WO2012157871A2

WO2012157871A2 - Plasma hydrogenation apparatus

Info

Publication number: WO2012157871A2
Application number: PCT/KR2012/003476
Authority: WO
Inventors: 홍용철; 이봉주; 신동훈
Original assignee: (주)그린사이언스
Priority date: 2011-05-18
Filing date: 2012-05-03
Publication date: 2012-11-22
Also published as: KR101329750B1; WO2012157871A3; KR20130027616A

Abstract

Disclosed is a plasma hydrogenation apparatus. According to one embodiment of the present invention, the plasma hydrogenation apparatus comprises: an electromagnetic wave supply portion for oscillating electromagnetic waves of preset frequency; a discharge tube for generating plasma from the electromagnetic waves supplied from the electromagnetic wave supply portion and a hydrogen gas or a mixture gas containing hydrogen; a gas supply portion for volutedly injecting the hydrogen gas or the mixture gas containing hydrogen into the discharge tube; a reactant supply portion for supplying a Si-Cl-based compound to the plasma generated inside the discharge tube; a reactor in which a Si-H-Cl-based compound is generated through the reaction of hydrogen atoms or ions dissociated by the generated plasma and the Si-Cl-based compound; and a product discharge portion for discharging the Si-H-Cl-based compound generated at the reactor.

Description

Plasma hydrogenation reactor

The present invention relates to a hydrogenation technique using plasma.

In recent years, as energy consumption soars and fossil fuels are gradually exhausted around the world, attention has been focused on solar energy as a sustainable energy source. In addition, in order to convert solar light into electrical energy, a solar cell substrate is required, and demand for polycrystalline silicon, which is a raw material of the solar cell substrate, is rapidly increasing.

In order to manufacture the poly-silicon as a raw material SiH-Cl compound _{_{(SiH x Cl y; x +}} y = 4; 0≤x, y≤4) is required and, in general, of the trichlorosilane (Trichloro-silane SiHCl ₃ ) or monosilane (SiH ₄ ) is used.

Conventionally, a large amount of silicon tetrachloride (SiCl ₄ ) is generated to produce the Si-H-Cl-based compound, and hydrogenation of the generated silicon tetrachloride with trichlorosilane is common. However, such a process using a conventional hydrogenation reaction requires a high pressure, the conversion yield is very low, about 20% or less, there was a difficulty in efficiently producing Si-H-Cl-based compounds such as trichlorosilane. In addition, the supply of polysilicon, which is a raw material of the solar cell substrate, is also very insufficient, which has been the biggest obstacle to the rapid development of solar power.

The present invention aims to produce Si-H-Cl based compounds economically and efficiently using plasma.

Plasma hydrogenation apparatus according to an embodiment of the present invention for solving the above problems, the electromagnetic wave supply unit for generating an electromagnetic wave of a predetermined frequency; A discharge tube in which a plasma is generated from the electromagnetic wave supplied from the electromagnetic wave supply unit and a mixed gas including hydrogen gas or hydrogen; A gas supply unit for injecting the hydrogen gas or the mixed gas including hydrogen into the discharge tube in a vortex form; A reactant supply unit supplying a Si-Cl based compound to the plasma generated inside the discharge tube; A reaction furnace in which a Si—H—Cl based compound is produced by a reaction between a hydrogen atom or a hydrogen ion dissociated by the generated plasma and the Si—Cl based compound; And a product discharge part for discharging the Si-H-Cl-based compound generated in the reactor.

In addition, the plasma hydrogenation reaction apparatus according to another embodiment of the present invention for solving the above problems, an electromagnetic wave supply unit for generating an electromagnetic wave of a predetermined frequency; A discharge tube in which a plasma is generated from the electromagnetic wave supplied from the electromagnetic wave supply unit and a mixed gas including hydrogen gas or hydrogen; A gas and reactant supply unit for injecting a gaseous Si-Cl-based compound in a vortex form together with the hydrogen gas or the mixed gas including hydrogen into the discharge tube; A reaction furnace in which a Si—H—Cl based compound is produced by a reaction between a hydrogen atom or a hydrogen ion dissociated by the generated plasma and the Si—Cl based compound; And a gas discharge part for discharging the Si-H-Cl-based compound generated in the reactor.

