TW200902442A - Reactor for producing silicon material for solar cell - Google Patents

Abstract

This invention provides a reactor for producing a silicon material for a solar cell, which can produce a silicon material for a solar cell at low cost in a continuous manner. Silicon having a diameter of several tens of micrometers to several hundreds of micrometers is continuously produced by a zinc reduction reaction of silicon tetrachloride with gasified silicon tetrachloride and gasified zinc. A reacting furnace (1) comprises a reaction chamber (2) and an output chamber (3) for withdrawing the produced silicon. A number of holes for supplying zinc is provided on a bottom plate (6) in a reaction chamber (2). Silicon tetrachloride is supplied into the reaction chamber (2) through an introduction pipe (21a) which stands up from the bottom plate (6). Further, a silicon seed, together with a carrier gas, is supplied into the reaction chamber (2) to promote the precipitation of granular silicon.

Description

200902442 IX. Description of the invention: [Ming jin 彳 彳 好 好 好 好 好 好 好 好 好 好 ^ 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明The present invention relates to a reaction apparatus for continuously producing a granular solar cell by using a fluidized layer of zinc to continuously vaporize a solar cell using a crucible of germanium and zinc. C. Precursor Background||Inventive Background 1 The raw materials for solar cells are mainly made of tantalum raw materials. In recent years, due to the expansion of the solar cell market, the price of raw materials for solar cells has skyrocketed. For the global environment, solar cells must be used at low cost. Popularization, from this point of view, the price increase will be a big problem. The manufacturing apparatus for producing niobium raw materials has disclosed various principles. For example, the method of manufacturing the raw material is widely used as a method generally called the open hearth method, and in the open hearth method, the purity is 11 to nine. In other words, 99 999999999% of high-purity semiconductors are used for the production of Shixia raw materials by the open-hearth method, and by-products such as ruthenium tetrachloride are produced. It is produced by re-melting the polycrystalline silicon for the semiconductor produced by the open-hearth method using the polycrystalline material for the semiconductor produced by the open-cell method, and the re-melting of the single crystal spinning or the like produced by the method. However, the open hearth method is used. The production of Shixi raw materials for solar cells has not kept pace with the expansion of the solar cell market, and the production has its limits, and it has caused an absolute shortage in the raw material market. Recently, in this case, the use of metallurgy, zinc reduction, etc. 5 200902442 2 (four), however, the Lai metallurgical method of Taishi Xi raw materials need purity of six nine to seven nine, that is, 99.9999%: on, quality Qualitative 'large amount of equipment investment or energy 4 in mass production, there are still many problems.吝 即 即 即 即 相 锌 锌 锌 锌 # # # # 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料In addition, the SiCl4_ is supplied from the elongated reaction to the 1st, and the seed crystal of the Shixi is supplied from the opposite end to generate the crushed particles. The inventors of the present invention have also developed a production of a stone-like material for a solar cell using a zinc reduction method, and a zinc reduction method is conventionally used to produce a needle-like or sheet-like stone material in a reaction furnace (Patent Document 1) And the patent document 2), however, the production of the solar cell material for the solar cell using the methods such as the gold-based method or the zinc reduction method is due to the difficulty of mass production or the difficulty in achieving cost reduction, etc. Knowing that it has not reached practical use. Non-Patent Document 1: Final Report on the Evaluation of Low-Cost, Product-Specific Chemical Processes (Phase I and Phase II) (Times starting from January 9th, D75, and July 9th, 1978) Project, Betley Columbus Lab dedicated to the California Institute of Technology Jet Propulsion Laboratory, July 9, 1978, 20 (FINAL REPORT (covering the period October 9, 1975, to

July 9, 1978) on EVALUATION OF SELECTED CHEMICAL PROCESS FOR PRODUCTION OF LOW - COST SILICON(phase I and II), Silicon material Task Low-cost Solar Array Project, to JEP PROPULSION LABORATORY, 200902442 CALIFORNIA INSTITUTE OF TECHNOLOGY from BATTELLE Columbus Laboratories, In the above-mentioned open hearth method, the object of the invention is to solve the problem to be solved by the invention in the open hearth method. It will produce by-products such as antimony tetrachloride, and the cost of its treatment is 'further'. Because of the open-furnace hydrogen reduction method, the number of equipment and procedures will increase due to the use of hydrogen. Slowness, so it is impossible to avoid the cost increase. For these reasons, it is not easy to achieve cost reduction in the production of the Shixia raw material by the flat furnace method, and at least there is a limit to the production method for mass production of the raw material for the solar cell. The production of tantalum raw materials for solar cells using the metallurgical method must improve the quality stability of the product, and must also improve the energy efficiency of the production line. Furthermore, since it is necessary to have large-scale equipment for mass production, it requires a large amount of money' Accordingly, the production of tantalum raw materials for solar cells using metallurgical methods has many unresolved problems and has not yet reached practical use. Moreover, the production of the raw material for the solar cell using the zinc reduction method is batch-produced, and therefore has the problem of continuous production without the 20-step method, and the non-patent document 1 is produced by the zinc reduction method using the fluidized layer. Not practical. The present invention is based on the foregoing technical background and achieves the following objects. SUMMARY OF THE INVENTION An object of the present invention is to provide a reaction apparatus for continuously producing a raw material for a solar cell for producing a raw material for a solar cell. 7 200902442 ... Another object of the present invention is to provide a reaction skirt for continuously manufacturing a solar cell material for a solar cell by means of a granular or powder form. Means for Solving the Problems In order to achieve the above object, the present invention adopts the following method. 5 tree _ related - then the reaction device is cut by the tetrachloropyre reduction method, and the above-mentioned four gas cut zinc reduction method uses the weathered four gas fossils and the already vaporized zinc, and at the same time A reaction device for producing a raw material for a solar cell. The reaction device for manufacturing the solar energy raw material for solar cells of the present invention is used for manufacturing a stone eve reaction device by using a four-gas fossil sulphate reduction method, and the above-mentioned four gasification fossils are used for gasification. The fourth gasification fossils have been gasified, and the reaction furnace of the above-mentioned reaction device is in the above-mentioned tetrachloride stone which has been gasified in the above-mentioned reaction furnace, so that the above-mentioned remarks and carrier gas are vaporized. The bottom of the reaction furnace is ejected to form a fluidized bed, and the zinc is subjected to a reduction reaction with the first 15 hafnium tetrachloride in the fluid layer, and a granular stone having a diameter of several to several mm is continuously produced. The reaction furnace for producing a reaction device for a raw material for a solar cell according to the present invention comprises: a reaction chamber for reacting the zinc with the antimony tetrachloride in the flow layer; and a take-out chamber The lower portion of the reaction chamber is used to take out the defects generated in the aforementioned reduction reaction and dropped by gravity. A plurality of zinc vapor supply ports for supplying the zinc are provided on the bottom plate of the reaction chamber, and the reaction chamber has an introduction tube for supplying ruthenium tetrachloride which is supplied from the bottom plate. Further, the take-out chamber is provided at the bottom of the reaction furnace and is connected to the reaction chamber of 20200902442, and the take-out chamber includes a third extraction chamber which is placed in the above-mentioned one which falls from the reaction chamber; and The second take-out chamber is for lowering the temperature of the crucible dropped from the first chamber of the A by gravity to a low temperature and taking it out. An introduction tube for a carrier gas provided with a carrier gas in the take-out chamber; and an exhaust pipe for chlorination, unreacted, unreacted tetrachloride, and a carrier gas which are generated simultaneously with the pulverization in the reaction. . In the reaction, zinc chloride formed at the same time as the ruthenium, unreacted ruthenium tetrachloride, and unreacted zinc are separated in a vapor state and discharged from the exhaust pipe. The zinc gas and the ruthenium tetrachloride which have been gasified can be used as a carrier gas 10, and the vaporized zinc is supplied from a through-hole which is disposed in the entire surface of the bottom plate of the reaction chamber, and is supplied and filled in the reaction furnace. The bottom plate has a plurality of through holes or gaps, and the generated turns are dropped from the take-out pipe or the plurality of through holes and/or the gaps provided on the bottom plate to the take-out chamber. The reactor is made of quartz or carbon stone ceramic material, and a plurality of heaters can be arranged on the side wall of the reaction chamber to control the temperature under the optimal conditions of the reaction, and form a plurality in the longitudinal direction of the reaction chamber. Temperature zone. The complex temperature zone is 75 (TC to 1200 ° C temperature zone, the complex temperature zone can be set to different temperature zones of 750 ° C to 1200 ° C, respectively, however, the flow temperature of the reduction reaction is preferably about 900 ° C to Η温度°C is temperature controlled by 20. The material of the first extraction chamber can be made of ceramic material such as quartz or carbon carbide, and the first extraction