JP2022045139A - Production method of cyclic hydrogenated silane compound - Google Patents

Abstract

To provide a production method of a cyclic hydrogenated silane compound which can safely and simply handle an aluminum complex produced by a reaction between a salt of a cyclic halosilane compound and a halogenated aluminum compound and obtain the cyclic hydrogenated silane compound with a reduced aluminum amount at high purity.SOLUTION: A production method of a cyclic hydrogenated silane compound comprises the steps of: bringing a salt (A) of a cyclic halosilane compound and a halogenated aluminum compound (B) into contact with each other in a solvent (C) to produce a cyclic halosilane compound (D) (1); bringing the cyclic halosilane compound (D) and metal hydride (E) into contact with each other in a solvent (F) to obtain a composition including a cyclic hydrogenated silane compound (G) and an aluminum complex (H) (2); and separating the aluminum complex (H) (3). The step of separating the aluminum complex (H) is at least two of (a) a filtering step, (b) a step of separating a reaction liquid, a concentrated liquid thereof, or a washed liquid thereof, and (c) a step of performing washing with an acidic aqueous solution.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a cyclic hydride silane compound.

Thin-film silicon is used for solar cells, semiconductors, and the like, and conventionally, the thin-film silicon is manufactured by a vapor deposition film forming method (CVD method) using monosilane or the like as a raw material. In recent years, as a simpler method for producing thin-film silicon, a method of applying a hydrogenated polysilane solution to a base material and firing it has also attracted attention.

Cyclic hydride silane compounds are often used as the hydride polysilane, and as a method for producing the cyclic hydride silane compound, for example, a salt of the cyclic halosilane compound and an aluminum halide compound (for example, a Lewis acid compound) are brought into contact with each other. A method for obtaining a cyclic halosilane compound and reducing the obtained cyclic halosilane compound by contacting it with a metal hydride is known (Patent Documents 1 and 2).

In Patent Document 1, a cyclic hydride silane compound obtained by reducing a cyclic halosilane compound with a metal hydride and then purifying it by concentration or distillation is formed together with an aluminum complex, but contains a large amount of aluminum compound. Since the presence of a large amount of aluminum affects the electrical characteristics of the thin film, the amount of the aluminum compound is reduced by washing with water.

U.S. Pat. No. 7498015 Japanese Unexamined Patent Publication No. 2017-95324

However, in Patent Document 1, the reaction between the salt of the cyclic halosilane compound and the aluminum halide compound, the contact between the mixture obtained by this reaction and chlorine gas, and then the reaction with the reducing agent are carried out, but the aluminum complex remains as a residue. There is a risk that it will precipitate in the reactor and stirring such as the reduction reaction will not proceed smoothly or will stop, and the aluminum complex may react with the moisture in the air to generate chlorine gas.

Furthermore, when the reduced cyclic hydride silane compound is subjected to water washing, the unreacted reducing agent may react violently with water to generate hydrogen, and the cyclic hydride silane compound is decomposed to reduce the purity and the like. There is a risk of

Further, also in Patent Document 2, there is room for efficiently separating the aluminum complex derived from the halogenated aluminum compound and improving the productivity of the cyclic hydride silane compound.

The present invention has been made by paying attention to the above circumstances, and an object of the present invention is to safely and easily handle an aluminum complex formed by a reaction between a salt of a cyclic halosilane compound and an aluminum halide compound. It is an object of the present invention to provide a method for producing a cyclic hydride silane compound, which can obtain a cyclic hydride silane compound having a reduced amount of aluminum with high purity.

The gist of the present invention that has solved the problem of the present invention is as follows.
[1] Step 1, in which the salt (A) of the cyclic halosilane compound and the aluminum halide compound (B) are brought into contact with each other in the solvent (C) to produce the cyclic halosilane compound (D), the cyclic halosilane compound (D) and the metal. Step 2 of contacting the hydride (E) in the solvent (F) to obtain a composition containing the cyclic hydride silane compound (G) and the aluminum complex (H), and step 3 of separating the aluminum complex (H). The steps of separating the aluminum complex (H) include (a) a filtration step, (b) a step of separating a reaction solution, a concentrated solution thereof or a cleaning solution thereof, and (c) a step of washing with an acidic aqueous solution. A method for producing a cyclic hydride silane compound, which comprises at least two or more of the above.
[2] The production method according to [1], which further comprises distilling the cyclic hydrogenated silane compound (G).
[3] The production method according to [1] or [2], wherein the molar concentration of the cyclic halosilane compound (D) in the step 2 is 0.150 mol / L or more.
[4] Any of [1] to [3], wherein the ratio of the molar concentration of the cyclic halosilane compound (D) in the step 2 to the number of silicon atoms contained in the cyclic halosilane compound (D) is 0.90 mol / L or more. The manufacturing method described in Crab.
[5] The step of separating the aluminum complex (H) is (a) a step of separating a reaction solution, a concentrated solution thereof or a cleaning solution thereof and (b) a filtration step, or (a) a reaction solution and a concentrated solution thereof. The production method according to any one of [1] to [4], which is a step of separating those cleaning liquids and a step of (c) washing with an acidic aqueous solution.
[6] The production method according to any one of [1] to [5], wherein at least one or more of the solvent (C) and the solvent (F) is an ether solvent.
[7] The production method according to any one of [1] to [6], wherein the cyclic hydrogenated silane compound (G) contains cyclopentasilane or cyclohexasilane.
[8] The production method according to [7], wherein the cyclic hydrogenated silane compound (G) is cyclohexasilane.

According to the present invention, it is possible to safely and easily handle an aluminum complex formed by a reaction between a salt of a cyclic halosilane compound and an aluminum halide compound, and to obtain a cyclic hydrogenated silane compound having a reduced amount of aluminum with high purity. can.

The method for producing a cyclic hydride silane compound of the present invention is a step 1 in which the salt (A) of the cyclic halosilane compound and the aluminum halide compound (B) are brought into contact with each other in the solvent (C) to produce the cyclic halosilane compound (D). , The step 2 of contacting the cyclic halosilane compound (D) with the metal hydride (E) in the solvent (F) to obtain a composition containing the cyclic hydride silane compound (G) and the aluminum complex (H), and the above. The step of separating the aluminum complex (H) includes the step 3 of separating the aluminum complex (H), and the step of separating the aluminum complex (H) is (a) a filtration step, (b) a step of separating a reaction solution, a concentrated solution thereof or a cleaning solution thereof. And (c) at least two or more steps of washing with an acidic aqueous solution.

