KR102267838B1 - Apparatus for manufacturing a nanostructure of silicon compound - Google Patents

Abstract

A first vacuum chamber, a carrier positioned in the first vacuum chamber and having solid silicon supported in the pores of a porous material, a heater for applying heat to the carrier, and silicon for moving the vaporized silicon gas from the carrier by the heat a raw material supply unit including a gas injection module; a second vacuum chamber into which one side of the silicon gas injection module is inserted to receive silicon gas; a reaction gas injection unit supplying a reaction gas into the second vacuum chamber; and a collecting unit for collecting the silicon compound generated by the reaction of the reaction gas and the silicon gas.

Description

Apparatus for manufacturing a nanostructure of silicon compound

The present invention relates to an apparatus for manufacturing a silicon compound nanostructure, and to an apparatus for manufacturing a silicon compound nanostructure capable of mass-producing a high-purity silicon compound by making a reaction rate between a reaction gas and a silicon gas constant.

Silicon is used as a variety of materials in the semiconductor display field, and a silicon compound depending on the reacting material is also widely used in various fields.

For example, silicon oxide has been recently studied as a material for anodes of lithium ion batteries. As a negative electrode of a lithium ion battery, a carbon electrode having excellent charging and discharging efficiency of the battery is generally used, and has a battery capacity of about 375 mAh/g. However, since the carbon electrode is limited to be used as a negative electrode material for a next-generation lithium ion battery that requires a gradually increasing battery capacity, a silicon nanostructure or a silicon oxide nanostructure is being studied as a material to replace the carbon electrode. As a manufacturing technology for silicon oxide nanostructures, a technology for manufacturing silicon oxide as an anode material by forming a _{Si-SiO x} /C core-shell structure, a technology for improving battery life by diversifying the oxygen content and particle size of _{SiO x,} A technique for forming a Si/SiO _x composite by forming a _{thin amorphous SiO x} sheath using a silicon nanowire is being developed.

In addition, since silicon carbide has excellent chemical resistance, oxidation resistance, heat resistance, and abrasion resistance, it is widely used in various fields such as reinforced composite materials, new aerospace materials, high-temperature reactive materials, and tools for semiconductor manufacturing processes. In general, silicon carbide can be prepared by applying a chemical vapor reaction using a liquid source such as _{CH 3} SiCl ₃ , (CH ₃ ) ₂ SiCl ₃ , (CH ₃ ) ₃ SiCl, SiCl ₄ as a source of silicon and carbon. have. It vaporizes the liquid source by bubbling it with a carrier gas such as hydrogen gas, supplies a mixture of the vaporized source and carrier gas to the vacuum chamber, and measures and controls the supply ratio, flow rate, temperature and pressure of the fluid, etc. It is a method that requires many accessories. In addition, since the sources themselves are toxic, handling is very difficult, and separate equipment such as a scrubber is required for the treatment of HCl, which is a by-product of the reaction, and there is a risk of equipment corrosion and environmental pollution.

Therefore, the silicon compound is a material with a wide range of applications and applications in modern industrial fields, but in the manufacturing method of the silicon compound as described above, the process process is complicated, the process control is difficult, and it undergoes a high-cost process, and the environment It is necessary to develop technology to solve the above problems because the problem of

Korean Patent Registration No. 10-0493960 (Registration Date: 2005. 05. 30.) Korean Patent Registration No. 10-1400883 (Registration Date: 2014. 05. 22.)

An object of the present invention is to provide an apparatus for manufacturing a silicon compound nanostructure capable of improving process control by simplifying the process compared to the prior art.

In addition, another technical problem to be achieved by the present invention is to provide an apparatus for manufacturing a silicon compound nanostructure capable of mass-producing a high-purity silicon compound by making a constant reaction rate between a reaction gas and a silicon gas.

The object of the present invention is not limited to the object mentioned above, and other objects not mentioned will be clearly understood by those of ordinary skill in the art to which the present invention belongs from the following description.

