oxygen atom of the illustrated polyether by the sulfur atom is mentioned.

  Examples of the polydentate phosphine include 1,2-bis (dimethylphosphino) ethane, 1,2-bis (diethylphosphino) ethane, 1,2-bis (dipropylphosphino) ethane, 1,2- Bis (dibutylphosphino) ethane, 1,3-bis (dimethylphosphino) propane, 1,3-bis (diethylphosphino) propane, 1,3-bis (dipropylphosphino) propane, 1,3-bis (Dibutylphosphino) propane, 1,4-bis (dimethylphosphino) butane, 1,4-bis (diethylphosphino) butane, 1,4-bis (dipropylphosphino) butane, 1,4-bis ( Bis (dialkylphosphino) alkanes such as dibutylphosphino) butane; 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphospho) Fino) propane, 1,4-bis (diphenylphosphino) bis (diarylphosphino) alkanes such as butane. Among these, 1,2-bis (diphenylphosphino) ethane is particularly preferable.

  The amount of the chelate-type ligand used may be appropriately set. For example, with respect to 1 mol of halosilane, it is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.1 mol or more, and preferably Is 50 mol or less, more preferably 40 mol or less, still more preferably 30 mol or less.

  The cyclic halosilane salt obtained by the above method (A) is preferably, for example, one represented by the following formula (13).

In the above formula (13), X ¹ and X ² each independently represent a halogen atom, L represents an anionic ligand, and p represents an integer of −2 to 0 as the valence of the ligand L. , K represents a counter cation, q represents an integer of 0 to 2 as the valence of the counter cation K, n represents an integer of 0 to 5, a, b and c are integers of 0 or more and “2n + 6” or less. (Where a + b + c = 2n + 6, a and c are not 0 at the same time), d is an integer of 0 to 3 (where a and d are not 0 at the same time), and e is an integer of 0 to 3 (however, D + e = 3), m is 1 to 2, s represents an integer of 1 or more, and t represents an integer of 1 or more.

<Method for liberating cyclic halosilane salt>
The cyclic halosilane salt may be free cyclic halosilane by reacting it with a Lewis acid. The free cyclic halosilane means a non-complex type cyclic halosilane such as Si ₅ Cl ₁₀ or Si ₆ Cl ₁₂ , for example. Specifically, when a salt of a cyclic halosilane is brought into contact with a Lewis acid, the Lewis acid acts electrophilically on an anionic ligand contained in the salt of the cyclic halosilane, and the anionic coordination from the salt of the cyclic halosilane. As the child is pulled out, the counter cation is released, and the corresponding free cyclic halosilane can be obtained.

  The kind of the Lewis acid is not particularly limited, but it is preferable to use a metal halide. Examples of the metal halide include metal chlorides, metal bromides, metal iodides, and the like, and metal chlorides are preferably used from the viewpoint of reactivity and ease of reaction control. The metal elements constituting the metal halide include group 13 elements such as boron, aluminum, gallium, indium and thallium, group 11 elements such as copper, silver and gold, group 4 elements such as titanium and zirconium, iron, zinc, Examples include calcium. Specific examples of Lewis acids include boron halides such as boron trifluoride, boron trichloride and boron tribromide; aluminum halides such as aluminum chloride and aluminum bromide; halogenations such as gallium chloride and gallium bromide. Indium halides such as indium chloride and indium bromide; Thallium halides such as thallium chloride and thallium bromide; Copper halides such as copper chloride and copper bromide; Silver halides such as silver chloride and silver bromide; Gold halides such as gold chloride and gold bromide; Titanium halides such as titanium chloride and titanium bromide; Zirconium halides such as zirconium chloride and zirconium bromide; Iron halides such as iron chloride and iron bromide; Zinc chloride And zinc halides such as zinc bromide; calcium halides such as calcium chloride and calcium bromide;

  The amount of the Lewis acid used may be appropriately adjusted according to the reactivity between the cyclic halosilane salt and the Lewis acid. For example, the amount is preferably 0.5 mol or more, more preferably, 1 mol of the cyclic halosilane salt. The amount is 1.5 mol or more, preferably 20 mol or less, more preferably 10 mol or less.