A feature of the present invention is that at least two steps (and preferably) of a filtration step, a reaction solution, a step of separating a concentrated solution thereof or a washing solution thereof, and a step of washing with an acidic aqueous solution are used for separating the aluminum complex. Distillation), and by combining these, it is possible to safely and easily handle the aluminum complex formed by the reaction between the salt of the cyclic halosilane compound and the aluminum halide compound, and the cyclic hydride silane compound with a reduced amount of aluminum. Can be obtained with high purity.

Hereinafter, steps 1 to 3 performed in the method for producing a cyclic hydride compound of the present invention will be described in order.

1. 1. Step 1 (Step to generate cyclic halosilane)
Step 1 is a step of contacting the salt (A) of the cyclic halosilane compound with the aluminum halide compound (B) in the solvent (C) to produce the cyclic halosilane compound (D).

Salt of cyclic halosilane compound (A)
The salt of the cyclic halosilane compound has a structure in which silicon atoms are connected to form a monoprime ring, and a halogen atom is bonded to at least one silicon atom constituting the monoprime ring, forming a salt. It is a compound. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The number of silicon atoms constituting the single element ring is not particularly limited, but 3 or more is preferable, 4 or more is more preferable, 5 or more is more preferable, 8 or less is more preferable, 7 or less is more preferable, and 6 or less is further preferable. preferable.

The cyclic halosilane compound may contain a silicon atom that does not form a monoprime ring. For example, a substituent containing a silicon atom (for example, a silyl group) is bonded to the silicon atom that constitutes the monoprime ring. May be. However, if a silicon atom that does not form a monoelement ring is contained, in the storage of the cyclic halosilane compound salt or the cyclic halosilane compound, or in the step of reducing the obtained cyclic halosilane compound to produce the cyclic hydride silane compound. Since the amount of silane gas generated tends to increase and the yield of the cyclic hydride silane compound tends to decrease, it is preferable that silicon atoms that do not form a monocyclic ring are not contained as much as possible.

It is preferable that at least one halogen atom is bonded to the monoelement ring formed from the silicon atom, and one or two halogen atoms are bonded to each of the silicon atoms constituting the monoelement ring. Is more preferable, and it is further preferable that two halogen atoms are bonded to each of the silicon atoms constituting the monoelement ring.

As the salt of the cyclic halosilane compound, it is preferable to use a compound represented by the following formula (1).

In the above formula (1), X ¹ and X ² each independently represent a halogen atom, L represents an anionic ligand, and p is an integer of -2 to -1 as the valence of the ligand L. Representing, K represents a counter cation, q represents an integer of +1 to +2 as the valence of the counter cation K, n represents an integer of 0 to 5, and a, b, and c are integers of 0 to 2n + 6, respectively. , A + b + c = 2n + 6, where 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 (where 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.

In the above formula (1), n represents the number of silicon atoms constituting the monoelement ring, and the value thereof is an integer of 0 to 5, preferably 1 or more, more preferably 2 or more, and preferably 4 or less. 3 or less is more preferable. It is particularly preferable that n is 3, that is, the compound represented by the formula (1) is preferably a 6-membered silicon single ring.

In the above formula (1), X ¹ represents a halogen atom bonded to a silicon atom constituting a ring, and X ² represents a halogen atom of a silyl group bonded to a silicon atom constituting the ring. Examples of the halogen atom of X ¹ and X ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. When there are a plurality of X ^1s , the plurality of X ^1s may be the same or different. When there are a plurality of X ^2s , the plurality of X ^2s may be the same or different.

In the above formula (1), a represents the number of halogen atoms bonded to the silicon atom constituting the ring, b represents the number of hydrogen atoms bonded to the silicon atom constituting the ring, and c represents the silicon constituting the ring. Represents the number of silyl groups attached to an atom. Further, d represents the number of halogen atoms of the silyl group bonded to the silicon atom constituting the ring, and e represents the number of hydrogen atoms of the silyl group bonded to the silicon atom constituting the ring. When c is 2 or more, the plurality of silyl groups bonded to the silicon atoms constituting the ring may be the same or different. a, b and c represent integers from 0 to 2n + 6 (where a + b + c = 2n + 6 and a and c are not 0 at the same time), a is an integer from 1 to 2n + 6 and b and c are integers from 0 to n + 5. It is preferable that a is an integer of n + 6 to 2n + 6, and b and c are integers of 0 to n.

If c is 0 in the above formula (1), side reactions such as a coupling reaction can be suppressed when the compound is reacted with the aluminum halide compound, or a salt of a cyclic halosilane compound or a salt thereof can be produced. The storage stability of the cyclic halosilane compound is improved, the generation of silane gas is suppressed in the step of reducing the obtained cyclic halosilane compound to produce the cyclic hydride silane compound, and the yield of the cyclic hydride silane compound is reduced. It is further preferable in that it can be enhanced. Further, it is particularly preferable that a is 2n + 6 and b and c are 0.

In the above formula (1), L represents an anionic ligand coordinated to a silicon atom constituting the ring, p represents the valence of the ligand L (an integer of -2 to -1), and m. Represents the number of ligands L (+1 to +2). Examples of the anionic ligand include halide ion, nitrate ion, cyanide ion and the like.

In the above formula (1), K represents a counter cation, q represents a valence of the counter cation K (an integer of +1 to +2), and depends on the valence and number of the ligand L and the valence of the counter cation K. Then, the values of s and t are determined respectively.

Examples of the counter-cation K include oniums (for example, phosphonium ion, ammonium ion, etc.), polyamine / SiH ₂ Cl ⁺ (for example, pedeta / SiH ₂ Cl ⁺ , Teeda / SiH ₂ Cl ⁺ , etc.) and the like. When the counter-cation K is onium, it is preferable because the yield of the cyclic halosilane compound is improved when the cyclic halosilane compound is produced by contacting with a salt of the cyclic halosilane compound.

As the oniums of the counter cation K, a phosphonium ion represented by the following formula (2) or an ammonium ion represented by the following formula (3) is preferable.