According to embodiments of the present invention it is possible to produce a large amount of hydrogen-related species, in particular Si-H-Cl-based compounds using a plasma hydrogenation reaction. In addition, since the plasma hydrogenation reaction is generated in a high temperature region of 3000K to 5000K or more, the efficiency of compound generation can be improved, and since the plasma of the present invention is generated in an atmosphere of 1 atmosphere, there is an advantage that the size and control of the plasma gasifier can be facilitated.

1 is a block diagram of a plasma hydrogenation apparatus 100 according to a first embodiment of the present invention.

2 is a block diagram of a plasma hydrogenation apparatus 200 according to a second embodiment of the present invention.

3 and 4 are vertical cross-sectional views showing a portion where the waveguide 112 and the discharge tube 114 are connected to the plasma

hydrogenation reaction apparatus

100 or 200 according to the present invention.

5A to 5C are horizontal cross-sectional views showing the detailed configuration of the gas supply unit 116 of the plasma hydrogenation reaction apparatus 100 according to an embodiment of the present invention.

6A and 6B are horizontal cross-sectional views illustrating detailed configurations of the reactant supply unit 118 of the plasma hydrogenation reaction apparatus 100 according to an embodiment of the present invention.

7 is a graph showing the degree of dissociation and ionization of hydrogen atoms with temperature.

Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. However, this is only an example and the present invention is not limited thereto.

In describing the present invention, when it is determined that the detailed description of the known technology related to the present invention may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted. In addition, terms to be described below are terms defined in consideration of functions in the present invention, which may vary according to the intention or custom of a user or an operator. Therefore, the definition should be made based on the contents throughout the specification.

The technical spirit of the present invention is determined by the claims, and the following embodiments are merely means for efficiently explaining the technical spirit of the present invention to those skilled in the art.

As shown, the plasma hydrogenation reaction apparatus 100 includes a power supply unit 102, an electromagnetic wave oscillator 104, a circulator 106, a directional coupler 108, a tuner 110, a waveguide 112, a discharge tube 114, The gas supply unit 116, the reactant supply unit 118, the reactor 120, and the product discharge unit 122 may be further included. The product separation unit 124 may be further included as necessary.

The power supply unit 102 supplies power required for driving the plasma hydrogenation reaction apparatus 100.

The electromagnetic wave oscillator 104 is connected to the power supply unit 102 and receives electric power from the power supply unit 102 to oscillate electromagnetic waves. In the present invention, an electromagnetic wave oscillator (magnetron) of commercial frequency is used, for example, an electromagnetic wave oscillator having a frequency of 2.45 GHz, or an electromagnetic wave having a frequency range of 902 to 928 MHz (915 MHz magnetron) or 886 to 896 MHz (896 MHz magnetron). An electromagnetic wave oscillator can be used.

The circulator 106 is connected to the electromagnetic wave oscillator 104, and outputs the electromagnetic wave oscillated by the electromagnetic wave oscillator 104, and simultaneously dissipates electromagnetic energy reflected by impedance mismatch to protect the electromagnetic wave oscillator 104.

The directional coupler 108 outputs electromagnetic waves transmitted through the circulator 106, and at the same time monitors the intensity of the incident wave and the reflected wave.

The tuner 110 adjusts the intensity of the incident wave and the reflected wave of the electromagnetic wave output from the directional coupler 108 to induce impedance matching so that the electric field induced by the electromagnetic wave is maximized in the discharge tube 114.

The waveguide 112 transmits electromagnetic waves input from the tuner 110 to the discharge tube 114.

As shown, the power supply unit 102, the electromagnetic wave oscillator 104, the circulator 106, the directional coupler 108, the tuner 110 and the waveguide 112 described above constitute the electromagnetic wave supply unit 126 in the present invention. The electromagnetic wave supply unit 126 generates electromagnetic waves and supplies them to the discharge tube 114.