chamber can be temperature controlled at 70 (TC to 1000 ° C, Further, the low temperature of the second take-out chamber is normal temperature. The second take-out chamber may have a carry-out mechanism for carrying out the generated crucible, and a metal core (heating line) capable of being energized inside the reaction chamber may be provided. Borrowing 9 200902442 to promote the temperature control to be higher than the enthalpy on the metal core of the furnace wall, increase the space occupation rate in the reaction chamber and improve the reaction rate of the reaction. It is preferable to have an introduction tube inside the reaction chamber, and the introduction tube A seed crystal for supplying a carrier gas and a diameter of /zm, and a carrier gas and a seed crystal are supplied from the inlet 5 to the flow layer of the reduction reaction. The seed crystal is grown as a core. And promote the formation of granular mites, The introduction pipe can also be used as the introduction pipe for the carrier gas. In order to prevent air from being mixed into the reaction chamber and to prevent the heat insulation effect of the reaction chamber from being lowered, the bottoms of the first extraction chamber and the second extraction chamber can be separated by a gate. If the drop 10 falls from the reaction chamber to the first take-out chamber and reaches a predetermined amount, the shutter will open and fall to the second take-out chamber. In the second take-out chamber, it is preferable to provide an inert carrier gas introduction tube. And a discharge pipe for discharging the inert carrier gas and the unreacted gas contained in the crucible dropped from the first extraction chamber. If 15 discharges the reaction gas accordingly, The shutter of the second take-out chamber is opened and the crucible is supplied to the transport program. The constituent elements constituting the present invention will be specifically described below. The specific reaction device for manufacturing the raw material for solar cells of the present invention should be provided with a separator for separating the crucible. The separator separates the crucible from the gas discharged from the reaction furnace, and the separator separates the micro-sized crucible from the gas discharged from the reaction furnace. Further, the separator is preferably separated by centrifugal force. The cyclone separator, and the crucible separated from the separator can be directly recovered, but it is preferably supplied to the reactor. Further, a heating mechanism can be disposed on the side wall of the separator to set the temperature in the separator. Temperature control, or a heating mechanism for heating the separator and the reaction 10 200902442 to both, to control the temperature of the separator and the inside of the reaction chamber. The heating mechanism can set the separator and the reaction chamber to For example, in a cylindrical heater, the heating mechanism is preferably configured to arrange a plurality of temperature zones in the longitudinal direction (vertical direction) of the reaction chamber, and is free to control the temperature of each of the aforementioned temperature zones. Based on the nose, the mechanism of the formation of cockroaches is studied. The mechanism for the formation of cockroaches in the reaction can be considered as follows. The formation of cockroaches is basically based on the growth of worm crystals with the core of Shixia crystal as the core. The crystal system plays the role of the Shiyue seed crystal, and the produced Shishijing seed crystal grows in the reaction chamber at 10° to grow and maintain its growth, and the crystal growth system is based on the product. Flow rate and concentration. 15 Fig. 7 is a schematic diagram showing the outline of private growth. The phase of the seed crystal produced by the phase is from several nm to several tens of nm, and the seed crystals generated in the initial stage will grow and form hundreds of nm to 1 In addition, the seed crystals of hundreds of nm to 1 m will grow to form tens of meters #m to hundreds of mm. β m and then 20 Figure 8 shows the pattern of broken crystal growth, the vertical axis of Figure 8 (4) gas concentration Csi (g), the horizontal axis of the chart shows the growth of the crystal The size, specifically, the half of the initial crushed seeds (four) set (four), the half of the Shi Xi particles (four) is set to R, the first I in the reaction chamber at the beginning of the reduction reaction will generate the Shixia seed crystal 'at this point in time, The concentration of Qian Mo's ear is roughly the same, and the weight is zero. In addition, the Shixia crystal seed is taken as the core and the crystal growth is carried out, and the Shi Xi ^ particles are generated. At this time, the heart species and the material core are roughly spherical, and the 7 series are from the half of the 11 200902442 R. Continue to grow to a radius r. As the Shixi particle grows, the concentration of Moxi's Moer will gradually increase. However, when the 矽 particle constitutes a predetermined size, the molar concentration Cs^ will no longer rise, which means saturated Ear concentration (Cs_). That is, the four gasification 矽 矽 辞 并 并 并 并 并 并 并 并 并 Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si . The inflow velocity of Wei si (g) generated by the reaction of four gas cuts with zinc and the balance of the velocity of solid helium Si (8) formed by helium Si (g) are saturated state, and the saturated molar concentration of the saturated state (: (4) The rate of formation of helium si(g) at a specific temperature and pressure is the inverse of the solid 矽Si(s) formed by self-helium Si(g) (attached to strontium and/or strontium particles) The speed) reaches the apparent balance state. The crystal growth can be modeled by the following formula: [Expression 1] R〇\ PmR0 ..... Test 1) 15 At this time 'R〇[m] The radius of the early Shiyue seed crystals, the radius of the product of the insect crystal growth, the molar density of the system, the diffusion coefficient of the Dti^xs-1 system, the retention time of the t system, Cs II 2〇1 XnT3xs—the molar concentration of the Ί system. Lg is dependent on the formula 'g crystal growth system; the band is m, the initial radius of the crystal seed, the radius R〇, the molar density, the diffusion coefficient D, and the graph of Fig. 9 shows the numerical simulation according to formula 1. As a result, the vertical axis of the graph represents the radius of 矽, and the horizontal axis of the graph reflects the surface _, and the _ table shows the tendency of the particle money. Effect of the Invention 12 200902442 According to the present invention, the following effects can be obtained. According to the present invention, the raw material of the solar cell for the solar cell using the fluidized layer zinc reduction method is continuously produced, and therefore, the production of the solar cell for the solar cell using the batch-type reduction method can be compared with In the case of a small number of units, the number of reactors can be efficiently produced, and the number of reactors can be reduced and the amount of equipment investment can be drastically reduced. Moreover, in the production of the Shixia raw material for a solar cell using the fluidized layer zinc reduction method of the present invention, it is possible to easily automate the extraction of the raw materials produced from the reactor, thereby greatly reducing the manufacturing cost of the raw material of the tantalum raw material. Moreover, the result of reducing the investment amount of such equipment and the manufacturing cost, and having the effect of greatly reducing the cost of the solar battery which is currently the biggest problem, contributes to the mass production and mass production of solar cells, and as a result, There is a significant contribution to the prevention of global warming. 'There is another'. Since the present invention can separate and reuse the small stones that are exhausted together with the exhaust gas, resources can be saved. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a reaction furnace according to a first embodiment of the present invention. Fig. 2 is a schematic flow chart showing the continuous manufacturing (矽 manufacturing equipment) of the crucible using the fluidized layer zinc reduction method. Fig. 3 is a schematic view showing an electrolysis program. 20 帛 4 is a reaction furnace according to a second embodiment of the present invention! 〇! Overview of the map. Fig. 5 is a schematic view showing a bottom plate 106 of a reactor 1〇1 according to a second embodiment of the present invention. Fig. 6 is a schematic view showing a configuration of a reaction furnace 1〇1 according to a second embodiment of the present invention. Figure 7 is a schematic representation of the reaction chamber. The state of the celestial crystal growth of the inner stone eve crystals. Figure 9 is a graph showing numerical simulation results according to Equation 1. Fig. 10 is a photograph of a raw material produced by each of the conditions A to c of Table 2 of Example 1, (4) when the condition is A, and when the condition is b, the 10th (c) is the condition C. 10 Fig. 11 is a graph showing the results of a sample sampled from condition B of Fig. 10 by x-ray analysis. Fig. 12 is a graph showing the results of analyzing the sample masses sampled from the _ condition B. EMBODIMENT OF THE INVENTION The first embodiment of the present invention is shown in the first embodiment of the present invention. FIG. 1 is a schematic view showing a reaction furnace 1 according to an i-th embodiment of the present invention, and a reverse layer (10) fluidized layer type. The reaction of the reduction reaction is carried out in a reaction furnace 'reaction furnace for refining the vaporized (4) and the silicon tetrachloride (SiCU) by a fluidized bed method and continuously forming a granular slave device' and the reaction furnace m is located The reaction 20 chamber 2 in the upper portion of the reaction furnace and the extraction chamber 3 located in the lower portion are constructed. The details of the reaction furnace, the configuration, and the function are described later, as will be described later. Fig. 2 is a schematic flow chart showing the continuous manufacturing (矽 manufacturing equipment) using the fluidized layer zinc reduction method. First, according to the fluidized layer zinc reduction method, a series of procedures for the manufacturing equipment of the crucible is explained, and then the detailed description is given. Implementation of the reaction furnace of the form of 200902442. Briefly, the continuous production system using the fluidized layer zinc reduction method is composed of a material supply program 10, a chlorination program 15, a distillation purification program 2, a reduction program 3, an electrolysis program 4, and a transfer program 5, The outline of each program is explained below. 