R ¹ to R ⁴ in the above formula (2) and R ⁵ to R ⁸ in the above formula (3) independently represent a hydrogen atom, an alkyl group, and an aryl group, respectively. In the above formula (2), R ¹ to R ⁴ may be different from each other, but it is preferable that they are all the same group. In the above formula (3), R ⁵ to R ⁸ may be different from each other, but it is preferable that they are all the same group.

The alkyl groups of 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, cyclohexyl group and the like. Alkyl groups having 1 to 16 carbon atoms are preferably mentioned, and alkyl groups having 1 to 8 carbon atoms are more preferable.

As the aryl group of R ¹ to R ⁴ and R ⁵ to R ⁸ , an aryl group having 6 to 18 carbon atoms such as a phenyl group and a naphthyl group is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. .. The R ¹ to R ⁴ and the R ⁵ to R ⁸ are preferably an alkyl group or an aryl group.

Specific examples of the salt of the cyclic halosilane compound represented by the above formula (1) include a salt of a tetradecachlorocyclohexasilane dianion complex ([Si ₆ Cl ₁₄ ^2- ]) and a tetradecabromocyclohexasi. Examples thereof include salts of a orchid-dianion complex ([Si ₆ Br ₁₄ ^2- ]). Further, as the counter ion, phosphonium ion or ammonium ion is preferable.

As the salt of the cyclic halosilane compound represented by the above formula (1), it is preferable to use the compound represented by the following formula (4) or the following formula (5). When such a compound is used as the salt of the cyclic halosilane compound, the formation of by-products and the formation of silane gas, which is a spontaneously ignitable gas, are suppressed when the salt of the cyclic halosilane compound is reacted with the aluminum halide compound. A halosilane compound can be easily produced. Further, the obtained cyclic halosilane compound can be reduced to efficiently produce a cyclic hydrogenated silane compound.

In the above formula (4) and the above formula (5), X ¹ , R ¹ to R ⁴ , R ⁵ to R ⁸ , n and a have the same meanings as described above, and X ³ represents a halogen atom. In addition, X ³ exists in the form of an ion in the above formula (4) and the above formula (5), and is a halide ion.

Examples of the halogen atom of X ³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

When there are a plurality of X ^3s , the plurality of X ^3s may be the same or different.

The above X ¹ and the above X ³ may be the same or different. In the above formula (4) and the above formula (5), if X ¹ and X ³ are all chlorine atoms, the cyclic hydrogenated silane compound can be produced at low cost.

In the above equation (4) and the above equation (5), n represents an integer of 0 to 5 and a represents an integer of 1 to 2n + 6, but it is particularly preferable that n is 3, in which case a is 6. The above is preferable, 9 or more is more preferable, and 12 or more is particularly preferable.

The salt of the cyclic halosilane compound may be a halosilane compound (preferably monosilane halide, more preferably trihalogenated silane, more preferably trichlorosilane) and a tertiary polyamine in contact with each other, or a halosilane compound and a phosphonium salt (preferably a phosphonium salt). It may be produced by contacting at least one of a quaternary phosphonium salt (preferably a quaternary ammonium salt) and an ammonium salt (preferably a quaternary ammonium salt), and the halosilane compound is contacted with at least one of the phosphonium salt and the ammonium salt. It is preferable to carry out the production by allowing the compound (hereinafter, also referred to as a cyclization coupling step).

For example, when trichlorosilane is used as the halosilane compound and a phosphonium salt is used, dodecachlorodihydrocyclohexasilane dianion salt (for example, [Ph ₄ P ⁺ ] ₂ [Si ₆ H ₂ Cl ₁₂ ] ^2- ), Tridecachlorohydrocyclohexasilane dianion salt (eg, [Ph ₄ P ⁺ ] ₂ [Si ₆ HCl ₁₃ ] ^2- ), tetradecachlorocyclohexasilane dianion salt (eg, [Ph ₄ P ⁺ ] ₂ [ A salt composed of a dianion and a phosphonium ion of a cyclic halosilane compound such as Si ₆ Cl ₁₄ ] ^2- ) can be obtained.

When trichlorosilane is used as the halosilane compound and an ammonium salt is used, dodecachlorodihydrocyclohexasilane dianion salt (for example, [Et ₄ N ⁺ ] ₂ [Si ₆ H ₂ Cl ₁₂ ] ^2- ), Tridecachlorohydrocyclohexasilane dianion salt (eg, [Et ₄ N ⁺ ] ₂ [Si ₆ HCl ₁₃ ] ^2- ), tetradecachlorocyclohexasilane dianion salt (eg, [Et ₄ N ⁺ ] ₂ [ A salt composed of a dianion and an ammonium ion of a cyclic halosilane compound such as Si ₆ Cl ₁₄ ] ^2- ) can be obtained.

The cyclization coupling step is a chelate type such as a polyether compound (preferably 1,2-dimethoxyethane), a polythioether compound, or a polydentate phosphine compound (preferably 1,2-bis (diphenylphosphino) ethane). It may be done in the presence of a ligand.

The cyclization coupling step may be carried out in the presence of a basic compound. Examples of the basic compound include (mono-, di-, tri-, poly-) amine compounds, and among them, monoamine compounds are preferably used. Specifically, for example, triethylamine, tripropylamine, tributylamine, trioctylamine, triisobutylamine, triisopentylamine, diethylmethylamine, diisopropylethylamine, dimethylbutylamine, dimethyl-2-ethylhexylamine, diisopropyl-2- Ethylhexylamine, methyldioctylamine and the like are preferable, and tributylamine is particularly preferable. As the basic compound, only one kind may be used, or two or more kinds may be used in combination.

The salt of the cyclic halosilane compound may be purified, if necessary, prior to the reaction with the aluminum halide compound. By purifying the salt of the cyclic halosilane compound to increase its purity, the formation of by-products can be suppressed by the reaction with the aluminum halide compound. The salt of the cyclic halosilane compound may be purified by a known purification method such as solid-liquid separation, distillation (solvent distillation), crystallization, and extraction. The solid-liquid separation means at this time is not particularly limited, and known solid-liquid separation means such as filtration, precipitation separation, centrifugation, and decantation can be used.

Halogenated aluminum compound (B)
Examples of the aluminum halide compound include a Lewis acid compound such as an aluminum fluoride compound, an aluminum chloride compound, an aluminum bromide compound, and an aluminum iodide compound.