The discharge tube 114 generates a plasma from the electromagnetic wave and the mixed gas containing hydrogen gas or hydrogen supplied from the electromagnetic wave supply unit 126, and the hydrogen (H) contained in the hydrogen gas or the mixed gas using the generated plasma. ₂ ) dissociates to generate hydrogen (H) in the atomic state or to generate hydrogen ions, and reacts the generated hydrogen atoms or hydrogen ions with the Si-Cl-based compound to generate a Si-H-Cl-based compound. Si-Cl-based compound which is a reactant in the present invention may be, for example, SiCl ₄ or SiCl ₂ and the like, Si-H-Cl-based compounds generated therefrom may be SiHCl ₃ or SiH ₂ Cl ₂ and the like.

As described above, the hydrogen gas or the mixed gas containing hydrogen injected into the discharge tube 114 stabilizes the generated plasma and forms a swirl in the discharge tube 114 to form an inner wall of the discharge tube 114 from a high temperature plasma flame. Will protect. In addition, hydrogen contained in the hydrogen gas or the mixed gas is reacted with the Si-Cl-based compound in the plasma to generate a Si-H-Cl-based compound. The mixed gas may be formed by mixing hydrogen with an inert gas containing at least one of argon, helium, or nitrogen.

The gas supply unit 116 injects hydrogen gas or a mixed gas containing hydrogen into the discharge tube 114 in a vortex form, and the reactant supply unit 118 supplies the Si-Cl-based compound to the plasma generated inside the discharge tube 114. do.

Reactor 120 is formed in a cylindrical shape is provided on the top of the discharge tube 114, between the hydrogen atoms or hydrogen ions dissociated by the generated plasma and the Si-Cl-based compound supplied from the reactant supply unit 118 It is a space where a Si-H-Cl-based compound is produced by the reaction. Detailed configurations of the gas supply unit 116, the reactant supply unit 118, and the reactor 120 will be described later.

The product discharge part 122 discharges the Si-H-Cl based compound generated by the plasma to the outside.

Meanwhile, as described above, the plasma hydrogenation apparatus 100 according to the present exemplary embodiment may further include a product separation unit 124. The product separator 124 separates impurities from the Si-H-Cl-based compound discharged from the product outlet 122 to discharge only pure Si-H-Cl-based compounds and reuses the separated impurities. . Product The product discharged from the discharging part 122 to the gas state, trichlorosilane (TCS, SiHCl ₃₎ in addition to Si-H-Cl based compounds, etc., the hydrogen gas supplied from the gas supply 116 or reactant supply 118 to The mixed gas, part of the Si-Cl-based compound remaining unreacted, and other impurities are included together. The product separation unit 124 removes impurities and the like from these products to purify only pure Si-H-Cl based compounds. In addition, the unreacted Si-Cl-based compound of the separated impurities in the reactor 120 is supplied to the reactant supply unit 118, the hydrogen gas or mixed gas containing hydrogen is supplied to the gas supply unit 116 to react Re-injection into the furnace 120 increases the reuse rate of the raw materials and at the same time reduces the manufacturing cost of the Si-H-Cl-based compound.

2 is a block diagram of a plasma hydrogenation apparatus 200 according to a second embodiment of the present invention. In the illustrated embodiment, the components represented by the same reference numerals as those of FIG. 1 are configured to substantially perform the same functions as the first embodiment, and thus redundant descriptions thereof will be omitted.

In the present embodiment, the gas supply unit 116 and the reactant supply unit 118 are not separated from each other, and the gas and reactant supply unit 202 is included instead of the first embodiment. The gas and reactant supply unit 202 is formed at the lower end of the discharge tube 114 to supply hydrogen gas or mixed gas and Si-Cl compound of the gas form in a swirl form to the discharge tube 114. It is composed.

