JPH0480849B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical field] The present invention relates to a compound having the general formula Si _x H _y O _z having at least one Si-H bond or Si-Si bond in the molecule.
(However, x is a positive integer greater than or equal to 1, y and z are positive integers not exceeding 2x+2 and 2x, respectively, and one of them is not 0, and if x=1, z is not 0). The present invention relates to a method for producing silicon hydride represented by the general formula Si _l H _2l+2 (l is a positive integer smaller than x) from a silicon compound. [Background Art] In recent years, with the development of the electronics industry, the demand for silicon for semiconductors such as polycrystalline silicon or amorphous silicon has increased rapidly.
Silicon hydride has recently become more important as a raw material for manufacturing silicon for semiconductors, and demand for silane (SiH ₄ ) and disilane (Si ₂ H ₆ ) in particular is expected to increase significantly in the future as raw materials for semiconductors for solar cells. It is expected. Several methods for producing silicon hydride have been known, among which a method for producing silicon hydride by reacting magnesium silicide with an acid has been known for a long time as a particularly easy and economical method. Mg ₂ Si＋4HClin H ₂ O or lig NH ₃ ――――――――――――――――→ 2MgCl ₂ +1/n Si _o H _2o+2 + (1-1/n) H _2However , this In this method, in addition to SiH ₄ and Si ₂ H ₆ , which have high utility value, a considerable amount of higher silane is produced. For example, when water is used as a solvent, the reaction can be carried out at room temperature and pressure, but Mg ₂ Approximately half of the Si in Si is represented by Si _p H _q O _r (p is a positive integer of 3 or more, q and r are positive integers not exceeding 2p+2 and 2p, respectively, and one of them is not 0). Since it is a silicon compound, it is not economical. Furthermore, it is known that higher silane is produced as a by-product when silicon hydride is produced by reducing silicon halides, for example, 2Si ₂ Cl ₆ +3lAlH ₄ in ether. ---→ When producing Si ₂ H ₆ by the reaction of 3LiCl + AlCl ₃ + 2Si ₂ H ₆ ,
Significant amounts of higher silanes such as Si ₃ H ₈ are produced. On the other hand, it has been reported that high-grade silane Si _n H _2n+2 (m is a positive integer of 2 or more) can be partially converted into SiH ₄ or Si ₂ H ₆ by thermal decomposition or silent discharge. , its conversion to SiH ₄ and Si ₂ H ₆ is low and still insufficient. In view of the above points, the present inventors have conducted extensive studies and found that most of the various silicon compounds produced as by-products in conventional methods are expressed by the general formula Si _x H _y O _z ; has at least one Si-H bond or Si-Si bond in its molecule, and by performing a reaction treatment with a specific substance, the desired SiH ₄ can be produced in high yield.
We discovered that it can be converted into silicon hydrides such as Si 2 H ₆ and Si ₂ H 6 . [Objective of the Invention] The object of the present invention is to solve various silicon compounds (these have _the general formula _Si The object of the present invention is to provide a method for converting O _z ) into economically valuable silicon hydrides such as SiH ₄ and Si ₂ H ₆ in high yields. [Disclosure of the Invention] According to the present invention, at least one Si-
General formula Si _x H _y O _z with H or Si-Si bond
(However, x is a positive integer greater than or equal to 1, y and z are positive integers not exceeding 2x+2 and 2x, respectively,
If either one is not 0 and x=1, then z
= not 0) and the general formula