The aluminum halide compound is preferably aluminum chloride or aluminum bromide, and more preferably an aluminum chloride compound from the viewpoint of reactivity and ease of control of the reaction.

The following compounds may be used in combination with the aluminum halide compound as long as the effects of the present invention are exhibited.
Specifically, titanium halides such as titanium chloride and titanium bromide; halogenated zirconium such as zirconium chloride and zirconium bromide; copper halides such as copper chloride and copper bromide; halogens such as silver chloride and silver bromide. Silver chemicals; gold halides such as gold chloride and gold bromide; boron halides such as boron trifluoride, boron trichloride, boron tribromide; gallium halides such as gallium chloride and gallium bromide; indium chloride, odor Halogenated indium such as indium oxide; Talium halide such as tallium chloride and talium bromide; Calcium halide such as calcium chloride and calcium bromide; Iron halide such as iron chloride and iron bromide; Zinc chloride and zinc bromide Such as zinc halide; etc.

The amount of the above-mentioned aluminum halide compound (preferably Lewis acid compound) to be used may be appropriately adjusted according to the reactivity between the salt of the cyclic halosilane compound and the aluminum halide compound, and is, for example, 1 mol of the salt of the cyclic halosilane compound. On the other hand, 0.5 mol or more is preferable, 1.5 mol or more is more preferable, 20 mol or less is preferable, and 10 mol or less is more preferable.

Solvent (C)
The contact between the salt of the cyclic halosilane compound and the aluminum halide compound (preferably Lewis acid compound) is carried out in a solvent or a dispersion medium (hereinafter, these are simply referred to as a solvent).
The solvent (C) (hereinafter, may be referred to as reaction solvent (I)) is preferably an organic solvent.
Examples of the solvent (C) include aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane and decane; aromatic hydrocarbon solvents such as benzene and toluene; and hydrocarbon solvents such as diethyl ether and tetrahydrofuran. , Cyclopentyl methyl ether, diisopropyl ether, methyl tertiary butyl ether and other ether solvents; and the like.

The solvent (C) is more preferably a hydrocarbon solvent. By using a hydrocarbon solvent, it becomes easy to carry out the residue dissolution treatment after contacting the salt of the cyclic halosilane compound with the aluminum halide compound (preferably Lewis acid compound).
Among them, the solvent (C) is particularly preferably an aliphatic hydrocarbon-based solvent, and most preferably hexane. Only one kind of these solvents may be used, or two or more kinds may be used in combination. In addition, in order to remove water and dissolved oxygen contained in the solvent, it is preferable to perform purification such as distillation and dehydration in advance.

The amount of the solvent (C) used is preferably 1 to 1000 parts by mass, more preferably 10 to 800 parts by mass, and further preferably 100 to 600 parts with respect to 100 parts by mass of the total amount of the salt of the cyclic halosilane compound and the aluminum halide compound. It is a mass part.

In other words, the amount of the solvent (C) used is usually preferably adjusted so that the concentration of the salt of the cyclic halosilane compound is 0.005 mol / L or more and 10 mol / L or less, and the more preferable concentration is 0. The concentration is 01 mol / L or more, a more preferable concentration is 0.05 mol / L or more, a more preferable concentration is 5 mol / L or less, and a further preferable concentration is 1 mol / L or less.

The method for contacting the salt of the cyclic halosilane compound with the aluminum halide compound (preferably Lewis acid compound) in the reaction solvent (I) is not particularly limited, and for example, (1) the salt of the cyclic halosilane compound and the Lewis acid compound. By dissolving or dispersing each of the above in a solvent in advance, a solution (or dispersion) of a salt of the cyclic halosilane compound and a solution (or dispersion) of the Lewis acid compound are prepared, and then these solutions (or dispersion) are prepared. , (2) A method of simultaneously or sequentially adding a salt of a cyclic halosilane compound and a Lewis acid compound to a solvent, (3) a method of adding a Lewis acid compound to a solution (or dispersion) of a salt of a cyclic halosilane compound. (4) A method in which a salt of a cyclic halosilane compound and a Lewis acid compound are charged and a solvent is added thereto; and the like can be mentioned.

The temperature at which the salt of the cyclic halosilane compound and the aluminum halide compound (preferably Lewis acid compound) are brought into contact with each other to carry out the reaction may be appropriately adjusted according to the reactivity, and is, for example, −80 ° C. or higher. Is preferable, −50 ° C. or higher is more preferable, −30 ° C. or higher is further preferable, 200 ° C. or lower is preferable, 150 ° C. or lower is more preferable, and 100 ° C. or lower is further preferable.

The time for contacting the salt of the cyclic halosilane compound with the aluminum halide compound (preferably Lewis acid compound) may be appropriately set according to the reaction temperature and the degree of progress of the reaction. Time or more is preferable, 2 hours or more is more preferable, and 3 hours or more is further preferable. The above time can be, for example, 24 hours or less. The above time is more preferably 20 hours or less, further preferably 15 hours or less.

Heating and / or stirring may be carried out in order to accelerate the reaction between the salt of the cyclic halosilane compound and the aluminum halide compound (preferably a Lewis acid compound).

The atmosphere when the salt of the cyclic halosilane compound and the aluminum halide compound (preferably Lewis acid compound) are brought into contact with each other to carry out the reaction is not particularly limited, but in order to suppress the oxidation of the cyclic halosilane compound and its salt, The oxygen concentration in the atmosphere is preferably 9% by volume or less, more preferably 5% by volume or less, further preferably 3% by volume or less, and particularly preferably 1% by volume or less.

Further, in order to suppress the hydrolysis of the cyclic halosilane compound and its salt, the water concentration in the above atmosphere is preferably 2000 ppm (volume basis) or less, more preferably 1500 ppm (volume basis) or less, and further preferably 1000 ppm (volume basis) or less. , 500 ppm (volume basis) or less is even more preferable, 150 ppm (volume basis) or less is particularly preferable, and 10 ppm (volume basis) or less is most preferable.

The reaction between the salt of the cyclic halosilane compound and the aluminum halide compound (preferably Lewis acid compound) is preferably carried out in an atmosphere of an inert gas (for example, nitrogen gas or argon gas), and is also carried out in the dark. It is also preferable.