In order to solve the above problems, the present invention provides a first vacuum chamber, a carrier located in the first vacuum chamber and having solid silicon supported in the pores of a porous material, a heater for applying heat to the carrier, and the carrier by the heat A raw material supply unit including a silicon gas injection module for moving the vaporized silicon gas from the; a second vacuum chamber into which one side of the silicon gas injection module is inserted to receive silicon gas; a reaction gas injection unit supplying a reaction gas into the second vacuum chamber; and a collecting unit configured to collect a silicon compound generated by the reaction of the reaction gas and the silicon gas.

The carrier may be one in which solid silicon is supported in pores of a porous material having a pore diameter of 0.05 to 1 mm.

The porous material may be graphite, aluminum nitride, or silicon carbide.

The heater may apply heat to the carrier in a temperature range of 1200 to 2000°C.

The apparatus for manufacturing the silicon compound nanostructure may include a carrier gas injection unit positioned at an upper portion spaced apart from the silicon gas injection module and the reaction gas injection unit to inject a carrier gas into the second vacuum chamber.

The reaction gas may be one or more mixed gases selected from argon, hydrogen, oxygen, and water vapor.

The silicon gas injection module includes a water-cooling insulator that blocks heat provided from the heater, a silicon gas injection line, and a water-cooling nozzle penetrating through the inside of the water-cooling insulator and cooling the outer circumferential surface of the silicon gas injection line. A nozzle cartridge may be provided.

The raw material supply unit may combine and replace the water cooling nozzle cartridge.

The collecting unit may include an inlet through which the silicon compound gas is introduced, and a collecting chamber in which the silicon compound gas passing through the inlet is cooled and condensed to form a silicon compound nanostructure.

The collection unit may include a filter installed inside the collection chamber to collect the silicon nanostructure, and a heat exchange means having a heat circulation tube in contact with the filter and through which a heat medium or refrigerant moves.

The filter may have a stacked structure, and the heat circulation tube may be interposed between the stacked filters so that a heat medium or a refrigerant may move between the filters.

The heat exchange means may include a heat exchanger connected to the reaction gas injection unit to supply energy for changing the state of the reaction gas.

The silicon compound nanostructure may have a mixed structure of nanoparticles or nanowires.

The apparatus for manufacturing a silicon compound nanostructure according to an embodiment of the present invention has the advantage of improving process control by simplifying the process compared to the prior art.

In addition, there is an advantage in that a high-purity silicon compound can be mass-produced by making the reaction rate of the reaction gas and the silicon gas constant.

1 is a cross-sectional view showing an apparatus for manufacturing a silicon compound nanostructure according to an embodiment of the present invention;
2 is a cross-sectional view showing the structure of a carrier of a raw material supply unit according to an embodiment of the present invention;
3 and 4 are cross-sectional views showing the structure of a collecting unit according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The embodiments introduced below are provided as examples so that the spirit of the present invention can be sufficiently conveyed to those skilled in the art. Accordingly, the present invention is not limited to the embodiments described below and may be embodied in other forms. In addition, in the drawings, the length, thickness, etc. of layers and regions may be exaggerated for convenience. Like reference numerals refer to like elements throughout.

1 is a cross-sectional view showing an apparatus for manufacturing a silicon compound nanostructure according to an embodiment of the present invention, FIG. 2 is a cross-sectional view showing the structure of a carrier of a raw material supply unit according to an embodiment of the present invention, and FIGS. 3 and 4 are It is a cross-sectional view showing the structure of the collecting unit according to an embodiment of the present invention.

1 to 4, the apparatus for manufacturing a silicon compound nanostructure according to an embodiment of the present invention includes a raw material supply unit 100 including a first vacuum chamber 110, a second vacuum chamber 200, and It may include a reactive gas spraying unit 300 and a collecting unit 500 .