5 [Material supply program] The material supply program 10 is a program for supplying metal bismuth (Si) of a material. The 矽 (Si) of the material is a metal yttrium having a purity of 97% to 99%, and the material supply program 10 is a material. The metal crucible is supplied to the chlorination procedure 15, and the material supply program 10 also supplies chlorine (Clz) gas to the chlorination procedure 15, and zinc (Zn) gas (not shown) is supplied to the reduction procedure 1030. Chlorine ((3⁄4) gas, zinc (Zn) gas is basically recycled in addition to the amount of reduction due to leakage, etc. [chlorination procedure] Chlorination procedure 15 is used to make materials The procedure for the formation of ruthenium tetrachloride (SiCl4) by the metal ruthenium (Si) and the gas (Ci2) gas is 15 and the reaction is represented by the following chemical formula. [Formula 2] Liquid-like gasification 矽The temperature is about 59 art boiling, and the ruthenium tetrachloride formed in the chlorination process 20 15 is supplied to the distillation refining process 20 in a gaseous state, because the reaction machine for performing the chlorination process is known as a reaction machine. Therefore, the description of the gas used in the chlorination process 15 is in principle recirculated by the chlorine gas generated in the electrolysis process 40. In this example, the material supplied to the gasification process 15 is 矽purity. 97% 15 200902442 ~99% of the gold, the gold material may not necessarily be powder, "In order to effectively carry out the gasification of the metal stone, it is suitable to supply to the gasification process 15 in the state of the powder. This embodiment The reaction furnace (10) is continuously manufactured by using the fluid layer type reduction method. The metal material has a purity of six nine to seven nine, that is, 5 99.9999% of the quality of Shi Xi. [Distillation refining procedure] steaming hall refining 2 〇彳 (4) to make gas and / or (four) tetrachloride eve (sicu) The steaming ship is used as a procedure for making a liquid. In the steaming system (4) 2 (), the liquid tetrachlorocene which is discharged from the reduction program 30 is supplied, and it is not possible to distill the liquid tetrachloride in the steaming station. The fossil eve is also supplied to the steaming furnace refining program 2, and the steaming method and apparatus for purifying the refining program 20 are known, and the steaming refining program 20 is not particularly special, and the known technique can be used. 'The elite tower used in the steam refining is provided with a tray of 20 to 25 sections in the tower, and the tray is provided with a plurality of sections 15 in the vertical direction in the horizontal direction. (4) (4) Dividing into the tower. The boiling point of the four fossils is 59t (latm), and the steaming refining program 20 has an evaporator (not shown), and the liquid of the four gasification fossils is evaporated by the evaporator. In the form of a gas, and by means of a flow meter, the gas discharged from the evaporator is detected. The gas flow rate of the fossils is controlled, and the amount of the base in the evaporator is controlled as described above. As described above, the functions of the steaming refining process, the fine (4), the evaporation (9) structure, and the function are well-known techniques, and the detailed description of the steps is omitted. [Reduction procedure] The reduction procedure 30 is used to make the gas four gasification enthalpy (SiCM and gas zinc (four) reaction Μ 状 slave (4) and is contrary, the generated Shi Xi 16 200902442 is the purity of six or more, that is, In the reduction procedure 30, the ruthenium tetrachloride and the zinc form a fluidized bed and react, and the reaction is described in detail in the description of the reactor 1 to be described later. The gasification crucible and the zinc system use an inert gas as a carrier gas, and the inert gas system is supplied to the reaction furnace 1 of the reduction program 30. The reduction reaction of the fluidized bed of the reduction program 30 is carried out in less than about 1 Torr (: 2 in a temperature ambient gas, and the reaction is represented by the following formula. [Expression 3] 1 〇 $ original procedure 30 The process of reducing the chlorination dream and making it into the stone eve and the gasification process, and the reduction process 30 is to reduce the four gas fossils and make the reaction furnace of the smashing and gasification. The reduction reaction of the flow layer by the reduction procedure Simultaneously, the chlorination (ZnCl2) can be generated simultaneously with Shi Xi (si), and further, the unreacted four gas fossils, unreacted zinc are discharged from the reduction process, and the self-reduction process is further discharged. The body gas is supplied to the electrolysis program by a gate (not shown) or the like which is discharged from the reduction process 3, and is supplied to the electrolysis program, and the electrolysis process 40 is electrolysis gasification. The procedure of reciting and making money and zinc. This beibei-shaped reaction furnace 1 continuously makes the metal 7 into a purity of six nine to seven nine by using the fluid layer type reduction method, that is, 2〇99_9999% The above-mentioned quality of Shi Xi. It is summarized in Table i below by using this month's reaction furnace 1; (4) Evaluation results of raw materials. 17 200902442 [Table 1] Sweat price quality (measurement method) Chemical analysis of Si raw materials produced Zn exchange amount 〇-5ppm or less (high-frequency induction plasma luminescence spectrometry··ICP- AES) Heavy metal cesium·one~ (Fe, Cr, Ni'Cu, Cd, Co, Μη, Mo, Na, Ni 'Pb, Ti, Sn, etc.) 0.1 ppm or less (High-frequency induction plasma luminescence spectrometry: ICP -AES) Polycrystalline polycrystalline purity ratio resistance (Ω ~ cm, 99.9999% (6N) or more substrate state> Grain of Si raw material manufactured by kg---- 1 lifetime 10~55 range 10/z Ses The number of diameters above /im is more than a few hundred-----____ Similarly, the carrier gas is also separated, and the gas system discharged from the reduction program 30 is discharged from the tube, and is supplemented by a gate (not shown) or the like. The gas of the tube is separated from the gas of the gas of the head 31, and the gas of the tube 31 can be separated by a gas (not shown) and the self-deducting gas is separated. Zinc. In addition, the separated four gas fossils can be supplied to the reduction program 30 and recycled, and the carrier gas is separated as well. It can be recycled in the reduction program 30, and the separated tetrachloride is passed through the tube η or directly to the distillation refining program 2〇. The emulsified yarn is in a gaseous state by discharging >· public, the next day UM N7 "tM head "3 j reduction procedure 30 takeout" 5 hai tetrachloride chlorite will be recovered and freeze-precipitated in a question (not shown) to form a liquid, χ, the liquid tetrachloride is supplied to the steam: refining procedure 20 And recirculating. In the reduction procedure, the material is grown into a filament shape by the above-mentioned material, and is taken out from the lower portion of the reactor i to the third discharge. The official 3rd position w is connected to the delivery device 50, and the delivery program, and & to the transfer program (hereinafter also referred to as "transfer") 5, and recorded to the later paragraph 18 15 200902442 制造 block manufacturing program 60 . Further, in the present embodiment, the transporting program 50 is a continuous conveyor such as a belt conveyor. However, the transporting program 50 may be a batch type in which the crucible is stored in the storage tank instead of the continuous conveying apparatus. In addition, in order to increase the particle size of the 矽5 crystal, if the carrier gas and the eutectic seed are mixed and supplied to the reaction furnace 1, and the crystallization seed crystal is grown as a core, it can be easily formed into a spherical shape. , spheroidal or ellipsoidal particle size. For example, Shixia crystal can use bismuth powder, and, for example, 矽 crystal can use 矽 powder with a diameter of 〆mi, and sometimes it is discharged with 1〇 from tube 31 or tube. The gas is discharged together, and the minute crucible can be utilized for separation from the gas. Further, the separation is preferably performed by a cyclone separation mechanism, and the separated micro-system is supplied as a seed crystal to the reaction furnace i, or The separated fine crucible can be discharged to the conveying device 50 as a product. 15 [Electrolysis procedure] The electrolysis procedure 40 is a procedure for electrolytically separating zinc chloride (ZnCl2) into zinc (Zn) and chlorine (Cl2), and the separated zinc is supplied to the reduction sequence 30 in a gaseous state and recycled. 'The separation gas is supplied to the chlorination process ^ and then to the soil (not shown). Fig. 3 is a view showing the outline of the electrolysis program. The electrolysis process 40 has an electrolytic cell 46, and the zinc chloride is separated in the electrolytic cell 46. Two electrodes 43 and 44 are disposed in the electrolytic cell 46, and are respectively connected to a direct current power source. The materials of the two electrodes 43 and the material are preferably carbon rods. However, the two ir electrodes 43 and 44 are not particularly limited in material and For the shape, other electrode materials of the known 200902442 can also be used. The electrolytic cell 46 is connected to the e 31 for supplying zinc chloride and for discharging the separated zinc (tetra) and chlorine (the tube of the (5), the 々I electrode (carbon rod) 43 system and the positive electrode, and the electrode (carbon rod) 44 is connected to the negative electrode: 'A pipe which is used to discharge gaseous chlorine is disposed near the carbon rod 43, and the gaseous chlorine is supplied to the chlorination program 15 and recycled. The carbon rod 44 is connected. The tube 42 for discharging the liquid is not shown, but the zinc can be vaporized by a known method, and the vaporized system is supplied to the reduction program 30 and recycled, and the following is shown. The reaction formula in the procedure 40 is solved. ' 10 [Expression 4] (Formula 4) 2C1' Cl2 + 2e' [Expression 5] (Equation 5)