Cyclic halosilane compound (D)
By contacting and reacting the salt of the cyclic halosilane compound with the aluminum halide compound (preferably Lewis acid compound), a free cyclic halosilane compound (non-complex type cyclic halosilane compound) is obtained together with the residue (aluminum complex). be able to. Such a non-complex type cyclic halosilane compound has higher solvent solubility than the complex type cyclic halosilane compound. Therefore, when the obtained non-complex type cyclic halosilane compound is brought into contact with a metal hydride and reduced, the reduction reaction of the cyclic halosilane compound can be carried out at a high concentration, and the cyclic hydride silane compound can be efficiently produced. can.

In the step of contacting the salt of the cyclic halosilane compound with the aluminum halide compound, for example, the cyclic halosilane compound represented by the following formula (6) is obtained from the salt of the cyclic halosilane compound represented by the above formula (1). Can be done.

In the above formula (6), X ¹ , X ² , a to e, and n have the same meanings as described above.

On the other hand, the cyclic halosilane compound obtained by reacting the salt of the cyclic halosilane compound with the Lewis acid compound may be purified as necessary in order to remove impurities. For the purification of the cyclic halosilane compound, known means such as solid-liquid separation, distillation (solvent distillation), crystallization, extraction and the like can be used.

2. 2. Step 2 (Step to obtain a composition containing a cyclic hydride compound and an aluminum complex)
Step 2 is a step of contacting the cyclic halosilane compound (D) with the metal hydride (E) in the solvent (F) to obtain a composition containing the cyclic hydride silane compound (G) and the aluminum complex (H). be.

The cyclic halosilane compound obtained by contacting the salt of the cyclic halosilane compound with the aluminum halide compound (Lewis acid compound) is reduced by contacting with a metal hydride by a known method (hereinafter referred to as a reduction step). There is) to produce the cyclic hydride silane compound (G).

The molar concentration of the cyclic halosilane compound (D) used for the reaction with the metal hydride (E) (that is, the molar concentration of the cyclic halosilane compound (D) in step 2) increases the yield and purity of the cyclic hydride silane compound. From the viewpoint, it is preferably 0.150 mol / L or more, more preferably 0.155 mol / L or more, still more preferably 0.160 mol / L or more, 0.165 mol / L or more, and preferably 1.000 mol / L or less. It is more preferably 0.900 mol / L or less, still more preferably 0.850 mol / L or less.
Here, the cyclic halosilane compound (D) (solution) or the metal hydride (solution) may be added all at once, or may be added continuously or stepwise. In that case, the molar concentration of the cyclic halosilane compound (D) in step 2 may be the molar concentration of the total amount of the cyclic halosilane compound used in step 2 with respect to the total amount of the solvent used in step 2.

The ratio of the molar concentration of the cyclic halosilane compound (D) to the number of silicon atoms contained in the cyclic halosilane compound (D) in the step 2 is preferably 0.90 mol / L or more, more preferably 0.95 mol / L or more, and further. It is preferably 1.00 mol / L or more, preferably 5.00 mol / L or less, more preferably 4.90 mol / L or less, and further preferably 4.80 mol / L or less.
The ratio may be a value that simultaneously satisfies the above-mentioned molar concentration of the cyclic halosilane compound (D), and can be applied to any of batch addition, continuous addition, and divided addition.

Metal hydride (E)
The metal hydride (E) is a conventionally known reducing agent, and is preferably at least one selected from the group consisting of an aluminum-based reducing agent and a boron-based reducing agent. Examples of the aluminum-based reducing agent include lithium aluminum hydride (LiAlH ₄ ; LAH), diisobutylaluminum hydride (DIBAL), and bis (2-methoxyethoxy) aluminum sodium hydride [“Red-Al” (Sigma Aldrich). Metal hydrides such as [registered trademark)] and the like can be mentioned. Examples of the boron-based reducing agent include metal hydrides such as sodium borohydride and lithium triethylborohydride, diborane and the like, and it is preferable to use metal hydrides. One type of reducing agent may be used, or two or more types may be used in combination. Of these, lithium aluminum hydride is particularly preferable.

The amount of the metal hydride (E) to be used may be appropriately set, and for example, the equivalent of hydride in the reducing agent to one silicon-halogen bond of the cyclic halosilane is preferably at least 0.9 equivalent or more. The amount of the metal hydride (E) 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. Equivalent. If the amount of the metal hydride (E) used is too large, the post-treatment takes time and the productivity tends to decrease. On the other hand, if the amount of the metal hydride (E) used is too small, the halogen remains unreduced and the yield tends to decrease.

Solvent (F)
The reduction reaction of the cyclic halosilane compound with a metal hydride is preferably carried out in the solvent (F). The solvent used here (hereinafter, may be referred to as reaction solvent (II)) is preferably an organic solvent, for example, a hydrocarbon solvent such as hexane or toluene; diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, diisopropyl ether, methyl tasher. An ether solvent such as lebutyl ether; and the like can be mentioned. Only one kind of these solvents may be used, or two or more kinds may be used in combination. The reaction solvent (II) used in the reduction step is preferably purified by distillation, dehydration or the like before the reaction in order to remove water and dissolved oxygen contained therein.

At least one or more of the solvent (C) and the solvent (F) is preferably an ether solvent, and the solvent (F) is more preferably an ether solvent.
The solvent (F) is preferably a solvent for the metal hydride (E), and the solvent (C) is preferably a solvent for the cyclic halosilane compound (D). Both the solvent (C) and the solvent (F) may be present.

As described above, the amount of the solvent (F) to be used may be any amount as long as the amount of the metal hydride is used, and is preferably 1 to 10000 parts by mass, more preferably 1 to 10000 parts by mass with respect to 100 parts by mass of the metal hydride. It is 100 to 5000 parts by mass, more preferably 400 to 2000 parts by mass.

In one aspect of the present invention, the reaction solution produced in the step 2 may be concentrated and recovered without concentrating the reaction solution produced in the step 2. In the case of concentrating the reaction solution, the upper layer may be recovered by separating the solution after concentrating the volume to 80% or more, more preferably 90% or more, still more preferably 95% or more of the original volume.
The reaction solution may be separated into a plurality of layers by concentration.
The plurality of layers include, for example, (i) an upper layer and a lower layer, (ii) an upper layer, an intermediate layer, a lower layer, and the like.
Concentration may be an operation of volatilizing the solvent contained in the reaction solution by changing the temperature, pressure, or the like, and examples thereof include decompression treatment and heat treatment.
The liquid separation may be an operation of extracting or taking out a layer containing a desired substance from a plurality of layers, and examples thereof include liquid separation by a decantation operation and liquid separation by a funnel.