  The reaction between the cyclic halosilane salt and the Lewis acid is preferably carried out in a solvent or dispersion medium (these are simply referred to as solvents). Examples of the solvent (reaction solvent) used in the reaction include hydrocarbon solvents such as hexane and toluene; ether solvents such as diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, diisopropyl ether, and methyl tertiary butyl ether. These organic solvents may use only 1 type and may use 2 or more types together. The reaction solvent is preferably subjected to purification such as distillation or dehydration before the reaction in order to remove water and dissolved oxygen contained therein.

  The reaction temperature for the reaction between the cyclic halosilane salt and the Lewis acid may be appropriately adjusted according to the reactivity. For example, the reaction temperature is preferably −80 ° C. or higher, more preferably −50 ° C. or higher, and still more preferably. Is −30 ° C. or higher, preferably 200 ° C. or lower, more preferably 150 ° C. or lower, and still more preferably 100 ° C. or lower.

  Next, the method (B) will be described.

In XR _n of the compounds I, X is coordinated to the annular halosilane to form an annular halosilane neutral complex. When X is P or P = O, X is trivalent and n indicating the number of R is 3. R is the same or different and represents a substituted or unsubstituted alkyl group or aryl group. R is more preferably a substituted or unsubstituted aryl group. When R is an alkyl group, examples thereof include a linear, branched or cyclic alkyl group, and include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Linear alkyl groups such as decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group; cyclic such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group An alkyl group having 1 to 16 carbon atoms such as an alkyl group is preferred. In addition, when R is an aryl group, an aryl group having about 6 to 18 carbon atoms such as a phenyl group and a naphthyl group is preferable.

In XR _n of the compound I, also when X is N, X is coordinated to the annular halosilane to form an annular halosilane neutral complex. However, the number of amino groups in the XR _n is 1. When X is N, X is trivalent and n indicating the number of R is 3. R is the same or different and represents a substituted or unsubstituted alkyl group or aryl group. R is more preferably a substituted or unsubstituted alkyl group. When R is an alkyl group, examples thereof include a linear, branched or cyclic alkyl group, preferably an alkyl group having 1 to 16 carbon atoms, and having 1 carbon atom such as a methyl group, an ethyl group, a propyl group, or a butyl group. -4 alkyl groups are more preferable, and alkyl groups having 1 to 3 carbon atoms are more preferable. In addition, when R is an aryl group, an aryl group having about 6 to 18 carbon atoms such as a phenyl group and a naphthyl group is preferable.

In XR _n when X is P and P = O or when X is N, the alkyl group may have an alkoxy group, amino group, cyano group, carbonyl group, sulfonyl group. Examples of the substituent that the aryl group may have include an alkoxy group, an amino group, a cyano group, a carbonyl group, and a sulfonyl group. Examples of the amino group include a dimethylamino group and a diethylamino group, but the number of amino groups is 1 or less in XR ₃ and is intended to exclude tertiary polyamines. The three Rs may be the same or different.

  When X is S, S = O, O, X is divalent and n indicating the number of R is 2. R has the same meaning as R in the case where X is P and P = O, and is a substituted or unsubstituted alkyl group or aryl group. R is more preferably a substituted or unsubstituted aryl group. When X is CN, X is monovalent and n indicating the number of R is 1. Also in this case, R has the same meaning as R in the case where X is P and P = O, and is a substituted or unsubstituted alkyl group or aryl group. R is more preferably a substituted or unsubstituted aryl group.

Specific examples of the compound I include triphenylphosphine (PPh ₃ ), triphenylphosphine oxide (Ph ₃ P═O), tris (4-methoxyphenyl) phosphine (P (MeOPh) ₃ ), Compounds in which P = O; compounds in which X is S═O such as dimethyl sulfoxide; compounds in which X is CN such as p-tolunitrile (also referred to as p-methylbenzonitrile).

  In the heterocyclic compound (Compound II) of (II) above, it is necessary to have an unshared electron pair in the ring, and this unshared electron pair is coordinated to the cyclic halosilane to neutralize the cyclic halosilane. Form a complex. Examples of such a heterocyclic compound include one or more substituted or unsubstituted heterocyclic compounds containing N, O, S, or P having a loan pair in the ring. The substituent that the heterocyclic compound may have is the same as the substituent that R may have when it is an aryl group. Examples of the heterocyclic compound include pyridines, imidazoles, pyrazoles, oxazoles, thiazoles, imidazolines, pyrazines, thiophenes, and furans. Specific examples include N, N-dimethyl-4-aminopyridine, tetrahydrothiophene, tetrahydrofuran and the like.