【formula】

[Formula] R ₈ =N- R ₉ ,

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] R ₂₄ −C≡N, R ₂₅ −N≡N−R ₂₆ or R ₂₇ −
At least one type of chain or cyclic nitrogen-containing organic compound selected from the group represented by N=N (wherein R ₁ to R ₂₇ are a hydrocarbon group having 1 to 20 carbon atoms or hydrogen) By carrying out a catalytic reaction, a method for producing silicon hydride having the general formula Si _l H _2l+2 (where l is a positive integer of 1 or more less than or equal to x) is provided.Hereinafter, the present invention will be explained in detail. The silicon compound used as a raw material in the present invention has the general formula Si _x H _y O _z (where x is a positive integer of 1 or more, y and z are positive integers not exceeding 2x+2 and 2x, respectively, one of which is not 0), and contains at least one Si--H bond or Si--Si bond in the molecule.
Specifically, for example, disilane (Si ₂ H ₆ ), trisilane (Si ₃ H ₈ ), n-tetrasilane (Si ₄ H ₁₀ ), isotetrasilane (Si ₄ H ₁₀ ), cyclohexasilane (Si ₆ H ₁₂ ), polysilene ((-SiH ₂ )- _o , disiloxane (Si ₂ H ₆ O), trisiloxane (Si ₃ H ₈ O ₂ ), tetrasiloxane (Si ₄ H ₁₀ O ₃ ), siloxene ((Si ₂ H ₂ O) _o ) etc. It is also possible to use a mixture of two or more of these, or a mixture thereof. Also, these can be used with a diluent such as ether, hydrocarbon or halogenated hydrocarbon, as described below. Alternatively, it can be used by dissolving or suspending it in an organic solvent, and can be used in any of the gas phase, liquid phase, and solid phase.Also, chain or cyclic nitrogen-containing organic compounds are defined by the general formula

【formula】

[Formula] R ₈ =N- R ₉ ,

【formula】

【formula】

【formula】

【formula】

【formula】

[Preferred form for carrying out the invention]

Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 Concentration 20wt in a separable flask with a capacity of 4
% aqueous hydrochloric acid solution and 300 g of diethyl ether were charged. In a hydrogen gas atmosphere, under conditions where the above mixture was refluxing (reaction concentration 35°C), 60 g of magnesium silicide (particle size 100 to 200 mesh,
782mmol-Si) over 200 minutes with stirring, 0.3
Addition continued at a constant rate of g/min. After the reaction is completed (after the addition of magnesium silicide), the temperature after the reaction is 0°C.
After cooling and standing still, a diethyl ether layer of approximately 0.4
was separated. The acidic aqueous solution in the reactor was heated to 80°C, and a small amount of dissolved diethyl ether was expelled and mixed with the diethyl ether layer separated into two layers. During the reaction, the gas generated during the two-layer separation and heating treatment operations of the acidic aqueous solution was initially −70
It was collected in a trap (trap ()) containing diethyl ether cooled to 0.degree. C., and then in a trap (trap ()) cooled at the temperature of liquid nitrogen. Next, the mixture of the diethyl ether layer after the two-layer separation and the ether in the trap () is distilled in a distillation column with about 3 plates to distill and separate SiH ₄ and Si ₂ H _{6 .} (bp−112℃), Si ₂ H ₆ (bp−14.5
Trap (℃) cooled at liquid nitrogen temperature
Added and collected inside. SiH ₄ , Si ₂ H ₆ , which remained in the trap () and the diethyl ether layer after distillation.
The amounts of Si ₃ H ₈ and Si ₄ H ₁₀ were analyzed and quantified by gas chromatography. The amounts of silanes in the trap () and diethyl ether layers were as shown below.