In one aspect of the present invention, the upper layer preferably contains a cyclic hydrogenated silane compound, and the lower layer preferably contains an aluminum complex. The lower layer may be concentrated under reduced pressure and subjected to filtration to remove the aluminum complex, and the lower layer from which the aluminum complex has been removed may be used together with the upper layer in the next step (preferably a distillation step).

Cyclic hydride silane compound (G)
The cyclic hydride silane compound has a monoprime ring composed of a series of silicon atoms, and is a compound composed of a silicon atom and a hydrogen atom. The cyclic hydride silane compound may have a hydrogen atom bonded to all the substituted positions of the silicon atom constituting the monoelement ring, or an unsubstituted silyl group bonded to the silicon atom constituting the monoelement ring. It may be. However, from the viewpoint of storage stability, it is preferable that the silicon atom other than the silicon atom constituting the monoprime ring is not contained. By reducing the cyclic halosilane compound instead of the salt of the cyclic halosilane compound, the generation of silane gas derived from the counter cation of the salt is not generated and the generation of silane gas can be suppressed as a whole, so that the cyclic hydrogenated silane compound can be obtained in high yield. It can be easily obtained.

The cyclic hydride silane compound obtained in the reduction step is preferably a compound represented by the following formula (12).
Si _z H _2z (12)

In the above formula (12), z represents the number of silicon atoms constituting the monoelement ring, and z is preferably 3 or more, more preferably 4 or more, further preferably 5 or more, still preferably 8 or less, and 7 or less. More preferably, 6 or less is further preferable.

The cyclic hydride silane compound is an oxygen-free substance. Therefore, the reduction step is preferably performed in an atmosphere of an inert gas such as nitrogen gas or argon gas.

The cyclic hydrogenated silane compound (G) preferably contains cyclopentasilane or cyclohexasilane, and is more preferably cyclohexasilane.

The content of cyclohexasilane is preferably 97% by mass or more, more preferably 97.5% by mass or more, still more preferably 98.0% by mass or more in 100% by mass of the cyclic hydride silane compound (G). It is preferably 100% by mass or less, but it may be 99.9% by mass or less or 99.7% by mass or less.
The content may be based on the area% obtained from gas chromatographic analysis.

Aluminum complex (H)
The aluminum complex (H) is preferably a salt of the halogenated aluminum compound formed by contacting the halogenated aluminum compound with the solvent (F) (preferably an ether solvent), and the main component is a salt of the halogenated aluminum compound. It is preferable to contain 50% by mass or more (preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more).

3. 3. Step 3 (Step of separating the aluminum complex)
Step 3 is a step of separating the aluminum complex (H).
The step of separating the aluminum complex (H) is at least two of (a) a filtration step, (b) a step of separating a reaction solution, a concentrated solution thereof or a washing solution thereof, and (c) a step of washing with an acidic aqueous solution. More than one.

The filtration step may be filtration performed at normal pressure and temperature, or may be filtration performed at varying pressure or temperature.
Examples of the filtration include natural filtration, vacuum filtration, pressure filtration, centrifugal filtration, hot filtration and the like.
For filtration, filter paper, glass fiber filter, membrane filter, filtration plate and the like can be used.
In the present invention, the filtration step is preferably performed on the upper layer or the lower layer in the reaction solution, the concentrated solution thereof or the cleaning solution thereof, and more preferably performed on the reaction solution, the concentrated solution thereof or the lower layer in the cleaning solution thereof.
In the present invention, the aluminum complex cannot be sufficiently removed only by the filtration step.

The liquid separation may be an operation of extracting or taking out a layer containing a desired substance from a plurality of generated layers, and may be an operation of separating the reaction liquid layer-separated during the reaction, an acidic aqueous solution, water, a solvent or the like. Those that separate the layer separated when washed, those that separate the layer separated by concentration or dilution, temperature change or pressure change, and those that separate the layer by adding an additive that promotes layer separation. It does not matter whether the liquid is separated or the like. The liquid separation is not particularly limited, and for example, the liquid may be separated by a known method, and examples thereof include a liquid separation by a decantation operation and a liquid separation by a funnel.

The reaction solution is a composition containing a cyclic hydride silane compound (G) and an aluminum complex (H), and the concentrated solution is a solution in which the solvent contained in the composition is volatilized by reducing the pressure or heating the composition. The cleaning solution is a solution after contacting the reaction solution or the concentrated solution thereof with the acidic aqueous solution, as will be described later.

The step of washing with an acidic aqueous solution may be an operation of bringing the reaction solution or its concentrated solution into contact with the acidic aqueous solution.
When washing with an acidic aqueous solution, the contact between the reaction solution containing the cyclic hydride silane compound or the concentrated solution thereof and the acidic aqueous solution is at least one of the reaction solution containing the cyclic hydride silane compound or the concentrated solution thereof and the acidic aqueous solution. It is preferable to drop one of them. By dropping one or both of the reaction solution containing the cyclic hydrogenated silane compound or the concentrated solution thereof and the acidic aqueous solution in this way, the metal hydride can be deactivated more mildly as compared with washing with water, and the generated heat generation can be generated. Can be adjusted by the dropping speed and the like.

The following three embodiments are preferable in the case of dropping one or both of the reaction solution containing the cyclic hydrogenated silane compound or the concentrated solution thereof and the acidic aqueous solution. That is, A) a reaction solution containing a cyclic hydrogenated silane compound or a concentrated solution thereof is charged in a reactor, and an acidic aqueous solution is dropped onto the reaction solution, and B) an acidic aqueous solution is charged in the reactor. A mode in which a reaction solution containing a cyclic hydrogenated silane compound or a concentrated solution thereof is dropped, C) a mode in which a reaction solution containing a cyclic hydrogenated silane compound or a concentrated solution thereof and an acidic aqueous solution are dropped simultaneously or sequentially in a reactor. be. Among these, the aspect B) is preferable, that is, it is preferable to drop the reaction solution containing the cyclic hydrogenated silane compound or the concentrated solution thereof into an acidic aqueous solution.
In the present invention, it is preferable to separate the upper layer and the lower layer in the reaction solution or the concentrate thereof by the step of separating the reaction solution or the concentrate thereof.