  Of the compounds I and II, a compound that is liquid at the reaction temperature can also serve as a solvent.

  The usage-amount of the said compound I and the said compound II should just be determined suitably, and 0.1-50 mol may be used for the said compound with respect to 6 mol of halosilanes, and it is preferable to use 0.5-3 mol.

The cyclic halosilane neutral complex obtained by the method (B) is formed from 3 to 8 (preferably 5 or 6, especially 6) silicon atoms of the halosilane used as a raw material, and the silicon atoms are connected. It is a complex containing a ring and can be represented by the general formula [Y] _l [Si _m Z _2m-a H _a ]. In the above general formula, Y is the above compound I or the above compound II, Z is the same or different and represents a halogen atom of Cl, Br, I or F, l is 1 or 2, and m is 3 -8, preferably 5 or 6, particularly preferably 6, a is 0-2 m-1, preferably 0-m.

  The halosilane cyclization reaction in the method (A) and the method (B) is preferably performed by adding a tertiary amine. By adding a tertiary amine, the hydrochloric acid produced can be neutralized.

  Examples of the tertiary amine used in the cyclization reaction include triethylamine, tripropylamine, tributylamine, trioctylamine, triisobutylamine, triisopentylamine, diethylmethylamine, diisopropylethylamine (DIPEA), dimethylbutylamine. , Dimethyl-2-ethylhexylamine, diisopropyl-2-ethylhexylamine, methyl dioctylamine and the like are preferable.

1 type may be used for the said tertiary amine and it may use 2 or more types together. Tertiary amines also include those coordinated to cyclic halosilanes. For example, amines that are not relatively bulky and highly symmetric, such as diethylmethylamine and triethylamine, coordinate relatively efficiently. It is thought that. However, since only the tertiary amine represented by XR _n of the compound I tends to lower the yield of the cyclic halosilane neutral complex, it is preferable to use a compound I other than the tertiary amine in combination.

  The tertiary amine is preferably used in an amount of 0.5 to 4 mol, particularly preferably 1 mol, relative to 1 mol of halosilane.

  In the present invention, although not limited, it is preferable not to use a tertiary polyamine having 2 or more carbon atoms and 3 or more amino groups. Use of the tertiary polyamine is not preferable from the viewpoint of safety because a salt of cyclic halosilane containing silicon as a counter cation is generated and silane gas is generated during storage or reduction reaction.

  The halosilane cyclization reaction in the above method (A) and the above method (B) can be carried out in an organic solvent, if necessary. As the organic solvent, a solvent that does not interfere with the cyclization reaction is preferable. For example, a hydrocarbon solvent (for example, hexane, heptane, benzene, toluene, etc.), a halogenated hydrocarbon solvent (for example, chloroform, dichloromethane, 1, Preferred are aprotic polar solvents such as 2-dichloroethane), ether solvents (for example, diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, diisopropyl ether, methyl tertiary butyl ether), and acetonitrile. Among these, chlorinated hydrocarbon solvents such as chloroform, dichloromethane and 1,2-dichloroethane are preferable, and 1,2-dichloroethane is particularly preferable. In addition, these organic solvents may use 1 type and may use 2 or more types together.

  The amount of the organic solvent used is not particularly limited, but it is usually preferable to adjust the halosilane concentration to be 0.5 to 10 mol / L, and more preferable concentration is 0.8 to 8 mol / L, even more preferable. The concentration is 1 to 5 mol / L.

  The reaction temperature in the cyclization reaction can be appropriately set according to the reactivity, and is, for example, about 0 to 120 ° C, preferably about 15 to 70 ° C. The cyclization reaction is recommended to be performed in an inert gas atmosphere such as nitrogen.

  After the cyclization reaction, it is preferable to include a step of washing the reaction solution containing the cyclic halosilane with a non-halogen solvent. That is, when the cyclization reaction is completed, a solution or dispersion of a cyclic halosilane (a cyclic halosilane salt, a free cyclic halosilane, a cyclic halosilane neutral complex, etc.) is formed. The resulting solid is concentrated or filtered, and the resulting solid is, for example, a halogen solvent such as chloroform, dichloromethane or 1,2-dichloroethane, an aprotic polar solvent such as acetonitrile, or a hydrocarbon solvent such as hexane, heptane, benzene or toluene. It may be purified by washing with a non-halogen solvent.