Zn2+ + 2e' - Zn [Loading out program] 15 The transfer program 50 is a program for carrying out the enthalpy generated in the restore program 30, and the system is cooled to room temperature at normal temperature and discharged from the reduction program 3, and the transfer program % is used for carrying out In the procedure of the Si block manufacturing program 60 in the latter stage, the Si block manufacturing program 60 in the subsequent stage is a program for producing a grained block such as an elliptical ball or a spherical ball produced in the reduction program 30, for example. For example, 20 the granular stone block is made into a material to manufacture a stone plate for a solar cell. Heretofore, a summary of a series of procedures for manufacturing equipment has been described in terms of a fluidized zinc reduction method, and a fluidized layer zinc reduction reactor is described in detail below. [Flow layer zinc reduction reactor] 20 200902442 Fig. 1 is a schematic view showing the outline of the reaction furnace 1 of the present invention, which is a fluidized bed type reduction reaction furnace, and the reaction furnace 1 is used for High-temperature reaction furnace in which the inert gas is used as a carrier gas for temperature control and flow rate control, and reduction reaction of zinc (Zn) and ruthenium tetrachloride (SiCl4) is carried out continuously and at high speed in the reaction furnace 1 . In the reactor 1, the granules are continuously formed, and the cerium is doped by the carrier gas in the carrier gas (see Fig. 2). It grows and effectively produces granular lumps of ellipsoidal or spherical shapes. Briefly, the reaction furnace is divided into a "removal chamber 3" by a reaction chamber 2 provided in a fluidized bed on the upper portion of the reactor 1 and a take-out chamber 3 installed in the lower portion of the reactor 1, and the second extraction chamber 4 and The second extraction chamber 5 is formed by the upper and lower chambers, and the high-purity stone is prepared in the reaction chamber 2, and the high-purity material is taken out from the take-out chamber 3. The reactor 1 has a container 7, and a reaction chamber 2 and a heater (not shown) for adjusting the temperature of the reaction chamber 2 are disposed in the container 7, and a plurality of zinc supplies are opened on the bottom plate 6 of the reaction chamber 2. The mouth is supplied with the vaporized zinc from the S 荨 zinc supply port of the bottom of the bottom plate 6, and is supplied and filled to the reaction to 2. This special word supply port is connected to the tube 42 of the electrolysis program (see Fig. 4). Further, the introduction tube 21aJ_ is placed on the bottom plate 6 and stands up from the bottom plate 6. 20 The introduction pipe 21a is connected to the pipe 21, and is used for supplying the vaporized four gasification ruthenium into the reaction chamber 2, and further supplying and vaporizing the gas and the gas into the reaction chamber 2 The fluidized layer is effectively subjected to a reduction reaction, whereby particles of a diameter of several to several mm can be produced at high speed and continuously by the reduction reaction of the reaction chamber 2. In the reduction reaction, zinc hydride is formed simultaneously with 矽 21 200902442, and in the reduction reaction, zinc chloride 'unreacted four gasification fossils, zinc, etc. are separated in a vapor state, and The exhaust pipes 31, 31a are discharged. The tetrachloride is used to carry out the reduction reaction, and the inert gas is used as the carrier gas, and the inert gas is supplied from the introduction tubes 34 and 35 (see the 28th), and i is supplied to the inert gas system from the introduction unit 35. In the reaction chamber 2, if the seed crystal is mixed with the inert gas towel for the self-guided person (4), it will be crystallized more efficiently as a core, and, in other words, the inert gas supplied from the introduction tube 34. It is supplied to the take-out chamber 3, and the unreacted gas 1 remaining in the take-out chamber 3 is stored by the inert gas supplied from the introduction pipe 34, and is continuously discharged from the discharge pipe 31a as shown in Fig. i. The discharged carrier gas is preferably separated from other gases and recycled, and the dream generated in the reduction reaction is dropped from the through holes and/or the gaps opened in the bottom plate 6 to the take-out chamber 3 provided to communicate with the bottom plate 6. Briefly, the through hole and/or the gap are arranged on the surface of the zinc supply port for supplying zinc, and the reaction chamber 2 is made of quartz according to the viewpoint of heat resistance and prevention of impurity incorporation. It is made of a ceramic material such as tantalum carbide, and a heater (not shown) is provided on the side wall of the reaction chamber 2. With the heater, the space of the reaction chamber 2 is split into 2 in the longitudinal direction (vertical direction), and the aforementioned spaces are formed at a temperature of 7 5 0 X: to about 1200 〇C, and the temperature ryg 1^·° is bad. From the specific temperature zones, the optimum conditions for each reaction are 'controlled' and the reaction is carried out in each temperature zone. The fossils supplied from the inlet pipe 2la and the words supplied from the refilling port provided on the bottom plate 6 are reacted in the entire space of «to 2, however, mainly in the upper field of the introduction pipe 22 200902442, the reaction is performed. The field is indicated by the dashed line in Fig. 1, and the field is reacted in the fluidized bed, and the temperature in the field is controlled in the range of about 9 ° C to 11 ° (Tc. The introduction pipe 35 provided on the bottom plate 6 of the reaction chamber 2 is supplied to the reaction chamber 2, and the carrier gas system is supplied to the take-out chamber 3 through the introduction pipe 34, and the carrier gas system introduced into the take-out chamber 3 is taken out and taken out. The gas in the chamber 3 is discharged from the discharge pipe 31a simultaneously with the gas. The exhaust gas discharged from the discharge pipe Ma contains zinc chloride, a carrier gas, and unreacted four gas fossils which are simultaneously generated in the reaction. In the evening, the exhaust gas system is separated and treated in the vapor 10 state, and is discharged from the discharge pipe 31a. Further, it is closed by the reaction furnace 1 and the electrolysis program 4 (not shown). Show), from the gas discharged from the reaction vessel (for The unreacted gas zinc, the four gas cut and the carrier gas, and the gasification word) are separated from the zinc chloride by the exhaust pipe 3 and 3la. The zinc chloride is transported to the electrolysis program.

15 electrolytic cell 46, and the carrier gas is an inert gas. For example, the carrier gas is an inert gas such as nitrogen or argon. 20 The stone formed in the reduction reaction is stirred and mixed by the carrier gas and crystallized and crystallized in the reaction chamber 2 to form a granular shape, and the size of the particles constitutes a diameter _~number_ size. In order to promote the growth of Shi Xi, a metal core can be disposed in the reaction chamber 2 (not _, the stone generated in the reduction reaction is attached to the metal core and crystallized, and a predetermined voltage is applied to the metal core and flows. The current promotes the growth of the crucible—the temperature of the metal core is controlled to be higher than the wall of the furnace. Accordingly, by performing the temperature of the metal core (4), the above-mentioned reduction and the reduction of the gold can be promoted, and the reaction in the furnace can be improved. The reaction efficiency of the space and the improvement of the reaction rate of the stone generated by the reduction reaction. The material of the metal core is preferably a core or a broken core, and in order to rapidly carry out the gas formed by the reduction reaction of the fluidized layer The phase is grown into a granular form, and it is preferable to supply the seed crystal together with the carrier gas, and the 50% of the stone will be attached to the seed crystal and grow into a granular stone. [Removal chamber] The first take-out chamber 4 is placed in a drop from the reaction chamber 2; and the second take-out chamber 5 is used to lower the temperature from the second take-out chamber 4 to a low temperature and take it out. The reaction furnace "produces the normal temperature Shi Xia 10 self-transportation program 50 companies After being discharged, the second take-out chamber 5 may be dropped and stored in the storage tank or the like provided in the transporting program 50, or may be stored in the second take-out chamber 5 and taken out at predetermined intervals. The crucible may be stored in the second take-out chamber 5 and taken out when the predetermined amount is formed. The material of the first take-out chamber 4 is made of a ceramic material such as quartz or tantalum carbide, I5. The internal or external heating is performed at a temperature of 700 ° C to 1000 ° C, and the introduction pipe 35 (see FIG. 2 ) for supplying the carrier gas to the reaction chamber 2 is connected to the second extraction chamber 4 . 2 The take-out chamber 5 is a mechanism for taking out the generated cockroaches, and lowering the temperature to a normal temperature and having a mechanism for carrying out the raw material generated by the sputum. Further, the second take-out chamber 4 is connected to the carrier gas guide 2, the immersing tube 35, and the four gas. The sputum tube 21 and the zinc gas supply tube 42. The bottom portions of the first extraction chamber 4 and the second extraction chamber 5 are separated by the shutters 8, 9 respectively, and are dropped from the reaction chamber 2 and then dropped to the first 1 takes out the chamber 4 and deposits it on the dam 8. If the amount reaches a predetermined amount, the door 8 is opened and dropped to the second Exit chamber 5. Since the first extraction chamber 4 may contain a certain amount of unreacted gas of 24 200902442, the carrier gas is supplied from the introduction tube 34 and flows for a certain period of time, and the unreacted gas is supplied from the exhaust pipe. 3ia is discharged, and then the shutter 9 of the second take-out chamber 5 is opened and dropped to the take-out chamber of the transport program 5, and the like, and taken out continuously at room temperature. 