The second vacuum chamber 200 provides a closed space for manufacturing the silicon compound nanostructure 23s, and the inside of the second vacuum chamber 200 is constant for manufacturing the silicon compound nanostructure 23s of high purity. It is desirable to maintain the degree of vacuum. For example, the vacuum degree of the second vacuum chamber 200 may be ^{10 -2} to 10 ^{-7 Torr.}

The raw material supply unit 100 for supplying the silicon gas to the second vacuum chamber 200 is located in the first vacuum chamber 110 and the first vacuum chamber 110 and solid silicon in the pores of the porous material 21 . A carrier 20 on which 22 is supported, a heater 120 for applying heat to the carrier 20, and a silicon gas injection module for moving the vaporized silicon gas from the carrier 20 by the heat can Accordingly, by applying heat to the carrier 20 , the solid silicon 22 supported in the pores of the porous material 21 may be vaporized and moved into the second vacuum chamber 200 .

That is, after the solid silicon 22 is supported in the pores of the carrier 20 , heat is applied to melt the silicon in the pores, and silicon gas may be formed through vaporization. For the support of silicon on the carrier 20, silicon in which silicon is previously supported in the carrier may be used, and solid silicon is first supported in the carrier due to high temperature during the vaporization of solid silicon, and then evaporated so that silicon gas is emitted. . To this end, the carrier is placed in a container made of a material that is stable even at the temperature at which it is vaporized, and the solid silicon may be loaded on the carrier of the porous material 21 .

When the solid silicon 22 exists in the pores of the porous material 21 and the temperature in the first vacuum chamber 110 rises, it may change into microdroplets of the same size as the pores and evaporate as the temperature rises. Even if the silicon supported in the carrier 20 is melted, the silicon gas can be efficiently supplied by evaporating in a state where the surface area is maximized.

Therefore, solid silicon is melted only in the pores of the porous material 21, and silicon is vaporized and emitted into the first vacuum chamber 110 uniformly and sequentially only through the pores, so that the silicon gas is constantly supplied to the second vacuum chamber ( 200) to maintain the gas pressure at a certain level. In addition, since the silicon gas is supplied into the second vacuum chamber 200 at a certain level, and finally a reaction with the reaction gas can be made at a constant rate, the time or the amount of reaction during which the silicon compound nanostructures 23s are generated is controlled. can do.

The carrier 20 may include a porous material 21 having a pore diameter (a) of 0.05 to 1 mm in order to effectively supply silicon gas for a reaction time with the reaction gas. As the size of the pores is smaller, the silicon gas may be evenly dissipated, but if the pores are too small, the dissipation may not be efficient, and if the size of the pores is too large, the effect of supporting the silicon gas on the carrier cannot be obtained. Furthermore, it is preferable that the porosity of the carrier 20 is 10 to 60%. If the porosity is too small, the amount of silicon that can be supported on the carrier decreases, so efficient diffusion may be difficult, and if the porosity is too large, the durability of the carrier is reduced. There is a problem with degradation.

In addition, in order to effectively supply the silicon gas, the heater 120 may apply heat to the carrier 20 in a temperature range of 1200 to 2000°C. Silicon has a melting point of 1414° C. and a boiling point of 3265° C. at room temperature, but when the pressure is lowered as in the inside of the first vacuum chamber 110, the boiling point may be significantly lowered. Therefore, in the case of heat treatment in a temperature range of 1200 to 2000° C. in a vacuum state, solid silicon evaporates into a gas through a liquid state, effectively supplying the silicon gas into the first vacuum chamber 110 and the second vacuum chamber 200. can In addition, in order to minimize the loss of heat provided from the heater 110 in the raw material supply unit 100 , the inside of the first vacuum chamber 110 may include a heat insulating material 130 .

The porous material 21 may be made of graphite, aluminum nitride, or silicon carbide, which is stable without chemical reaction in the above temperature range to minimize the influence on the formation of the silicon compound nanostructure 23s.