  It is preferable to include a step of washing with a halogen solvent prior to washing with the non-halogen solvent. The amine hydrochloride can be removed by washing with a halogen solvent, and the halogen solvent can be removed by washing with a non-halogen solvent.

The cleaning using the halogen solvent and the cleaning using the non-halogen solvent may be performed once each or twice or more.
The aluminum content in the cyclic halosilane is sufficiently reduced by these washing, filtration steps, crystallization, adsorption and the like.

The cyclic halosilane can be obtained as a highly pure solid by purification. However, if desired, it can be obtained as a composition containing a cyclic halosilane containing impurities. The composition containing cyclic halosilane preferably contains 80% by mass or more of cyclic halosilane, more preferably 90% by mass or more, and still more preferably 95% by mass or more. The upper limit is, for example, 99.99% by mass. Examples of the impurity include a solvent, a residue of the compound I or the compound II, a decomposition product of a cyclic halosilane, a halosilane polymer, and the like. The content of the impurity in the composition containing cyclic halosilane is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and the lower limit is, for example, 0.01% by mass. %.
The cyclic halosilane thus obtained is preferably used as the halosilane of the present invention.

<Reduction method of cyclic halosilane (preparation method of cyclic hydrogenated silane)>
By including a step (reduction step) of reducing the cyclic halosilane (a cyclic halosilane salt, a free cyclic halosilane, a cyclic halosilane neutral complex, etc.), a hydrogenated silane containing a cyclic hydrogenated silane can be produced. The reduction step is preferably performed in the presence of a reducing agent.

The reducing agent that can be used in the reduction step is not particularly limited, but it is preferable to use one or more selected from the group consisting of an aluminum-based reducing agent and a boron-based reducing agent. Examples of the aluminum reducing agent include lithium aluminum hydride (LiAlH ₄ ; LAH), diisobutylaluminum hydride (DIBAL), sodium bis (2-methoxyethoxy) aluminum hydride [“Red-Al” (manufactured by Sigma-Aldrich). (Registered trademark)] and the like. Examples of the boron-based reducing agent include metal hydrides such as sodium borohydride and lithium triethylborohydride, and diborane. It is preferable to use a metal hydride. In addition, 1 type may be used for a reducing agent and it may use 2 or more types together.

  What is necessary is just to set the usage-amount of the reducing agent in the said reduction | restoration process suitably, for example, it is preferable that the equivalent of the hydride in a reducing agent with respect to one silicon-halogen bond of cyclic halosilane shall be 0.9 equivalent or more. The amount of the reducing agent used is more preferably 1.0 to 50 equivalents, still more preferably 1.0 to 30 equivalents, particularly preferably 1.0 to 15 equivalents, and most preferably 1.0 to 2 equivalents. When the amount of the reducing agent used is too large, post-treatment takes time and the productivity tends to decrease. On the other hand, when the amount of the reducing agent used is too small, the halogen remains without being reduced, and the yield tends to decrease.

  The molar ratio of cyclic halosilane / reducing agent is preferably 1: 3-4, more preferably 1: 3. When the range is exceeded, the reduction reaction proceeds excessively, and the amount of normal hexasilane that is a ring-opened product may be increased.

  In the reduction step, a Lewis acid catalyst may be used in combination with the reducing agent as a reduction aid. Lewis acid catalysts include chlorides such as aluminum chloride, titanium chloride, zinc chloride, tin chloride and iron chloride; bromides such as aluminum bromide, titanium bromide, zinc bromide, tin bromide and iron bromide; Iodides such as aluminum, titanium iodide, zinc iodide, tin iodide and iron iodide; fluorides such as aluminum fluoride, titanium fluoride, zinc fluoride, tin fluoride and iron fluoride; A metal compound is mentioned. These may use 1 type and may use 2 or more types together.

  The reaction in the reduction step can be performed in the presence of an organic solvent, if necessary. Examples of the organic solvent include hydrocarbon solvents such as hexane and toluene; ether solvents such as diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, diisopropyl ether, and methyl tertiary butyl ether; These organic solvents may be used alone or in combination of two or more. Further, the organic solvent solution obtained when producing the cyclic halosilane may be used as it is as the organic solvent solution in the reduction step, or the organic solvent is distilled off from the organic solvent solution containing the cyclic halosilane to obtain a new one. An organic solvent may be added to perform the reduction step. The organic solvent used for the reaction in the reduction step is preferably purified by distillation or dehydration before the reaction in order to remove water and dissolved oxygen contained therein.