5 Other Embodiments The present invention is for manufacturing A second embodiment of a reaction apparatus for a raw material for a solar cell, and a fourth embodiment of the present invention are a schematic view of a reactor 101 and a separator 200 according to a second embodiment of the present invention. In the reactor 1 of the first embodiment, the structure of the separator 2 is added to the reactor 10, and the reactor 101 of the second embodiment is basically the same as the reactor 1 of the first embodiment. However, the detailed structure is different. Here, only the reaction furnace 101 and the separator 200 will be described, and other configurations and functions are the same as those of the first embodiment, and the description thereof will be omitted. [Reaction Furnace] 15 The reaction furnace 101 is a fluidized bed type zinc reduction reactor, and the reaction furnace 101 is used for reducing the vaporized (Zn) and the four vaporized cerium (siCl4) by a fluidized bed method. The apparatus of the Shiki is continuously generated, and the reactor 101 is connected to the separator 200 which is separable and other gases. The reactor 101 is schematically illustrated by the reaction chamber 102 located at the upper portion of the reactor 101 and at 20 The lower portion of the take-out chamber 103 is constructed. The reactor 1 〇1 is used for temperature control and flow rate control using an inert gas as a carrier gas, and the reduction reaction of zinc (Zn) and ruthenium tetrachloride (SiCU) which has been vaporized in the reactor 101 is high speed and A reaction furnace that efficiently performs a reduction reaction. By the reaction furnace 101, the granular granules are continuously produced, and the Shihwa crystal system 25 200902442 is supplied from the introduction tube 111 into the reaction chamber 1 () 2, and the crystal seed crystal can be used as a core and the ruthenium crystal can be grown. And effectively produce a granular stone eve. The seed crystal can be regarded as a seed crystal in the initial stage of growth, and the reaction furnace 101 includes a reaction chamber 1〇2 which is not placed in the flow layer in the upper portion of the reaction furnace 101; and 5 is continuously disposed in the lower portion of the reaction chamber 102. The first take-out chamber 104. The lower portion of the first take-out chamber 104 is continuously connected to the second take-out chamber 1〇5, and the reaction chamber 1〇2 has a vertically long cylindrical structure in which the inside is hollow, and as shown in Fig. 4, the reaction chamber 102 is The two-stage structure of the upper zone i〇2a and the lower zone 1〇21) is formed, and the upper zone 102a and the lower zone i〇2b each have a cylindrical structure 10 having a hollow inside. The inner diameter of the inner hole of the upper portion 102a is larger than the inner diameter of the inner hole of the lower portion 1〇21?, and the upper portion is connected with the shishi area of the T area (four) shop (four) tapered cylindrical portion, and the two inner portions are connected The holes are continuous. The reactor 1〇1 system has its own function.卩 heating the heating mechanism of the reaction chamber 1〇2, if the heating mechanism 12 can control the internal temperature of the 15 reaction chamber 102 to a desired temperature, the heating can be performed by any heating principle. These heating mechanisms are known, and the heating mechanism 120 of this example is an electrothermal heater that conducts electric current to heat. Although not shown, the reaction chamber 102 and the heating mechanism 12 are housed in a 2-inch container or the like, and the heating mechanism 120 has a shape similar to that of the reaction chamber 1 2, in other words, the heating mechanism 120 is There is a structure capable of efficiently heating the reaction to 102. As shown in Fig. 4, the reaction chamber 1〇2 is composed of the upper portion 1〇2a and the lower portion 102b. Therefore, the heating mechanism 12 is configured by the second heating mechanism 120a. And the second heating mechanism 120b, the second heating mechanism 12〇& is added 26 200902442 The hot upper portion 102a 'the second heating mechanism 120b heats the lower portion i〇2b. In the second embodiment, the first! The heating mechanism 12〇3 and the second heating mechanism 120b have the same structure. However, depending on the temperature of the upper region 1〇2a and the lower region 1〇, it is also possible to use a different structure that can be easily heated to its temperature. The heating mechanism of the different heating principle, the structure of the first heating mechanism 120a and the second heating mechanism 120b will be described later. The majority of the steam supply port is formed in the bottom plate 1〇6 of the reaction chamber 102 to form an opening, and the vapour supply port is supplied from the entire bottom of the bottom plate 1〇6, and the vapor is filled in the reaction. Inside the chamber 102. In addition, in order to rise from the bottom plate 106, the introduction pipe 21a is disposed to be exposed at a lower portion of the lower portion i2b, and the introduction pipe 21a is connected to the tube 21 of the silicon tetrachloride which is supplied with vaporization, and is introduced. The tube 21a is for supplying the vaporized four gas fossils to the reaction chamber 1〇2. Further, the zinc vapor is supplied from the tube 42 to the bottom plate 1 〇6 to be described later in the lower portion i2b, and accordingly, the ruthenium tetrachloride is supplied from the 15 introduction pipe 213 and the sulphur vapor is supplied from the bottom plate 106. The vaporized zinc and the flowing layer of antimony tetrachloride in the reaction chamber 2 are effectively subjected to a reduction reaction. According to the reduction reaction, the particles, the powder, and the like having a diameter of several to several mm are produced at a high speed and continuously, and the tetrachlorides supplied from the introduction tube 21 & are reacted with zinc to form a granular stone. On the eve of the day, or alternatively, the silicon tetrachloride supplied from the tube is reacted with zinc to crystallize and crystallize the crystal, and the reaction is carried out in the entire reaction chamber. However, the reaction is mainly Concentrated in the central (central) field of the reaction chamber 102. If the bottom plate 106 can generally introduce the zinc vapor supplied from the tube 12 into the chamber 102, it can be of any shape, and the lanthanum generated in the reaction chamber 1〇2 falls due to gravity, and The lower portion 1〇2b enters the first take-out chamber 丨〇4, at which time the 矽 system penetrates the bottom plate 106 and enters the first take-out chamber 104 from the reaction chamber 1〇2. Therefore, the bottom plate 1〇6 must have a majority that can pass through. Through hole or 5 gaps. Fig. 5 is a view showing an example of a bottom plate 1〇6 which includes a plurality of zinc vapor supply holes 107 which can introduce zinc vapor from the tube 42 into the reaction chamber 1〇2; and an annular gap through which the crucible can pass 1〇8. As shown in Fig. 5, the bottom plate 1〇6 is composed of a plurality of concentric annular tubes. In the example illustrated in Fig. 5, the bottom plate 106 is connected by a ring tube l〇9a' l〇9b. 109c and 109d are connected by concentric circles to a four-fold pipe, that is, a pipe of a four-curvature annular pipe, and each of the pipes 109a, 109b, 109c, and 109d is connected to the pipe 42a or the pipe 42b. The tube 109d and the tube 109a are connected to each other by the tube 11b, and the tube i〇9a is connected to the tube 42b, and the tube l〇9b and the tube l〇9c are connected to each other by the tube 11〇a, and The tube 1〇9b is connected to the tube 42a, and the tube 42a and the tube 42b are connected to the tube 42 (not shown). The tubes 10a, 109b, 10c, and 109d open the plurality of steam supply holes 107 at predetermined intervals, respectively, and the steam supplied from the tubes 42 passes through the tubes 42a and 42b, and passes through the tubes 10a, 109b. 109c and 109d are supplied to the reaction chamber 102, respectively. 20 The steam supplied from the tube 42 to the tube 42a is supplied into the reaction chamber 1〇2 through the tube 1〇%, the tube 11〇a, and the tube 10〇9c, and the zinc supplied from the tube 42 to the tube 42b simultaneously with the supply. The vapor is supplied to the reaction chamber 102 through the tube 109a, the tube 110b, and the tube 109d. The size of the zinc vapor supply hole 107 provided in the tubes i〇9a, l〇9b, 109c, and 109d and the two vapor supply holes 107 are provided. The interval must be optimized according to the size of the chamber 102, the pressure of the supplied steam, the flow rate, the flow rate, and the like. Similarly, the outer diameters and inner diameters of the tubes of the tubes 109a, 10b, 109c, and 109d are the same, or the arrangement intervals of the tubes 5a, 109b, 109C, and i〇9d in the direction of the radius 5 must be based on the reaction chamber 102. The size, the pressure of the supplied zinc vapor, the flow rate, the flow rate, and the like are optimized, that is, in the reaction chamber 1〇2, in order to cause the turbulent flow of the vapour vapor and the antimony tetrachloride, the particles are randomly and effectively contacted and manufactured. Granules must be optimized. In the present embodiment, the size of the reaction chamber 102 is a cylindrical shape having a length of 90 cm to 150 cm and an inner diameter of 20 cm to 40 cm. 10 In this example, the tube 42a and the tube 42b have a tubular shape with an inner diameter of 2 cm to 4 cm, and in this example, the inner diameters of the tubes 'tubes l〇9a, i〇9b, l〇9c, and 109d are 2 cm. 4cm tubular. In the reaction chamber 2, depending on the case, if the barrier plate 110 or the like is provided to promote the growth of the crucible, it is only necessary to generate a turbulent flow and promote the reaction between the reciprocating and the four gasification, and the obstruction plate 11〇 The raw material supplied with the anti-15 is directly reacted into the exhaust pipe 31c without being reacted. [Product] When the reduction reaction in the reaction chamber 102 having such a configuration is carried out, a granular granule can be continuously formed in the reaction to 102, and in the reduction reaction, zinc hydride is formed at the same time as the stone eve. The produced zinc oxide, unreacted hafnium tetrachloride, zinc or the like is separated from the reaction chamber 102 in a vapor state and discharged from the exhaust pipe 31c. The exhaust pipe 31c is connected to the pipe 31d, and the gas discharged from the exhaust pipe 3ic and the pipe 31d may contain minute turns, which are preferably separated and reused by the separator 200 or the like in the subsequent stage. 29 200902442