One side of the silicon gas injection module provided in the raw material supply unit 100 may be inserted into the second vacuum chamber 200 to provide silicon gas. In addition, the silicon gas injection module may include a water-cooling nozzle cartridge (C), the water-cooling nozzle cartridge (C) is a water-cooling insulator 140 for blocking the heat provided from the heater 120, and silicon gas injection It may include a line 150 and a water cooling nozzle (not shown) penetrating the inside of the water cooling insulating material 140 and cooling the outer peripheral surface of the silicon gas injection line 150 . Therefore, by controlling the temperature of the outer peripheral surface of the silicon gas injection line 150, the nozzle of the silicon gas injection line 150 can be prevented from being clogged, and the temperature of the silicon gas moving into the second vacuum chamber 200 is controlled. As a result, the reaction gas and the reaction for forming the silicon nanostructure can be made more efficiently. Furthermore, the water-cooled nozzle cartridge (C) is provided with a chamber coupling hole 160 on the outer surface of the raw material supply unit 100, a silicon gas injection line passing between the first vacuum chamber 110 and the second vacuum chamber 200. (150) can be supported more firmly.

The silicon gas injection line 150 may include one or more, so that the injection amount of the silicon gas may be adjusted according to the amount of the reaction gas provided or the reaction rate.

In addition, the raw material supply unit 100 may combine and replace the water cooling nozzle cartridge (C). Therefore, even if the silicon gas injection line 150 is aged, it is possible to further increase the lifetime of the silicon compound nanostructure manufacturing apparatus by replacing and combining the water cooling nozzle cartridge (C), thereby helping to reduce the process cost.

The reaction gas injection unit 300 for supplying the reaction gas into the second vacuum chamber 200 may be provided at a position corresponding to the silicon gas injection line 150 of the raw material supply unit 100 . The reaction gas may be one or more mixed gases selected from argon, hydrogen, oxygen, and water vapor, and the silicon compound nanostructures 23s produced at this time may be made of silicon oxide.

In addition, when the reaction gas contains carbon, the silicon compound nanostructure 23s generated at this time may be made of silicon carbide. For example, it may be selected from materials capable of reacting as a precursor to form silicon carbide. These materials are generally selected from materials containing silicon and materials containing carbon, such as silane or chlorosilane, and may contain components capable of forming into silicon carbide.

The apparatus for manufacturing the silicon compound nanostructure is located at an upper portion spaced apart from the silicon gas injection module and the reaction gas injection unit 300 to inject a carrier gas into the second vacuum chamber 200 , the carrier gas injection unit 400 . ) may be included.

The carrier gas injection unit 400 may inject the carrier gas into the upper portions of the silicon gas injection line 150 and the reaction gas injection unit 300 of the silicon gas injection module in order to increase the reaction rate between the silicon gas and the reaction gas. . That is, the carrier gas may be injected to increase the reaction rate or movement speed of the silicon compound gas 23g generated by the reaction of the reaction gas and the vaporized silicon gas. Therefore, the carrier gas may not participate in the chemical reaction of the silicon gas and the reaction gas, but may be injected for the purpose of increasing the reaction rate or movement rate, and argon or hydrogen gas may be used as the carrier gas.

The collection unit 500 for collecting the silicon compound generated by the reaction of the reaction gas and the silicon gas may be located above the carrier gas injection unit 400 . The collecting unit 500 includes an inlet 520 through which the silicon compound gas 23g is introduced, and the silicon compound gas 23g passing through the inlet 520 is cooled and condensed to form a silicon compound nanostructure 23s. The chamber 510 may be formed.

The collecting unit 500 includes a filter 550 installed inside the collecting chamber 510 to collect the silicon nanostructures 23s, and a heat circulation pipe 560 in contact with the filter 550 and through which a heat medium or refrigerant moves. ) may include a heat exchange means having a.

That is, the silicon compound gas 23g is formed due to the silicon gas and the reaction gas vaporized in the carrier 20 , and the silicon compound gas 23g may move to the inlet 520 due to the carrier gas. Thereafter, the silicon compound gas 23g moved into the collection chamber 510 through the collection chamber inlet line 525 is cooled by the filter 550 having the thermal circulation tube 560, and the silicon compound nanostructure 23s ) can be aggregated and collected. The silicon compound nanostructure 23s may have a mixed structure of nanoparticles or nanowires.