The acidic aqueous solution may be an aqueous solution of hydrochloric acid, nitric acid, sulfuric acid or the like. A preferred acidic aqueous solution is an aqueous solution of sulfuric acid.
The concentration of the acidic aqueous solution is, for example, 0.1 to 20% by mass, preferably 0.5 to 15% by mass, and more preferably 1 to 10% by mass.

As specific steps for separating the aluminum complex, (i) a filtration step and a reaction solution, a step of separating the concentrated solution or a cleaning solution thereof, (ii) a filtration step and a step of cleaning with an acidic aqueous solution, (iii) a reaction solution. , A step of separating the concentrated solution or its cleaning solution and a step of cleaning with an acidic aqueous solution, (iv) a filtration step, a reaction solution, a step of separating the concentrated solution or its cleaning solution, and a step of cleaning with an acidic aqueous solution. And so on.

Above all, the step of separating the aluminum complex (H) is (a) a reaction solution and a concentrated solution thereof from the viewpoint of safely and easily handling the aluminum complex generated by the reaction between the salt of the cyclic halosilane compound and the halogenated aluminum compound. Alternatively, it is preferable that the steps are a step of separating the cleaning liquids thereof and (b) a filtration step, or (a) a step of separating the reaction liquid, a concentrated liquid thereof or the cleaning liquids thereof, and (c) a step of washing with an acidic aqueous solution. , (A) a step of separating the upper and lower layers formed by the reaction solution, the concentrated solution thereof or their cleaning solution, (b) the step of filtering the obtained lower layer, or (c) the reaction solution or the concentrated solution thereof being acidic. The step of washing with an aqueous solution and (a) the step of separating the upper layer and the lower layer formed by the washed washing liquid are more preferable.
The lower layer obtained by the liquid separation may be subjected to a filtration step, and the filtered lower layer may be combined with the upper layer.

The cyclic hydride silane compound obtained in the above reduction step may be purified in order to increase the purity. As a method for purifying the cyclic hydride compound, known purification methods such as solid-liquid separation, distillation, crystallization, and extraction can be adopted.
Above all, it is preferable to further include distilling the cyclic hydrogenated silane compound after performing the step of separating the aluminum complex.
By separating the aluminum complex and then distilling the cyclic hydride silane compound, a cyclic hydride silane compound having a reduced amount of aluminum can be obtained with high purity.

The solution containing the purified cyclic hydride silane compound is further purified by distillation, but after concentrating the solution containing the cyclic hydride silane compound as necessary, a high concentration of the cyclic hydride silane compound (preferably cyclohexasilane) is obtained. It may be distilled. This distillation is preferably vacuum distillation. The method of distillation under reduced pressure is not particularly limited, and the distillation may be carried out in a known distillation column or under light-shielding conditions. The above distillation is preferably carried out by dividing the fraction into a plurality of fractions, and only an appropriate fraction may be selected from the obtained fractions.

In particular, the distillation (particularly vacuum distillation) may be performed twice or more. For example, a solution containing a cyclic hydride silane compound is distilled under reduced pressure to retain an appropriate content of the cyclic hydride silane compound (particularly cyclohexasilane). After the fraction is recovered (first distillation), the recovered fraction is distilled again under reduced pressure to recover a fraction having an appropriate content of cyclic hydride silane compound (particularly cyclohexasilane) (second distillation), and further required. The operation of repeating the second distillation may be performed according to the above.

The purity of the cyclic hydride silane compound (hereinafter, also referred to as “the cyclic hydride silane compound” of the present disclosure) obtained by the production method of the present disclosure, that is, the cyclic hydrogen in the cyclic hydride compound-containing composition of the present disclosure. The content of the silane compound is preferably 97.5% by mass or more, more preferably 98.0% by mass or more, still more preferably 98.5% by mass in 100% by mass of the cyclic hydride compound (G). % Or more, preferably 100% by mass or less, but may be 99.9% by mass or less or 99.7% by mass or less. Preferably, cyclohexasilane is in the above range.

The concentration of aluminum contained in the cyclic hydrogenated silane compound of the present disclosure or the cyclic hydride compound-containing composition of the present disclosure is preferably 3000 ppm or less, more preferably 2500 ppm or less, still more preferably 2000 ppm or less, still more preferably 1500 ppm or less. It is preferably 0.01 ppb or more.

Although the present invention has been described above, a combination of two or more of the preferred embodiments of the present invention described above is also a preferred embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and the present invention shall be carried out with modifications to the extent that it can be applied to the above and the purposes described below. Of course, they are all possible, and they are all included in the technical scope of the present invention.

Aluminum content measurement analyzer: Multi-type ICP emission spectroscopic analyzer (ICPE-9000 manufactured by Shimadzu Corporation)
The pretreatment was performed by the following procedure. First, in a glove box under a nitrogen atmosphere, 50 μL of a cyclic hydride compound was placed in a PFA (polytetrafluoroethylene) container having a capacity of 100 mL, and then 2500 μL of 12.5% TMAH (hydrotetramethylammonium aqueous solution) was placed. .. The lid was lightly closed and allowed to stand overnight to inactivate it. After standing overnight, the mixture was diluted with 5% HNO ₃₄₅ ml and allowed to stand overnight to complete the pretreatment.
The Al content of the pretreated cyclic hydrogenated silane compound was measured with ICPE-9000 manufactured by Shimadzu Corporation.