On the other hand, the plasma hydrogenation reaction apparatus 200 according to the present embodiment may further comprise a separate product separation unit 204. The product separator 204 separates impurities from the Si-H-Cl-based compound discharged from the product outlet 122 to discharge only pure Si-H-Cl-based compounds, and reuses the separated impurities. . As described above, the product discharged in the gaseous state from the product discharge unit 122 includes hydrogen gas supplied from the gas and the reactant supply unit 202 in addition to Si-H-Cl-based compounds such as trichlorosilane (TCS, SiHCl ₃ ). To a portion of the mixed gas or the remaining Si-Cl-based compound that is not reacted, and other impurities are included. The product separation unit 204 removes impurities and the like from these products to purify only pure Si-H-Cl based compounds. In addition, the unreacted Si-Cl-based compound, hydrogen gas, or a mixed gas containing hydrogen in the reactor 120 among the impurities is supplied to the gas and the reactant supply unit 202 to be re-introduced into the reactor 120. Injecting increases the reuse rate of raw materials and at the same time reduces the manufacturing cost of Si-H-Cl based compounds.

hydrogenation reaction apparatus

100 or 200 according to the present invention.

As shown, the discharge tube 114 is connected to the waveguide 112 to provide a space 300 in which the plasma is generated by the electromagnetic waves input through the waveguide 112. The discharge tube 114 is formed in a cylindrical shape to vertically align the waveguide 112 at a point corresponding to 1/8 to 1/2 of the wavelength in the waveguide 112, preferably 1/4, from the end of the waveguide 112. It may be installed to penetrate, and may be made of quartz, alumina, or ceramic for easy transmission of electromagnetic waves. The discharge tube supporter 302 formed to surround the waveguide 112 at the outer surface of the waveguide 112 supports the discharge tube 114 such that the discharge tube 114 is stably inserted into the waveguide 112 and fixed.

The reactor 120 is formed on the upper end of the discharge tube 114, and is formed in a cylindrical shape having the same diameter as the discharge tube 114.

The gas supply unit 116 is formed at the lower end of the discharge tube 114, and the reactant supply unit 118 is formed at the lower end of the reactor 120 as shown in FIG. 3 or the discharge tube 114 as shown in FIG. 4. It may be formed at the lower end of the). In addition, when the hydrogen gas or the mixed gas and the Si-Cl-based compound in the form of gas are injected together as in Example 2, the gas supply unit 116 of FIGS. 3 and 4 serves as the gas and reactant supply unit 202. In this case, a separate reactant supply unit 118 may be omitted. Therefore, the description of the gas supply unit 116 of the first embodiment is applicable to the gas and reactant supply unit 202 of the second embodiment as it is not otherwise mentioned in the following description.

As shown, the gas supply unit 116 of the plasma hydrogenation reaction apparatus 100 according to an embodiment of the present invention includes one or more gas supply pipe 400. Each of the gas supply pipes 400 is configured to supply hydrogen gas or a mixed gas containing hydrogen into the discharge tube 114, one end of which is connected to the inside of the discharge tube 114.

The gas supply pipe 400 may be formed in an appropriate number inside the gas supply unit 116 as necessary. 4A illustrates an embodiment in which two gas supply pipes 400 are formed, and FIGS. 4B and 4C illustrate embodiments in which four and six gas supply pipes 400 are formed, respectively. The gas supply pipe 400 may be arranged at equal intervals around the discharge pipe 114 in the gas supply part 116.

The gas supply pipe 400 is supplied to the discharge tube 114 such that the supplied hydrogen gas or mixed gas rotates in a swirl form along the inner circumferential surface of the discharge tube 114. To this end, as shown, the gas supply pipe 400 may be configured such that hydrogen gas or mixed gas discharged into the discharge tube 114 is discharged along the inner circumferential surface of the discharge tube 114 (ie, parallel to the inner circumferential surface). It is connected to the inside. To this end, the gas supply pipe 400 is configured so that the advancing direction of the gas supply pipe 400 and the parallel to the inner peripheral surface of the discharge pipe 114 in the vicinity of one end connected to the discharge pipe (114). In this case, the supplied hydrogen gas or the mixed gas rotates in one direction in the discharge tube 114 to have a vortex shape.