The vacuum pump 540 provided in the collecting unit 500 may stop the operation of the vacuum pump when a predetermined amount of the silicon compound nanostructure 23s is collected. At this time, the pressure inside the collection chamber 510 is temporarily increased, and the silicon compound nanostructures 23s are gathered in the lower part of the collection chamber 510 by gravity, or constant air is injected by the vacuum pump 540 to filter the filter. 550 By applying an outward pressure, the silicon compound nanostructures 23s collected in the filter 550 may be collected in the lower portion of the collection chamber 510 . In addition, the silicon compound nanostructure 23s may be obtained by opening the collecting port provided in the lower portion of the collecting chamber 510 .

That is, in order to obtain the collected silicon compound nanostructures 23s, the collection chamber 510 may include a collecting port and a collecting port opening/closing plate 510a on one side or a lower portion. Furthermore, in order to prevent air from flowing back into the second vacuum chamber 200 through the collection chamber inlet line 525 when the vacuum pump 540 is stopped, one end of the collection chamber inlet line 525 is A backflow prevention opening/closing plate 525a may be provided.

That is, the vacuum pump 540 is operated while the silicon compound gas 23g is introduced and the silicon compound nanostructure 23s is collected in the filter 550, and the backflow prevention opening/closing plate 525a is connected to the collection chamber inlet line 525 ) and the collecting port opening/closing plate 510a may close the collecting port. After that, while the silicon compound nanostructure 23s collected in the filter 550 is obtained to the outside, the vacuum pump 540 is stopped or air is injected into the collection chamber 510, and the backflow prevention opening/closing plate 525a) closes the collecting chamber inlet line 525, and the collecting port opening/closing plate 510a may open the collecting port.

Furthermore, the filter 550 has a stacked structure, and the heat circulation tube 560 is interposed between the stacked filters so that a heat medium or a refrigerant can move between the filters. The filter 550 is stacked, for example, in the form of a non-woven fabric/metal mesh, a metal powder sintered body/glass fiber/metal mesh, or a metal mesh with large pores/metal mesh with medium pores/metal mesh with small pores, etc. It may be laminated.

Therefore, by increasing the contact area between the heat circulation tube 560 and the filter 550, heat exchange efficiency between the heat circulation tube 560 and the filter 550 can be increased, and the filter 550 is made of a metallic material. In this case, the heat circulation tube 560 and the filter 550 may be fixedly coupled using welding.

When the heat circulation tube 560 is located on the front surface of the filter 550, the silicon compound nanostructure 23s is attached to the surface of the heat circulation tube 560 or between the heat circulation tube 560 and the filter to achieve heat exchange efficiency. This can be reduced, and since there may be difficulty in cleaning, the heat circulation tube 560 is preferably interposed in the rear surface of the filter 550 or inside the filter 550 .

In addition, the heat exchange means may include a heat control unit 570 connected to the heat circulation pipe 560 to control the temperature of the filter 550 . Accordingly, heat exchange between the filter 560 and the heat circulation tube 560 may be performed regularly by adjusting the heat control unit 570 , or may be performed during the time input to the heat control unit 570 , and the heat control unit 570 . Therefore, the temperature of the filter 550 can also be controlled.

Furthermore, the heat exchange means may include a heat exchanger that is connected to the reaction gas injection unit 300 to supply some energy for a change in the state of the reaction gas. Therefore, by helping the heat supplied by the thermal circulation pipe to supply heat of vaporization for gas generation of the reactive gas injection unit 300 , energy loss can be minimized and process costs can be reduced.

As described above, the apparatus for manufacturing a silicon compound nanostructure according to an embodiment of the present invention uses a solid silicon-supported carrier as a raw material supply unit and controls the amount of silicon gas that reacts according to the heat applied to the process process than in the prior art. It has the advantage of improving process control by simplifying the process. In addition, there is an advantage in that it is possible to mass-produce high-purity silicon compound nanostructures by making the reaction rate of the reaction gas and the silicon gas constant.