Through hole or gap 1 〇 8 drilled on the bottom plate 106, for example, used as Shi Xijing

It is a crystal growth and crystallization to form particles, • it adheres or condenses, or the size of the particles is a diameter of several tens / / m ~ hundreds of "m". [Carrier gas] The carrier gas system is supplied from the introduction tube 21 10 and/or the introduction tube 42 simultaneously with zinc vapor and zinc chloride, and the carrier gas system is supplied from the tube 111 in the same manner. The carrier gas system utilizes an inert gas, and the carrier gas system supplies the stirring for the reaction to 102, the adjustment of the gas concentration, etc., and if the carrier gas has no influence on the reduction reaction and the product thereof, any type of gas may be used. For example, the carrier gas system is an inert gas such as nitrogen or argon. The unreacted gas, the carrier gas, and the like remaining in the second extraction chamber 5 are continuously discharged from the tubes 31b and 31a. The carrier gas discharged from the chambers is preferably separated from other gases in order to reduce the amount of carrier gas used. The carrier gas is recycled. [Heating Temperature] By the heating mechanism 120, different temperature zones of about 75 CTC to about 20 1200 ° C are formed in the longitudinal direction of the reaction chamber 102, and the heating mechanism 120 can heat the reaction chamber 102 to 900 ° C or more to 1300 ° C. However, the heating temperature of the heating mechanism 120 can be used to heat the reaction chamber 102 to at least 1000 ° C to 100 ° C. The reaction chamber can be 'reacted under the optimum conditions of the reaction by the temperature zones'. Temperature control is carried out in 102 and the reaction is carried out. 30 200902442 In the second embodiment, the reaction chamber 1〇2 is longitudinally divided into two space benefits for control, and the two spaces are formed from the upper side as the upper area l〇2a and the lower area 102b. Heating is carried out in the following temperature range. The reason for dividing the reaction chamber 10 2 into two spaces is to allow the small ruthenium particles to remain in the main reaction portion for a long period of time 5, and the main reaction for generating the ruthenium reaction is carried out in the upper region 102a for the upper region 1 In 〇2&, the particle size of the 矽 seed crystal of the number "claw to tens/zm is increased to a number of 100". Therefore, it is necessary to make the seed crystals of the number /m to tens of μm long-term retention in the upper region 102a. Accordingly, the apparent velocity of the lower region 1〇21 must be made (reverse 10 gas and carrier gas). The speed of moving upward from below is higher than the apparent speed of the upper zone 102a. The drop of the ruthenium particles occurs at the following times: in the ruthenium particles, the buoyancy caused by the dynamic pressure blown from the apparent velocity below and the mass of the ruthenium particles which grow at the moment of crystallization and increase the mass When the balance is damaged. 15 In principle, when the mass of the ruthenium particles is greater than the buoyancy caused by the dynamic pressure, it will fall due to its own weight. Therefore, since the velocity of the object falling due to gravity is proportional to the square of time, therefore, The final velocity at which the particle size of the particle is dropped by gravity can also be said to be greater than the apparent velocity. Therefore, the velocity of the gas 20 in the region of the lower region of the lower region of the crucible is eventually increased. Since the retention time of the ruthenium in the upper region 102 & is increased, the strontium seed crystals can be retained in the upper region 10a and grow. In order to retain the seed crystal in the upper region 102a before it grows to the particle size of the number #, it is necessary to increase the apparent velocity of the lower region. For example, in order to maintain the final particle of greater than 200 #m in the lower region 102b, At the apparent speed of the drop speed 31 200902442, the upper zone l〇2a and the lower zone i〇2b are formed into two spaces having different inner diameters and the inner diameter of the upper zone 102a is 2〇cm~6〇cm, the lower part is £ The position within 102b is formed to be 5 cm to 10 cm. If it is assumed that the gas flowing from the lower zone i〇2b into the upper zone i〇2a is uncompressed, the velocity of the upper zone i〇2a is lower than that of the lower zone l〇2b by the continuous mode described in the fluid mechanics. Gas speed. The upper area i〇2a is tied to 9〇〇. 〇 ~ 1050 ° C for heating, the lower area i 〇 2b is between 900t ~ 950. (: heating is performed, and the 'extraction chamber 104 is 950 ° C to 100 (the TC is heated, and the take-out chamber 105 is heated at 950 ° C to 1000 ° C. Although not shown, the 10 exit chamber 105 is taken. A heating mechanism is provided around the temperature, and temperature control can be performed in the above temperature range. [Supply speed of raw materials and raw materials] In the second embodiment, the size of the reaction chamber 102 is 9 cm to 150 cm in length. The inner diameter of the region l〇2a is 20 cm to 40 cm, and the inner diameter of the lower region i〇2b is 15 cm to 10 cm. Further, in the second embodiment, the materials supplied to the reactor 101 of the size are not However, it is limited to this, but can be supplied by the following flow rate. For example, zinc (Zn) supplied from the tube 42 can be supplied by the following flow rate. The linear velocity of the zinc outlet is 3 m/sec to 20 m/sec. The flow rate is supplied. Preferably, it is 7 m/sec to 10 m/sec. Specifically, the linear velocity of the zinc vapor outlet is the rate at which zinc (Zn) is supplied to the reaction chamber 102 from the vapor supply port 1〇7. The ruthenium tetrachloride (SiCl4) supplied from the tube 21 can be supplied by the following flow rate, and the ruthenium tetrachloride (SiCl4) is blown out. The linear velocity is supplied to the outlet port of 'an' tetrachloride (SiCl4) at a flow rate of 3 m/sec to 20 m/sec. 200902442 Linear velocity barium tetrachloride is supplied from the tube 21a to the reaction chamber 1〇2 The materials supplied to the reaction chamber 102 are not limited thereto, and are preferably supplied in the reaction chamber 102 of the present example by the following flow rates: reaction gases of zinc (Zn), cerium tetrachloride (siCl4), and carrier gas. The above-mentioned apparent velocity is supplied at a flow rate of 〇〇3 m/sec to 5 〇.7 m/sec. However, the apparent velocity is the average flow velocity of the cross section of the tube, and the ruthenium tetrachloride (the line of the outlet of SiCl) The speed (the speed of the discharge port of the introduction pipe 21a) is supplied at a flow rate of 3 m/sec to 20 m/sec, and preferably 7 m/sec to 10 m/sec., and zinc (Zn) supplied to the reaction furnace 101. It is supplied with a molar ratio of 2.1 to ruthenium tetrachloride (SiCl4). However, in actual equipment, it is operated by an effective correction value based on actual operating data and the like. Zn) is a vapor-based mixed carrier gas, and the carrier gas mixed with the Zn vapor is preferably 0.1 to 0 with respect to zinc (Zn). The range of .5 : 1. The vapor of the tetrachloride (siCl4) is supplied by a mixed carrier gas, and the carrier gas mixed with the vapor 15 of the ruthenium tetrachloride (SiCl4) is preferably 0.1 with respect to the gasified ruthenium (SiCl4). Further, the number of the twin crystals supplied to the reaction chamber 102a is preferably the number of the outer diameter of the number #m. The supplied crystal seed crystals are preferably 4% to 6% of the amount of the eve of the eve. Specifically, if the average amount of enthalpy generated in one hour is 10 kg, the supply amount 20 of the eutectic seed crystals will constitute an average of 4 〇〇g to 600 g per hour. The twin seed system is supplied simultaneously with the carrier gas, and the zinc gas supplied from the introduction tube 21a and the zinc supplied from the zinc vapor supply port 107 provided on the bottom plate 10.6 react in the entire space in the reaction chamber 102. However, the reaction is mainly carried out in the upper region of the introduction pipe 21a, which is reacted in a flowing layer in a turbulent state, and the temperature in the field of the 2009 200902442 is in the dynasty. The range of c is controlled. The exhaust gas discharged from the e31e discharge contains zinc chloride, _gas, unreacted four gas cuts and non-reverse flames generated in the reaction. Treatment, and ^ end from the tube, tube discharge. Further, by means of a gate (not shown) provided on the middle of the reaction fineness and the electrolysis process 4, the zinc containing the unreacted gas is separated from the tetrachloro-cut, the chlorine of the gas material, and the exhaust pipe is closed. Both are separated from the vaporized zinc and the chlorination is transported to the electrolysis process tank 46. 10 [Extraction chamber] The second extraction to the 1〇5 system is used to reduce the temperature of the Shixia to a low temperature and is taken out. The hair system that has been lowered to near normal temperature is supplied to the transport program %, and enters the stone of the second extraction chamber 1G5. The eve will be dropped and stored in the storage tank provided in the transfer program brother, or the Shi Xi system will be stored in the second take-out chamber 1〇5, and the collision door 1〇9 will be opened I5 and taken out every predetermined time. Or, the Shi Xi system is stored in the second take-out chamber 1〇5, and when the predetermined amount is formed, the shutter 109 is opened and taken out. The material of the first take-out chamber 104 is made of a ceramic material such as quartz or tantalum carbide, and is first taken out to the fourth system and heated from the inside or the outside at 7 inches. The temperature is controlled to 1000 ° C, and the introduction tubes 21 and 42 for supplying the carrier gas to the reaction chamber 20 1〇 are disposed in the first extraction chamber 104. Further, in Fig. 4, the tube 111 is disposed to penetrate the wall of the reaction chamber 1〇2, and the tube U1 is disposed to discharge the seed crystal in the upper portion 102a of the reaction chamber 102. However, the tube 111 may be disposed in the first take-out chamber 104 and extended in the extension direction, and the front end 111a may be disposed in the reaction chamber 1〇2, and the second take-out chamber 34 200902442 105 may be divided to extract the wonderful room. And lowering the temperature of the Shixia to substantially normal temperature, and the second take-out chamber 1〇5 has a mechanism for carrying out the raw material generated by the raw material, and the bottom portions of the first take-out chamber 104 and the second take-out chamber 105 are respectively blocked by the block. The doors 108, 109 are separated, and after falling from the reaction chamber 1〇2, they are dropped to the third chamber 5 and stored. If the crucible reaches a predetermined amount or a predetermined time elapses, the shutter 108 is opened and the crucible is dropped to the second take-out chamber 5, and gas such as unreacted gas may enter the second take-out chamber 5'. 