  The amount of the organic solvent used for the reduction reaction is preferably adjusted so that the concentration of the cyclic halosilane is 0.01 to 1 mol / L, more preferably 0.02 to 0.7 mol / L, still more preferably. It is 0.03-0.5 mol / L. By performing the reaction in the above range, the content of impurities such as halogen elements contained in the hydrogenated silane composition tends to be significantly reduced.

  The reduction can be performed by bringing a cyclic halosilane and a reducing agent into contact with each other. In contacting the cyclic halosilane and the reducing agent, it is preferable to contact in the presence of a solvent. In order to bring the cyclic halosilane and the reducing agent into contact with each other in the presence of a solvent, for example, (a) the reducing agent is added to the cyclic halosilane solution or dispersion as it is, and (b) the cyclic halosilane solution or dispersion is reduced. A mixing procedure such as adding a solution or dispersion in which an agent is dissolved or dispersed in a solvent, or (c) adding a cyclic halosilane and a reducing agent simultaneously or sequentially into the solvent may be employed. Among these, the embodiment (b) is particularly preferable.

  Further, upon contact between the cyclic halosilane and the reducing agent, it is preferable to drop at least one of the cyclic halosilane solution or dispersion and the reducing agent solution or dispersion into the reaction system in which the reduction is performed. By dropping one or both of the cyclic halosilane and the reducing agent in this way, the heat generated by the reduction reaction can be controlled by the dropping speed, etc., so that, for example, it is possible to reduce the size of the capacitor, etc. An effect leading to improvement is obtained.

  Preferred embodiments in the case of dropping one or both of the cyclic halosilane and the reducing agent include the following three embodiments. That is, A1) A mode in which a solution or dispersion of a cyclic halosilane is charged in a reactor and a solution or dispersion of a reducing agent is dropped into the reactor. B1) A solution or dispersion of a reducing agent is charged in the reactor. A mode in which a solution or dispersion of a cyclic halosilane is dropped into this, C1) A mode in which a solution or dispersion of a cyclic halosilane and a solution or dispersion of a reducing agent are dropped simultaneously or sequentially into a reactor. Among these, the aspect of A1) is preferable.

  In the case where one or both of the cyclic halosilane and the reducing agent are added dropwise in the above aspects A1) to C1), the concentration of the cyclic halosilane solution or dispersion is preferably 0.01 mol / L or more, more preferably 0.02 mol / L or more, more preferably 0.04 mol / L or more, particularly preferably 0.05 mol / L or more. If the concentration of the cyclic halosilane is too low, the amount of solvent that must be distilled off when isolating the target product increases, so that productivity tends to decrease. On the other hand, the upper limit of the concentration of the cyclic halosilane solution or dispersion is preferably 1 mol / L or less, more preferably 0.8 mol / L or less, and still more preferably 0.5 mol / L or less.

  The lower limit of the temperature at the time of dropping (specifically, the temperature of the dropping solution or dispersion) is preferably −198 ° C. or higher, more preferably −160 ° C. or higher, and further preferably −100 ° C. or higher. Moreover, the upper limit of the temperature at the time of dripping becomes like this. Preferably it is +150 degrees C or less, More preferably, it is +100 degrees C or less, More preferably, it is +80 degrees C or less, Most preferably, it is +40 degrees C or less. The temperature of the reaction vessel (reaction temperature) may be appropriately set according to the type of cyclic halosilane or reducing agent, and usually the lower limit is preferably −198 ° C. or higher, more preferably −160 ° C. or higher. More preferably, it is −100 ° C. or higher. The upper limit of the temperature of the reaction vessel (reaction solution) is preferably + 150 ° C. or less, more preferably + 100 ° C. or less, still more preferably + 80 ° C. or less, and particularly preferably + 40 ° C. or less. When the reaction temperature is low, decomposition and polymerization of the intermediate product and the target product can be suppressed, so that the yield is improved. The reaction time may be appropriately determined according to the progress of the reaction, and is usually 10 minutes to 72 hours, preferably 1 hour to 48 hours, more preferably 2 hours to 24 hours.

As an example, a scheme example using trichlorosilane as the halosilane, triphenylphosphine (PPh ₃ ) as the compound I, and N, N-diisopropylethylamine (DIPEA) as the tertiary amine in the above method (B) is shown below.