Although the above has been described with reference to preferred embodiments of the present invention, those skilled in the art can variously modify and change the present invention within the scope without departing from the spirit and scope of the present invention as set forth in the claims below. You will understand that it can be done.

20; carrier
21; porous material
22; solid silicon
23 g; silicon compound gas
23s; Silicon compound nanostructure
100; Raw material supply department
110; 1st vacuum chamber
C; Water Cooling Nozzle Cartridge
200; second vacuum chamber
300; Reaction gas injection part
400; carrier gas injection unit
500; collection unit
510; collection chamber
520; inlet
540; vacuum pump
550; filter
560; heat circulation tube
570; heat control unit

Claims (13)

A first vacuum chamber, a carrier positioned in the first vacuum chamber and having solid silicon supported in the pores of a porous material, a heater for applying heat to the carrier, and silicon for moving the vaporized silicon gas from the carrier by the heat a raw material supply unit including a gas injection module;
a second vacuum chamber into which one side of the silicon gas injection module is inserted to receive silicon gas;
a reaction gas injection unit supplying a reaction gas into the second vacuum chamber; and
Including; a collecting unit for collecting the silicon compound generated by the reaction of the reaction gas and the silicon gas;
The silicon gas injection module includes a water-cooling insulator that blocks heat provided from the heater, a silicon gas injection line, and a water-cooling nozzle penetrating through the inside of the water-cooling insulator and cooling the outer circumferential surface of the silicon gas injection line. An apparatus for manufacturing a silicon compound nanostructure comprising a nozzle cartridge.
The method of claim 1,
The carrier is an apparatus for manufacturing a silicon compound nanostructure, characterized in that solid silicon is supported in the pores of a porous material having a pore diameter of 0.05 to 1 mm.
3. The method of claim 2,
The porous material is an apparatus for manufacturing a silicon compound nanostructure, characterized in that graphite, aluminum nitride or silicon carbide.
The method of claim 1,
The heater is an apparatus for manufacturing a silicon compound nanostructure, characterized in that for applying heat to the carrier in a temperature range of 1200 to 2000 ℃.
The method of claim 1,
The silicon compound nano-structure manufacturing apparatus, the silicon gas injection module and the silicon compound characterized in that it comprises a carrier gas injection unit located in the upper spaced apart from the reaction gas injection unit to inject the carrier gas into the second vacuum chamber. An apparatus for manufacturing a nanostructure.
The method of claim 1,
The reaction gas is an apparatus for manufacturing a silicon compound nanostructure, characterized in that at least one mixed gas selected from argon, hydrogen, oxygen, and water vapor.
delete The method of claim 1,
The raw material supply unit, a silicon compound nanostructure manufacturing apparatus, characterized in that it is possible to combine and replace the water cooling nozzle cartridge.
The method of claim 1,
The collection unit comprises an inlet through which the silicon compound gas flows, and a collection chamber in which the silicon compound gas passing through the inlet is cooled and condensed to form a silicon compound nanostructure.
10. The method of claim 9,
The collecting unit includes a filter installed inside the collecting chamber to collect the silicon nanostructure, and a heat exchange means having a heat circulation tube in contact with the filter and through which a heat medium or a refrigerant moves. manufacturing equipment.
11. The method of claim 10,
The filter has a stacked structure, and the heat circulation tube is interposed between the stacked filters so that a heating medium or a refrigerant moves between the filters.
11. The method of claim 10,
The heat exchange means, the device for manufacturing a silicon compound nanostructure, characterized in that it comprises a heat exchanger connected to the reaction gas injection unit to supply energy for a change in the state of the reaction gas.
The method of claim 1,
The silicon compound nanostructure is an apparatus for manufacturing a silicon nanostructure, characterized in that it has a mixed structure of nanoparticles or nanowires.

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