As shown, the reactant supply unit 118 of the plasma hydrogenation reaction apparatus 100 according to an embodiment of the present invention includes one or more reactant supply tubes 500, and the discharge tube 114 and the reactant supply tubes 500. Si-Cl-based compound is supplied to the plasma formed inside the reactor (120).

The reactant supply pipe 500 may also be formed in an appropriate number inside the reactant supply unit 118 as necessary. Like the gas supply pipe 400, the reactant supply pipe 500 may also be formed in the reactant supply unit 118. It can be arranged at equal intervals around.

In one embodiment, the reactant supply pipe 500 may be supplied to the reactor 120 so that the supplied Si-Cl compound rotates in a vortex form along the inner circumferential surface of the reactor 120. To this end, as shown in FIG. 6A, the reactant supply pipe 500 discharges Si-Cl based compounds discharged into the reactor 120 along the inner circumferential surface of the reactor 120 (ie, parallel to the inner circumferential surface). Is connected to the inside of the reactor 120 so as to. To this end, like the gas supply pipe 400, the reactant supply pipe 500 should also be configured such that the advancing direction of the reactant supply pipe 500 is parallel to the inner circumferential surface of the reactor 120 near one end connected to the reactor 120. In this case, the supplied Si-Cl-based compound rotates in one direction inside the reactor 120 to have a swirl shape. At this time, the rotation direction of the vortex preferably corresponds to the rotation direction of hydrogen gas or mixed gas.

In another embodiment shown in FIG. 6B, the reactant supply pipe 500 may be formed to face the center of the plasma formed inside the discharge pipe 114. In this case, since the Si-Cl-based compound ejected through the reactant supply pipe 500 is directly injected toward the center of the plasma having a high temperature, the reaction of the Si-Cl-based compound may occur more easily.

Hereinafter, the reaction in the reactor 120 and the reactor 120 will be described.

The reactor 120 is provided above the discharge tube 114, and is a space where plasma-hydrogenation reaction occurs by plasma formed in the discharge tube 114. The plasma hydrogenation reaction is a concept that is distinguished from the general hydrogenation reaction, whereas the hydrogenation reaction generally means a chemical reaction between molecular hydrogen (H ₂ ) and a compound or element in the presence of a catalyst, Means chemical reaction with dissociated hydrogen atoms or hydrogen ions in a chemically highly reactive plasma.

In order to dissociate or ionize the hydrogen molecules as described above, the hydrogen molecules should be heated as shown in a graph of the relationship between dissociation degree and ionization degree according to the temperature of FIG. 7. It is very difficult to dissociate hydrogen. Accordingly, the present invention is configured to easily dissociate hydrogen molecules by using plasma, and to generate Si-H-Cl-based compounds from Si-Cl-based compounds.

As can be seen in FIG. 7, hydrogen molecules begin to dissociate at 2000K and almost all hydrogen molecules dissociate when the temperature reaches about 7000K (0.23 at 3500K, 0.45 at 4000K, 0.75 at 4500K, 0.75 at 5000K). 0.9). In addition, the slope of dissociation degree is greatest between 3000 and 5000K, and the number of highly reactive hydrogen atoms is rapidly increased. Therefore, in the present invention, the temperature of the space in which the plasma inside the reactor 120 is formed is configured to maintain a temperature between 3000K and 5000K, and if necessary, is provided with heat insulating means surrounding the inner circumferential surface of the reactor 120 or By providing at least one of the heat transfer means for maintaining the temperature inside the reactor 120 in the above range by receiving an external power source to ensure that the inside of the reactor 120 maintains the optimum temperature. On the other hand, in view of the above dissociation degree, if SiCl ₄ is injected into the reaction material to obtain SiHCl ₃ , that is,

H ₂ + SiCl _4- > SiHCl ₃ + HCl

When the reaction occurs, the optimum molar ratios of hydrogen and SiCl ₄ to temperatures 3500K, 4000K, 4500K and 5000K are 5: 1, 2.2: 1, 1.3: 1 and 1.1: 1, respectively.