When trichlorosilane is used as a starting material and the above compound I is triphenylphosphine (PPh ₃ ), usually a complex containing 6-membered dodecachlorocyclohexasilane (dodecachlorocyclohexasilane and triphenylphosphine) as shown in the above scheme. Becomes a neutral complex ([PPh ₃ ] ₂ [Si ₆ Cl ₁₂ ]). Since this cyclic halosilane neutral complex contains no silicon atoms in addition to the silicon atoms forming the ring structure, no silane gas or organic monosilane is generated during reduction, alkylation or arylation. Can be suppressed.

  The yield / yield of the cyclic halosilane neutral complex generated by this cyclization reaction can be calculated using the methylation reaction represented by the following scheme in which the complex reacts quantitatively.

A method for obtaining cyclohexasilane by reducing the cyclic halosilane neutral complex (for example, [PPh ₃ ] ₂ [Si ₆ Cl ₁₂ ]), for example, when LiAlH ₄ is used as a reducing agent, is represented by the following scheme. expressed.

  The reduction reaction is usually preferably performed in an atmosphere of an inert gas such as nitrogen gas or argon gas.

  The cyclic hydrogenated silane containing cyclohexasilane produced by the reduction reaction is, for example, solid-liquid separated from a reaction solution obtained after the reduction (solid impurities such as by-products), and then the solvent is distilled under reduced pressure. Thereafter, the cyclic hydrogenated silane is isolated, for example, by distillation.

  The above-mentioned solid-liquid separation method can be preferably employed because filtration is simple, but is not limited thereto, and for example, a known solid-liquid separation method such as centrifugation or decantation can be appropriately employed.

That is, it is preferable to include a step of performing solid-liquid separation at least twice after reducing the cyclic halosilane. For example, after a liquid and a solid containing a cyclic hydrogenated silane are once separated into solid and liquid (first separation), the liquid containing the cyclic hydrogenated silane is preferably concentrated and a hydrocarbon solvent (such as hexane) is used as a dilution solvent. After the addition, preferably the solid that has been concentrated and precipitated is separated again (second separation), and the operations from the first separation to the second separation may be repeated as necessary. It is more preferable to perform solvent dilution, concentration, and solid-liquid separation once or more after the first separation, and may be repeated a plurality of times.
The solid-liquid separation may be performed twice or three times or more. The number of solid-liquid separations is not particularly limited, but the upper limit is about 5 or less in consideration of productivity.

  Next, after concentrating the solution containing the cyclic hydrogenated silane obtained by the solid-liquid separation as necessary, the concentrated cyclic hydrogenated silane (preferably cyclohexasilane) is distilled. This distillation is preferably vacuum distillation. The method for distillation under reduced pressure is not particularly limited, and may be performed in a known distillation column.

For example, after distilling a solution containing cyclic hydrogenated silane under reduced pressure and collecting a fraction having an appropriate cyclic hydrogenated silane (particularly cyclohexasilane) content (first distillation), the recovered fraction is again distilled under reduced pressure. Then, a fraction having an appropriate content of cyclic hydrogenated silane (particularly cyclohexasilane) may be collected (second distillation), and the second distillation may be repeated as necessary.
When the cyclic hydrogenated silane is distilled, the aluminum content is reduced to the ppb order, and when the distillation is performed a plurality of times, the aluminum content is further reduced.

The thus obtained hydrogenated silane such as cyclic hydrogenated silane is preferably used as the hydrogenated silane of the present invention.
The polysilane composition of the present invention is obtained by mixing a hydrogenated silane and a halosilane (preferably a cyclic halosilane) before reducing the hydrogenated silane. In other words, the hydrogenated silane is a reaction product of a halosilane for preparing a hydrogenated silane and a reducing agent (preferably a hydrogenated silane purified by distillation after the reduction reaction), and the halosilane is a halosilane for external addition. preferable.
Here, the externally added halosilane is not an unreacted halosilane contained in the reaction product of the hydrogenated silane preparation halosilane and the reducing agent, but a reaction product of the hydrogenated silane preparation halosilane and the reducing agent. It refers to a halosilane added from the outside to a hydrogenated silane.
The halosilane for preparing hydrogenated silane and the halosilane for external addition may have the same structure or different structures, but are preferably the same. One or more types of halosilane for preparing hydrogenated silane and halosilane for external addition may be used.
The mixture of halosilane and hydrogenated silane is preferably a solution, and may contain a solvent as described above.