Measurement of the content of cyclic hydride silane compound In a glove box under a nitrogen atmosphere, the obtained cyclic hydride silane compound is diluted to about 1% with cyclopentyl methyl ether, and the solution is measured by gas chromatography (GC). did. The content of the cyclic hydride compound was calculated by the area percentage method.
(Gas chromatography (GC) analysis method)
Measurement method: GC FID method Analyzer: GC2014 manufactured by Shimadzu Corporation
Column: DB-5MS 0.25 μm (Film) x 0.25 mm (Diam) x 30 m (Length) (Agilent Technologies)
Vaporization chamber temperature: 250 degrees Detector temperature: 280 degrees Temperature rise condition: 50 degrees for 5 minutes, 20 degrees / minute for 250 degrees, 10 degrees / minute for 280 degrees for 10 minutes

Example 1
(1) Example of Production of Salt (A) of Cyclic Halosilane Compound After replacing the inside of a 300 mL four-necked flask equipped with a thermometer, condenser, dropping funnel and agitator with nitrogen gas, tetraethylammonium bromide 123 is placed in this flask. 5.5 g (0.59 mol), 490.0 g (2.64 mol) of tributylamine and 702.7 g of dichloromethane were added. Then, while stirring the solution in the flask, a solution consisting of 238.1 g (1.76 mol) of trichlorosilane and 117.2 g of dichloromethane was slowly added dropwise from the dropping funnel under 25 ° C. conditions. After completion of the dropping, the mixture was stirred as it was for 2 hours, and then stirred while heating at 50 ° C. for 6 hours to carry out a cyclization coupling reaction. After the reaction, the obtained solid was filtered and purified to obtain 102.7 g of a cyclic halosilane compound salt (A).

(2) Production Example of Cyclic Halosilane Compound (D) Under a nitrogen atmosphere, 15.0 g of the white solid obtained in (1) above and the aluminum chloride compound (B) were placed in a 300 mL three-necked flask equipped with a stirrer. 4.6 g of a certain powdered aluminum chloride (AlCl ₃ ) was added, and 98.7 g of hexane as a solvent (C) was further added. In a light-shielded state, the mixture was stirred and reacted for 3 hours under room temperature conditions, and then filtered and concentrated to obtain a hexane solution (concentration: about 40% by mass) of the cyclic halosilane compound (D).

(3) Production Example of Cyclic Hydrogenated Silane Compound (G) 25 g of the hexane solution of the cyclic halosilane compound (D) obtained in (2) above was placed in a 100 mL three-necked flask equipped with a dropping funnel and a stirrer. .. After replacing the inside of the flask with nitrogen gas, while stirring the solution in the flask, a diethyl ether solution of lithium aluminum hydride (concentration: about 1.0 mol) as a metal hydride (E) from the dropping funnel under the condition of 0 ° C. / L) 76 mL was gradually added dropwise, and then the mixture was stirred at 25 ° C. for 1 hour to carry out a reduction reaction. After the reaction, the reaction solution was separated into two layers by reducing the pressure, and the lower layer contained an aluminum complex (H). This lower layer was separated by liquid separation, concentrated under reduced pressure until the hexane concentration became 5% or less, and then filtered to remove the precipitated aluminum complex (H). The lower layer from which the aluminum complex (H) has been removed is mixed with the upper layer, purified by distillation, and subjected to gas chromatography as a cyclic hydride silane compound (G) with an area purity of 99% and an aluminum concentration of 1300 ppm. 1.6 g was obtained.

Example 2
(3) Production Example of Cyclic Hydrogenated Silane Compound (G) 25 g of the hexane solution of the cyclic halosilane compound (D) obtained in Example 1 (2) above was placed in a 100 mL three-necked flask equipped with a dropping funnel and a stirrer. I put in. After replacing the inside of the flask with nitrogen gas, while stirring the solution in the flask, a diethyl ether solution of lithium aluminum hydride (concentration: about 1.0 mol) as a metal hydride (E) from the dropping funnel under the condition of 0 ° C. / L) 76 mL was gradually added dropwise, and then the mixture was stirred at 25 ° C. for 1 hour to carry out a reduction reaction. After the reaction, the obtained reaction solution was separated into two layers, and the lower layer contained an aluminum complex (H). This two-layer separated solution is slowly added dropwise to a 5% sulfuric acid aqueous solution, and after stirring for 10 minutes, the lower layer of the two-layer separated layer is extracted, the upper layer is distilled and purified, and gas chromatography is performed as a cyclic hydride silane compound (G). Chromatography gave 1.6 g of cyclohexasilane having an area purity of 99% and an aluminum concentration of 160 ppm.

According to the present invention, an aluminum complex formed by a reaction between a salt of a cyclic halosilane compound and an aluminum halide compound can be handled safely and easily. Cyclic hydride silane compounds with a reduced amount of aluminum and high purity are useful as silicon raw materials used in, for example, solar cells and semiconductors. Further, in the semiconductor field, it can be used for the production of SiGe compounds and the production of SiGe films by mixing or reacting with Ge compounds.

Claims (8)

Step 1, in which the salt (A) of the cyclic halosilane compound and the aluminum halide compound (B) are brought into contact with each other in the solvent (C) to produce the cyclic halosilane compound (D).
Step 2 of contacting the cyclic halosilane compound (D) with the metal hydride (E) in the solvent (F) to obtain a composition containing the cyclic hydride silane compound (G) and the aluminum complex (H), and the aluminum. Step 3 to separate the complex (H)
Including
The step of separating the aluminum complex (H) is at least two of (a) a filtration step, (b) a step of separating a reaction solution, a concentrated solution thereof or a washing solution thereof, and (c) a step of washing with an acidic aqueous solution. A method for producing a cyclic hydride silane compound, which comprises one or more. The production method according to claim 1, further comprising distilling the cyclic hydrogenated silane compound (G). The production method according to claim 1 or 2, wherein the molar concentration of the cyclic halosilane compound (D) in the step 2 is 0.150 mol / L or more. The production according to any one of claims 1 to 3, wherein the ratio of the molar concentration of the cyclic halosilane compound (D) in the step 2 to the number of silicon atoms contained in the cyclic halosilane compound (D) is 0.90 mol / L or more. Method. The step of separating the aluminum complex (H) is (a) a step of separating a reaction solution, a concentrated solution thereof or a cleaning solution thereof and (b) a filtration step, or (a) a reaction solution, a concentrated solution thereof or a method thereof. The production method according to any one of claims 1 to 4, which is a step of separating the cleaning liquid and (c) a step of washing with an acidic aqueous solution. The production method according to any one of claims 1 to 5, wherein at least one or more of the solvent (C) and the solvent (F) is an ether solvent. The production method according to any one of claims 1 to 6, wherein the cyclic hydrogenated silane compound (G) contains cyclopentasilane or cyclohexasilane. The production method according to claim 7, wherein the cyclic hydrogenated silane compound (G) is cyclohexasilane.