The generation mechanism of the Si-H-Cl-based compound generated in the reactor 120 by the plasma is as follows.

H _2- > 2H

H _2- > H ₂ ⁺ + e

H. + SiCl _4- > SiCl _3. + HCl

SiCl ₃ ㆍ + H ·-> SiHCl ₃

_{_{SiCl 4 + e -> SiCl 2}} + Cl 2 -

SiCl ₂ + H _2- > SiH ₂ Cl ₂

SiCl ₂ + H-> SiH ₂ Cl ₂

SiCl ₂ + H--> SiCl

SiCl + H--> Si + HCl

H ₂ ⁺ + Cl ₂ --> 2HCl

According to the above-described configuration, the present invention can produce a large amount of hydrogen-related species, especially Si-H-Cl-based compounds using the plasma hydrogenation reaction. In addition, it is possible to use the high temperature region of more than 3000K to 5000K by using the plasma to increase the efficiency of compound generation, and since the plasma of the present invention is generated in an atmosphere of 1 atm, there is an advantage that the size and control of the plasma gasifier can be facilitated. .

Although the present invention has been described in detail with reference to exemplary embodiments above, those skilled in the art to which the present invention pertains can make various modifications to the above-described embodiments without departing from the scope of the present invention. Will understand.

Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined by the claims below and equivalents thereof.

[Description of the code]

100, 200: plasma hydrogenation reaction device

102: power supply unit 104: electromagnetic wave oscillator

106: circulator 108: directional coupler

110: tuner 112: waveguide

114: discharge tube 116: gas supply unit

118: reactant supply 120: reactor

122: product outlet 124, 204: product separator

202: gas and reactant supply unit 300: plasma generation space

302: discharge tube support

Claims

An electromagnetic wave supply unit oscillating an electromagnetic wave of a preset frequency;

A discharge tube in which a plasma is generated from the electromagnetic wave supplied from the electromagnetic wave supply unit and a mixed gas including hydrogen gas or hydrogen;

A gas supply unit for injecting the hydrogen gas or the mixed gas including hydrogen into the discharge tube in a vortex form;

A reactant supply unit supplying a Si-Cl based compound to the plasma generated inside the discharge tube;

A reaction furnace in which a Si—H—Cl based compound is produced by a reaction between a hydrogen atom or a hydrogen ion dissociated by the generated plasma and the Si—Cl based compound; And

Plasma hydrogenation apparatus comprising a product outlet for discharging the Si-H-Cl-based compound produced in the reactor.
The method of claim 1,

The electromagnetic wave oscillated by the electromagnetic wave supply unit has a frequency range of 2.45 GHz, 902 to 928 MHz or 886 to 896 MHz.
The method of claim 1,

The mixed gas is configured by mixing hydrogen with an inert gas containing at least one of argon, helium, or nitrogen, plasma hydrogenation reaction apparatus.
The method according to claim 1 or 3,

The gas supply unit, at least one gas supply pipe formed in the lower end of the discharge tube for supplying the hydrogen gas or the mixed gas into the discharge tube, plasma hydrogenation apparatus.
The method of claim 4, wherein

The one or more gas supply pipes may be connected to an inside of the discharge tube so that the hydrogen gas or the mixed gas supplied into the discharge tube is discharged in parallel with the inner circumferential surface of the discharge tube, thereby supplying the hydrogen gas supplied into the discharge tube. And the mixed gas is configured to form a swirl in the discharge tube.
The method of claim 1,

The reactant supply unit, at least one reactant supply pipe is formed in the lower end of the reactor to supply the Si-Cl-based compound into the reactor, plasma hydrogenation reactor.
The method of claim 6,

The one or more reactant supply tubes are formed such that one end connected to the inside of the reactor faces the center of the plasma formed inside the reactor, such that the Si-Cl compound supplied through the reactant supply tubes is the central portion of the plasma. A plasma hydrogenation reaction device, configured to be ejected toward.
The method of claim 6,