In order to perform doping as necessary, it is preferable to further include a step of mixing and / or contacting a compound having at least one element selected from Group 13 and Group 15.
The elements of Groups 13 and 15 and the compound (nucleophile) containing the element are as described above.

Mixing and / or contacting is preferably performed in the presence of an inert gas such as nitrogen gas or argon gas.
The mixing and / or contacting temperature may be, for example, about −40 to 60 ° C., preferably about 0 to 40 ° C.
The time for mixing and / or contacting may be, for example, about 1 to 72 hours and about 5 to 36 hours.
Moreover, when mixing and / or contacting, it is preferable to carry out under light-shielding conditions.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.

<Production Example 1>
_4. Production of halosilane (dodecachlorocyclohexasilane (Si ₆ Cl ₁₂ )) A mixture containing [Ph ₄ P ⁺ ] ₂ [Si ₆ Cl ₁₄ ²⁻ ] in a 200 ml two-necked flask equipped with a stirrer under a nitrogen atmosphere 0 g and 1.3 g of powdered aluminum chloride AlCl ₃ were added, and 84 g of benzene was added thereto. After stirring and reacting at room temperature for 1 hour, benzene was distilled off under reduced pressure. Subsequently, 67 g of n-hexane was added to the obtained white solid, stirred for 1 hour, allowed to stand overnight, and then filtered. From 77 g of the colorless and transparent filtrate obtained by filtration, 2.0 g of a white solid was obtained by distilling off hexane under reduced pressure. ^{When 29} Si NMR was measured, it was confirmed that Si ₆ Cl ₁₂ was formed.

<Production Example 2>
Preparation of hydrogenated silane Production of cyclic halosilane ([Ph ₃ P] ₂ [Si ₆ Cl ₁₂ ]) After the inside of a 3 L four-necked flask equipped with a thermometer, a condenser, a dropping funnel and a stirring device was replaced with nitrogen gas, 155 g (0.591 mol) of triphenylphosphine as a coordination compound, 458 g (3.54 mol) of diisopropylethylamine as a basic compound, and 1789 g of 1,2-dichloroethane as a solvent were added. Subsequently, while stirring the solution in the flask, 481 g (3.54 mol) of trichlorosilane as a halosilane compound was slowly added dropwise from a dropping funnel under 25 ° C. conditions.

  After completion of the dropwise addition, the mixture was stirred as it was for 2 hours, and then heated and stirred at 60 ° C. for 8 hours to carry out a cyclization coupling reaction to obtain a uniform reaction solution. The obtained reaction solution was concentrated, 7200 g of chloroform was added, the mixture was stirred and washed at room temperature for 1 hour, filtered, and the filtration residue was dried under reduced pressure to obtain a white solid (crude product).

Subsequently, 5-fold amount (based on mass) of dehydrated hexane was added to the white solid obtained above, and the mixture was stirred and washed at room temperature for 24 hours, followed by filtration. The obtained filtration residue was washed and filtered again with hexane in the same procedure as described above, and the obtained filtration residue was dried under reduced pressure to obtain a cyclic halosilane compound (bis (triphenylphosphine) dodecachlorocyclohexaci). A refined product of the run ([Ph ₃ P] ₂ [Si ₆ Cl ₁₂ ]) was obtained. All steps from washing to drying were performed in a nitrogen atmosphere. When the obtained purified product was measured by gas chromatography, the purified product contained 1% by mass of chloroform and 1% by mass of amine salt (amine hydrochloride) as the halogenated hydrocarbon compound.

B. Production of cyclohexasilane (Si ₆ H ₁₂ ) In a 10 L flask under a nitrogen atmosphere, the above Production Example 2 A.1. 1099 g of the purified product of cyclic halosilane obtained in the above and 5226 g of diethyl ether were added and stirred at −40 ° C. In this, 2005 g of 1M diethyl ether solution of LiAlH ₄ was dropped from the dropping funnel. After completion of dropping, the mixture was stirred at −40 ° C. for 3 hours to carry out a reduction reaction. Thereafter, the temperature of the reaction liquid was raised to room temperature, followed by solid-liquid separation (decantation) under a nitrogen atmosphere, and the diethyl ether solvent was distilled off from the obtained liquid 6974 g under reduced pressure, and then 3810 g of dehydrated hexane was added. Thereafter, diethyl ether and hexane were again distilled off under reduced pressure and concentrated, followed by solid-liquid separation (filtration) to remove the precipitated solid. After the solvent was further distilled off from the obtained filtrate, the solvent was filtered off and 160 g of crude cyclohexasilane product was obtained as a filtrate.