31a, the fairy is discarded, and then the shutter 109 is opened and dropped to the take-out room of the transport program 5, and the like. When the 内 in the ten-chamber 105 is taken out by a predetermined amount or a predetermined time elapses, the shutter 109 is opened and the shovel is dropped from the second take-out chamber 5 to the take-out chamber of the transport program 5, and the like. [Separator] A separator 2 is added to the reactor 101, and the separator 2 is a cyclone separator, and the separator 200 is composed of a separation chamber 2〇1, a tube 2〇5, a tube 204, 15 is formed by the third extraction chamber 202, the tube 203, and the like. The tube 205 is connected to the tube 31d, in other words, the front end of the official 31d is the tube 205, and the tube 2〇5 is disposed in a tangential direction toward the cylindrical separation chamber 201 in order to cause swirling. The tube 204 serves as a tube for sucking out the gas in the separation chamber 201, and the exhaust gas discharged from the tube 31c contains minute stones, and the separator 2 is separated from the gas by the exhaust gas 20, and is separated. The stone system enters the reactor 1〇2 through the lowermost tube 203 of the separator 200. The tube 204 is a tube for discharging the gas in the separation chamber 201, and the suction port of the front end of the tube 204 is disposed on the lower side than the tube 205, and this is set by the cyclone principle to separate the crucible. That is, the gas supplied from the discharge port at the tip end of the tube 205 and the minute sputum are not directly sucked into the suction port of the tube 204, and the gas system supplied from the discharge port of the tube 205 is circulated in the separation chamber 201 and then sucked to The suction port of the tube 204. The lanthanum is spirally moved and dropped along the inner peripheral wall of the separation chamber 201 by centrifugal force during the rotation in the separation chamber 201. At this time, since the cooker 5 has a mass, it can be separated from the tube by centrifugal force. The center of 204 is dropped to the third take-out chamber 202. Further, the stone system enters the reaction chamber 1〇2 through the tube 203, and the minute lanthanum entering the reaction chamber 102 has a function as a core for growing the granular ruthenium, which is necessary for the reduction reaction. The amount of the 矽10 seed crystal from the tube 111 can be stopped. In this case, the ruthenium seed is not supplied from the tube ill in the reduction reaction, and the ruthenium separated by the separator 200 can be reused as the eutectic seed crystal. . On the other hand, it is also possible to optimize the supply amount of the material for the reduction reaction and the carrier gas, and to use only the ruthenium separated by the separator 2 as a seed crystal. The separator 200 is attached to a temperature of 900. (:~1000. (: heating, as shown in Fig. 15 of Fig. 4) The heating mechanism of the separator 200 may be the same heating mechanism as the heating mechanism 120c of the separator 200 and the heating mechanism 120 of the reaction chamber 1〇2. However, as will be described later, in order to precisely perform the heating of the separator 200, the heating mechanism of the separator 200 shown in Fig. 6 and the heating mechanism of the reaction chamber 1〇2 use other heating means 120c. 2 At this time, the separator 200 is heated by the heating mechanism 120c, and the reaction furnace 101 is heated by the heating mechanism 120. However, the heating mechanism 120c is the same principle as the heating mechanism 120, and accordingly, if the separator 200 borrows By heating by the independent heating mechanism 120c, the temperature in the separator 2 can be easily controlled, and the temperature of the separator 2〇〇36 200902442 can be controlled by the temperature different from the temperature in the reaction chamber 102. [Material of Reactor, etc.] The reaction chamber 102 has high heat resistance, and may be any material if it is not incorporated into the crucible of the product. In this example, it is made of quartz or tantalum or the like. Made of carbon, similarly, tube 4 2a, 42b may be composed of quartz or carbon material, and the tubes 109a, 109b, 109c and 10' of the bottom plate 106 may be formed of quartz or carbon material. 'The' tubes 110a, 110b may be made of quartz or carbon. The material of the first extraction chamber 104 is made of a ceramic material such as quartz or tantalum carbide, and the material of the second extraction chamber 105 is made of a ceramic material such as quartz 10 or tantalum carbide, and the separator 200 It is made of a ceramic material such as quartz or tantalum carbide. [Others] Fig. 6 is a schematic view showing another modification of the reactor 101 according to the second embodiment of the present invention, as shown in Fig. 6 In the reaction chamber 1〇2 of the 〇1, the upper and lower portions are all of the same inner diameter and have a cylindrical shape. As shown in Fig. 6, the diameter of the second extraction chamber 1〇5 is reduced as it goes downward. In the conical structure, the tube 31b is configured to enter the second take-out chamber from the first take-out chamber 104. The reaction furnace 101 shown in Fig. 6 has the same inner diameter because of the upper limit of the reaction chamber 102, so that the upper and lower portions cannot be made. The gas velocity changes, however, it has a simple structure and a control of the gas flow rate. Brief Description of the Invention Example 1 The following is a description of the experimental example in the above reactor experiment. The experiment of Example 1 was carried out using the reactor 1〇1 shown in Fig. 6 to perform the reaction furnace 101. The reaction chamber 102 has an inner diameter of 3 mm and a height of 37 200902442 900 mm. The raw material for the production of ruthenium is supplied to the reaction chamber 102 which has been heated to a predetermined temperature to carry out 'specifically, four in the reaction chamber 102. The ruthenium chloride is supplied from the tubes 21 and 32 in confusion with the carrier gas, and the four gasifications are reacted with the zinc in the reaction chamber 102 to form ruthenium. 5 The experiment of the first embodiment is carried out in batch mode, that is, the generated stone will fall and accumulate in the first separation chamber 104'. If the stack of the first separation chamber 104 constitutes a certain amount, the shutter 108 is opened. The sputum 109 is dropped from the first separation chamber 104 to the second separation chamber 105', and if the stone slab accumulated in the second separation chamber 105 constitutes a certain amount, the sputum 109 is opened and taken out. The extracted stone was analyzed and the gas, the helium tetrachloride gas, and the carrier gas were simultaneously supplied to the chamber. The carrier gas system argon gas has a flow rate of 3.1 m/see when supplying zinc gas and carrier gas, and a flow rate of 3.4 m/sec when supplying four gasification gas and carrier gas, and again, reciprocating with four gasification hard The raw material has a Znf^Sicl4:^ molar ratio of 2:1. Table 2 shown below shows the experimental conditions of the examples and the characteristics of the raw materials. The first block of Table 2 indicates the sign of the experimental conditions, and the second block of Table 2 indicates the inside of the reaction chamber 1〇2. The temperature, column 3 of Table 2 shows the shape of the crucible formed in the reaction chamber 1〇2. The fourth block of Table 2 indicates the size of the crucible generated in the reaction chamber 102. When the size is spherical or granular, the particle size indicates the particle size. When the size is 20, the length is expressed by the slenderness. Column 5 of Table 2 shows the drawing number of the product photograph generated by each of the conditions A to C, and the condition A of the table A is the temperature in the reaction chamber 102: 1000X: 'The reaction chamber described here The temperature in 1〇2 is the wall temperature of the central portion of the reaction chamber 102 (the same applies hereinafter). Further, the generated enamel is needle-like or coral-like, and its size is almost 100 38 200902442 or more. The photograph of the cockroach generated by shooting the condition A is the first 〇 (a). The condition B in Table 2 is that the temperature in the reaction chamber 1〇2 is 1〇5〇. 〇 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 111 111 111 111 111 111 111 111 111 111 111 111 111 111 111 111 111 111 111 111 111 111 111 111 111 111 111 The condition c in Table 2 is that the temperature in the reaction chamber 102 is 110 (rc, and the generated fluorene-based fine particles are almost 10/Zm or less. The photograph of the enthalpy generated by shooting the condition C is the i-th. 〇 (c) Fig. _ [Table 2] Photograph of the size product of the temperature product of the conditional reaction chamber. Photograph A 1000°c Needle shape, coral shape 100 or more, 10th (a) condition B 1050°C granule 10~100 /2 m 10th (b) condition C 1100°c microparticle 10/zm or less 10(c) is high in the collection rate of the product under the condition A, and the product is produced under the condition b The acquisition rate is medium. The acquisition rate of the product is the lowest when the condition C is used. The so-called acquisition rate is defined by the amount of Si acquisition/theoretical amount. If these results are studied, the following conditions can be explained. A generates a large enthalpy, and it is physically difficult to continuously flow from its shape, so it is suitable for batch reaction. In the case of condition B, almost granules are formed, and the granules are continuous.