The one or more reactant supply pipes are connected to the inside of the reactor so that the Si-Cl-based compound supplied into the reactor is discharged in parallel with the inner circumferential surface of the reactor, thereby supplying the inside of the reactor. The Si-Cl-based compound is configured to form a swirl in the interior of the reactor, the plasma hydrogenation reaction apparatus.
The method of claim 8,

The at least one reactant supply pipe is configured to form a vortex in the same direction as the hydrogen gas or the mixed gas supplied from the gas supply unit Si-Cl-based compound discharged, the plasma hydrogenation reaction apparatus.
The method of claim 1,

The reactant supply unit, at least one of the reactant supply tube is formed in the lower end of the discharge tube for supplying the Si-Cl-based compound into the discharge tube, plasma hydrogenation apparatus.
The method of claim 1,

The reactor includes at least one of thermal insulation means or heat transfer means surrounding the inner circumferential surface of the reactor so that the inner space in which the plasma is formed maintains a temperature between 3000K and 5000K.
The method of claim 1,

The plasma hydrogenation reaction apparatus further comprises a product separation unit for separating impurities from the Si-H-Cl-based compound discharged from the product discharge unit to discharge only pure Si-H-Cl-based compound.
The method of claim 12,

The product separation unit, the unreacted Si-Cl compound of the separated impurities in the reactor to supply the reactant supply unit, the hydrogen gas or a mixed gas containing hydrogen to the gas supply unit, plasma hydrogenation reaction Device.
An electromagnetic wave supply unit oscillating an electromagnetic wave of a preset frequency;

A discharge tube in which a plasma is generated from the electromagnetic wave supplied from the electromagnetic wave supply unit and a mixed gas including hydrogen gas or hydrogen;

A gas and reactant supply unit for injecting a gaseous Si-Cl-based compound in a vortex form together with the hydrogen gas or the mixed gas including hydrogen into the discharge tube;

A reaction furnace in which a Si—H—Cl based compound is produced by a reaction between a hydrogen atom or a hydrogen ion dissociated by the generated plasma and the Si—Cl based compound; And

Plasma hydrogenation apparatus comprising a gas discharge for discharging the Si-H-Cl-based compound generated in the reactor.
The method of claim 14,

The electromagnetic wave oscillated by the electromagnetic wave supply unit has a frequency range of 2.45 GHz, 902 to 928 MHz or 886 to 896 MHz.
The method of claim 14,

The mixed gas is configured by mixing hydrogen with an inert gas containing at least one of argon, helium, or nitrogen, plasma hydrogenation reaction apparatus.
The method according to claim 14 or 16,

The gas and reactant supply unit includes a plasma and at least one gas and reactant supply tube formed at a lower end of the discharge tube to supply the hydrogen gas or the mixed gas and the Si-Cl based compound in the form of gas into the discharge tube. Hydrogenation reactor.
The method of claim 17,

The one or more gas and reactant supply tubes are connected to the inside of the discharge tube such that the hydrogen gas or the mixed gas and the Si-Cl compound in the form of the gas supplied into the discharge tube are discharged in parallel with the inner circumferential surface of the discharge tube. And the hydrogen gas or the mixed gas supplied to the inside of the discharge tube and the Si-Cl based compound in the gas form form a swirl in the inside of the discharge tube.
The method of claim 14,

The reactor includes at least one of thermal insulation means or heat transfer means surrounding the inner circumferential surface of the reactor so that the inner space in which the plasma is formed maintains a temperature between 3000K and 5000K.
The method of claim 14,

The plasma hydrogenation reaction apparatus further comprises a product separation unit for separating impurities from the Si-H-Cl-based compound discharged from the product discharge unit to discharge only pure Si-H-Cl-based compound.
The method of claim 20,

The product separation unit, the plasma hydrogenation apparatus for supplying a mixed gas containing an unreacted Si-Cl compound and hydrogen gas or hydrogen in the reaction furnace of the separated impurities to the gas and reactant supply unit.