[Table] Furthermore, colorimetric analysis of the amount of Si in the diethyl ether layer revealed that the content was 324 mmol. In addition, the IR spectrum revealed that the silicon compound contained a considerable amount of Si-O-Si bonds in addition to Si-Si bonds and Si-H bonds. Add diethyl ether to this and diethyl ether solution ()
Got 0.5. The Si concentration in this solution () is 0.653
mmolSiatm/mlsolm, and the concentrations of Si ₃ H ₈ and Si ₄ H ₁₀ are 0.032 mmol/mlsolm. and 0.020 m, respectively.
It was mol/mlsolm. Pour 5.0 ml of dimethylformamide into a reactor with an internal volume of about 50 ml and equipped with a reflux condenser set at -15°C, and then add 10 ml of the above diethyl ether solution () and conduct the reaction at 25°C. Ta. The reaction was carried out with stirring, the atmospheric gas was hydrogen, and the gas produced was collected in a trap cooled at the temperature of liquid nitrogen. After 2 hours, the reaction was stopped, and the amounts of SiH ₄ , Si ₂ H ₄ and Si ₂ H ₆ in the trap were analyzed and quantified by gas chromatography. The amounts of SiH ₄ and Si ₂ H ₆ are 2.04 mmol and 2.04 mmol, respectively.
It was 0.22 mmol, which corresponds to 37.9% of the eigen in diethyl ether used as the reaction solution. Also
The generation ratio of SiH ₄ and Si ₂ H ₆ was (SiH ₄ /Si ₂ H ₆ = 4.64) based on silicon atoms. Examples 2 to 11 In Example 1, diethylamine, triethylamine, tributylamine, aniline, N-methylaniline,
Pyridine, α-picoline, ethylenediamine,
An experiment was carried out in the same manner as in Example 1, except that 5 ml each of N,N-dimethylacetamide and aqueous ammonia (concentration 28 wt%) were used. The results are shown in Table 1. Example 12.13.14 In Example 1, the reaction between magnesium silicide and hydrochloric acid was carried out using tetrahydropyran, dioxane, and tetrafluorodichloride ethane instead of diethyl ether, and solutions of the silicon compounds shown below were respectively prepared. Obtained.

[Table] An experiment was carried out in the same manner as in Example 1, except that 10 ml of the above solution and 5 ml of dimethylformamide were used instead of the diethyl ether solution (2). The results are shown in Table 1. Example 15.16 In Example 1, Si ₃ H ₈ and SiH ₃ OSiH ₂ OSiH ₃ were used instead of the diethyl ether solution ().
The experiment was conducted in the same manner as in Example 1, except that a diethyl ether solution containing 0.224 mmol/mlsolm of each was used. The results are shown in Table 1. Example 17 A cylindrical reactor with an internal volume of approximately 50 ml and equipped with a reflux condenser set at −15°C was charged with 10 ml of dimethylformdehyde, and Si ₃ H ₈ gas diluted with hydrogen gas (concentration 5.5vol%) to 1mmol/hr
The air was blown at a constant rate of 6 hours at room temperature. The generated gas is collected in a trap cooled with liquid nitrogen, and after the reaction is completed, SiH ₄ ,
The amount _{of Si2H6} was quantified. The results are shown in Table 1.

【table】

[Effects and industrial applicability of the invention]

As described above, the present invention uses various methods to convert a part of _the silicon compound represented by the general formula Si _x H _y O _z that is produced as a by-product in the production of silicon hydride such as SiH ₄ and Si ₂ H 6. By contacting with a nitrogen-containing compound, it can be converted into useful SiH ₄ , Si ₂ H ₆ , etc. very easily and with good yield, and it must be said that its industrial applicability is extremely high. Note that the method of the present invention can be applied to conventional SiH ₄ , Si ₂ H ₆
It goes without saying that by applying the present invention to a silicon hydride production process such as the above, the economic efficiency of the process itself is greatly improved.

Claims (1)

[Claims] 1. General formula Si _x H _y O _z (where x
is a positive integer greater than or equal to 1, and y and z are each 2x
+2, a positive integer not exceeding 2x, one of which is not 0, and if x = 1, z is not 0) and the general formula [Formula] [Formula] R ₈ = N- R ₉ , [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] R ₂₄ − C≡N, R ₂₅ −N=N−R ₂₆ or R ₂₇ −N≡N (in the formula
R ₁ to R ₂₇ are a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, or hydrogen. According to
A method for producing silicon hydride represented by the general formula Si _l H _2l+2 (where l is a positive integer smaller than x). 2 Silicon compounds (Si _x H _y O _z ) have the general formula Si _x H _2x+2
(x is a positive integer of 2 or more). 3 Silicon hydride Si _l H _2l+2 is SiH ₄ or Si ₂ H ₆
The method according to claim 1. 4. The method according to claim 1, wherein the silicon compound is dissolved in an organic solvent.