139 g of the obtained cyclohexasilane crude product was distilled under reduced pressure (conditions: internal liquid temperature 41 to 53 ° C., pressure 120 to 200 Pa) to obtain 51 g of cyclohexasilane crude distilled product (GC purity (area%): 95.4% to 98.1%). Next, 114 g of the obtained cyclohexasilane crude distillation product was again distilled under reduced pressure (conditions: internal liquid temperature 35 to 43 ° C., pressure 60 to 97 Pa) to obtain 106 g of cyclohexasilane main distillation product (GC purity (area %): 98.0% to 99.1%).
<Chromatography (GC) conditions>
Detection: FID
Column: Capillary column of poly (5% diphenyl / 95% dimethyl) siloxane phase, 0.25 μm × 0.25 mm × 30 m
Vaporization chamber temperature: 250 ° C
Detector temperature: 280 ° C
Temperature rising conditions: 1) Holding at 50 ° C. for 5 minutes, 2) Heating up to 250 ° C. at a heating rate of 20 ° C./min, 3) Heating up to 280 ° C. at a heating rate of 10 ° C./min, 4) 10 at 280 ° C. Minute hold

<Example 1>
Production of polysilane composition In a nitrogen atmosphere, 265 mg (0.45 mmol) of dodecachlorocyclohexasilane (Si ₆ Cl ₁₂ ) obtained in Production Example 1 was placed in a 50 mL eggplant-shaped flask, and then 17.6 g of benzene was added. And dissolved. By adding 81 mg (0.45 mmol) of the cyclohexasilane main product (Si ₆ H ₁₂ ) obtained in Production Example 2 to the obtained solution and stirring for 24 hours at 25 ° C., a colorless transparent solution was obtained. A polysilane composition having a molar ratio of Si ₆ Cl ₁₂ and Si ₆ H ₁₂ of 1: 1 was obtained (the aluminum content was about 1000 ppb in the polysilane composition).

Claims (13)

A halosilane represented by the general formula Si _m X _2m (m = 3 to 8, X is a halogen element) and a hydrogenated silane (n = 3 to 8) represented by the general formula Si _n H _2n , Content is 0.01 ppb-1000 ppm on a mass basis, The polysilane composition characterized by the above-mentioned.   The polysilane composition according to claim 1, wherein the hydrogenated silane is a reaction product of a halosilane for preparing a hydrogenated silane and a reducing agent, and the halosilane is a halosilane for external addition.   The polysilane composition according to claim 1 or 2, wherein the purity of the hydrogenated silane is 90% by mass or more.   The polysilane composition according to any one of claims 1 to 3, wherein a content (mass basis) of the halosilane is 0.01 to 10 mol with respect to 1 mol of the hydrogenated silane.   The polysilane composition according to any one of claims 1 to 4, wherein at least a part of the halogen element contained in the halosilane is substituted with at least one element selected from Group 13 and Group 15. The polysilane composition according to claim 1, wherein the halosilane is a cyclic halosilane represented by the general formula Si _m X _2m (m = 5 to 6, X is a halogen element).   The polysilane composition according to claim 6, wherein the cyclic halosilane is a cyclic chlorosilane.   The polysilane composition according to claim 7, wherein the cyclic chlorosilane is dodecachlorocyclohexasilane. The polysilane composition according to any one of claims 1 to 8, wherein the hydrogenated silane is a cyclic hydrogenated silane (n = 5 to 6) represented by a general formula Si _n H _2n .   The polysilane composition according to claim 9, wherein the cyclic hydrogenated silane is cyclohexasilane. A method for producing a polysilane composition into which a hetero element is introduced,
Mixing and / or mixing a halosilane represented by the general formula Si _m X _2m (m = 3 to 8, X is a halogen element) and a hydrogenated silane represented by the general formula Si _n H _2n (n = 3 to 8) Or the process made to contact is mentioned, The aluminum content is 0.01 ppb-1000 ppm by mass reference | standard, The manufacturing method characterized by the above-mentioned.   The method according to claim 11, wherein the mixture of the halosilane and the hydrogenated silane is a solution.   The method according to claim 11 or 12, further comprising a step of mixing and / or contacting a compound having at least one element selected from Group 13 and Group 15.