The ground flow 'at condition 3 is the optimum condition for continuously generating enthalpy by continuous operation. In the case of condition c, since the collection rate is low, it is less suitable in mass production than the other two conditions A and B. X-ray analysis is performed by X-ray analysis of samples from condition B. The X-ray analysis system is based on X-ray per unit (X' pertMPD) manufactured by SPECTRIS 20 (Tokyo, Minato-ku, Japan). The X-ray source is a copper (Cu) Κα line with a wavelength of 1.5418A 39 200902442, the 11th image shows the result of the X-ray analysis, and the vertical axis of the 11th chart shows the diffraction reflection using the X-ray source. Intensity, the horizontal axis of the graph represents the diffraction angle 20, and the analytical system shows that the sample is pure ruthenium. Further, the impurity amount of the sample was analyzed, and Fig. 12 shows the result of the analysis. 5 The impurity mass was manufactured by Yokogawa Analytical Systems Co., Ltd. (Hachioji City, Tokyo, Japan) ICP-MAS device (Agilent (Agilent) 7500s) to determine 'from the chart of Figures 11 and 12, the sample of condition B is 99.99992% and 99.999967%, which means that the lowest 6N can be generated. From the experimental results, it can be seen that depending on the temperature in the reaction chamber 102, 10 different shapes can be generated, and the residence time of the raw materials in the reaction chamber 102 is determined according to the flow rate of the raw material supplied to the reaction chamber 102, and then The residence time of the raw materials retained in the reaction chamber 102 of course affects the shape and size of the crucible. INDUSTRIAL APPLICABILITY The reactor of the present invention can be used in the production of solar cells for the production of high-purity germanium produced by the reactor of the present invention, and can be used for materials for solar cells without problems. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a reaction furnace 1 according to a first embodiment of the present invention. Fig. 2 is a schematic flow chart showing the continuous manufacturing (矽 2〇 manufacturing equipment) by the fluidized layer zinc reduction method. Figure 3 is a schematic diagram showing the electrolysis program 40. Fig. 4 is a schematic view showing a reaction furnace 101 according to a second embodiment of the present invention. Fig. 5 is a schematic view showing a bottom plate 200902442 106 of a reactor 101 according to a second embodiment of the present invention. Fig. 6 is a schematic view showing another modification of the reactor 1〇1 according to the second embodiment of the present invention. Fig. 7 is a schematic view showing the state in which the seed crystal is epitaxially grown in the reaction chamber. Figure 8 is a graph showing the growth pattern of Shi Xizhi's insect crystal. Figure 9 is a graph showing numerical simulation results according to Equation 1. In the first diagram, when the product photograph '10th (8) diagram condition A generated by each of the conditions A to c of Table 2 of the first embodiment is used, the first 〇(9) diagram condition is called, and the 10th 10th (c) diagram is Condition C. Fig. 11 is a graph showing the results of a sample sampled from condition B of Fig. 10 by x-ray analysis. Figure 12 shows a graph showing the results of sample masses sampled from the first condition B. J 10...Material supply program 15...chlorination procedure 20". Steamer refining procedure 15 [Main component symbol description 1,101...reactor

2,102...reaction chambers 3,103...take out chambers 4,104...first take-out chambers 5,105...second take-out chambers 6,106."bottom plate 7...containers 8,9,108 ' 109·.. blocking doors 21, 31, 31b, 31d, 31e, 31f, 32, 33, 41, 42, 42a, 42b, 109a, 109b, 109c, 109d, 110a, 110b, 203 > 204 > ..f 21a,34,35, 111.·Introduction tube 41 200902442 30...Reduction procedure 107...zinc vapor supply holes 31a, 31c...exhaust pipe 110".obstruction plate 40...electrolysis program 111a." front end 43,44...electrodes 120,120c...heating mechanism 46...electrolytic cell HOa...first heating mechanism 50...transportation program 120b...second heating mechanism 60...block manufacturing program 200...separation The upper portion 201...the separation chamber 102b...the lower portion 202...the third extraction chamber 42

Claims (1)

200902442 X. Patent application scope: 1. A reaction device for manufacturing raw materials for solar cells, which is used to manufacture a reaction device for ruthenium by the method of ruthenium tetrachloride, and the above four gasification words The reduction method uses the vaporized ruthenium tetrachloride and the zinc which has been gasified, and the reaction furnace of the above reaction apparatus is vaporized in the foregoing ruthenium tetrachloride which has been gasified in the aforementioned reactor, and has been vaporized. The zinc and the carrier gas are ejected from the bottom of the reaction furnace to form a fluidized layer, and the zinc and the foregoing antimony tetrachloride are subjected to a reduction reaction in the fluidized layer' and continuously generate a diameter number "xn~mm The grainy stone eve. 10 2. The reaction apparatus for manufacturing a raw material for a solar cell according to the first aspect of the patent application, wherein the reaction furnace comprises: a reaction chamber for causing the zinc and the foregoing tetrachloride to be in the fluid layer a middle reactor; and a take-out chamber disposed at a lower portion of the reaction chamber, and for taking out the above-mentioned flaws generated in the above-mentioned reduction reaction and falling by gravity, and further provided on the bottom plate of the reaction a plurality of zinc vapor supply ports for supplying the zinc, and the reaction chamber has an introduction tube for ruthenium tetrachloride for supplying the ruthenium tetrachloride and rising from the bottom plate, and the extraction chamber is provided in the reaction. The bottom of the furnace is connected to the reaction chamber, and the take-out chamber includes: the first take-out chamber is placed in the front of the reaction chamber; and the second take-out chamber is used to The temperature of the above-mentioned first room drop is lowered to a low temperature and taken out. 43 200902442 3. The reaction apparatus for manufacturing a raw material for a solar cell according to the second aspect of the patent application, wherein the take-out chamber is provided with: a carrier gas introduction tube for the carrier gas; and an exhaust pipe for discharging In the reduction reaction, the vaporization generated at the same time as the above-mentioned ruthenium, the unreacted zinc, the unreacted ruthenium tetrachloride, and the carrier gas. 4. The reaction apparatus for producing a raw material for a solar cell according to the third aspect of the patent application, wherein the carrier gas system is an inert gas. 5. The 10th reaction apparatus for producing a raw material for a solar cell according to the second aspect of the patent application, wherein the zinc is supplied from a plurality of through holes and/or slits provided in the entire bottom plate, and is supplied and filled. The aforementioned reaction chamber. 6. The reaction apparatus for manufacturing a raw material for a solar cell according to the second aspect of the patent application, wherein the bottom plate has a plurality of second through holes or between 15 gaps, and the generated lanthanum is disposed on the bottom plate. The second through hole and/or the gap are dropped into the take-out chamber. 7. The reaction apparatus for producing a raw material for a solar cell according to the second aspect of the patent application, wherein the reactor is made of a ceramic material such as quartz or tantalum carbide. 20. The reaction apparatus for manufacturing a raw material for a solar cell according to claim 2 or 7, wherein a plurality of heaters are disposed on a side wall of the reaction chamber to provide the foregoing under the optimum conditions of the reduction reaction. Temperature control is performed in the reaction chamber, and a plurality of temperature zones of a plurality of temperatures are formed in the longitudinal direction of the reaction chamber. 44 200902442 9. The reaction apparatus for manufacturing a raw material for solar cells according to item 8 of the patent application, wherein the plurality of temperature zones are temperature zones of 850 ° C to 1200 ° C. 10. The reaction apparatus for manufacturing a raw material for a solar cell according to the eighth aspect of the patent application, wherein the fluidized bed temperature of the reaction chamber is temperature controlled in a range of about 900 ° C to 11 ° C. 11. The reaction apparatus for producing a raw material for a solar cell according to the second or third aspect of the patent application, wherein the material of the first extraction chamber is a ceramic material such as quartz or tantalum carbide. 10. The reaction apparatus for producing a raw material for a solar cell according to the second or third aspect of the patent application, wherein the first extraction chamber is temperature-controlled at 700 ° C to 1000 ° C. 13. The reaction apparatus for producing a raw material for a solar cell according to the second aspect of the patent application, wherein the temperature of the low temperature is normal temperature. A reaction apparatus for producing a raw material for a solar cell according to the second aspect of the invention, wherein the second take-out chamber has a carry-out mechanism for continuously carrying out the generated crucible. 15. The reaction apparatus for manufacturing a raw material for a solar cell according to the second aspect of the patent application, wherein an energizable gold 20 core is disposed inside the reaction chamber, and the temperature is controlled to be higher than the foregoing reaction. The chamber wall promotes the precipitation of the ruthenium on the metal core, increases the space occupation ratio in the reactor, and improves the reaction rate of the reduction reaction. 16. The reaction apparatus for manufacturing a raw material for a solar cell according to the second aspect of the patent application, wherein the inside of the reaction chamber has an introduction tube, and the 45 200902442 introduction tube is used for supplying a carrier gas and a diameter number // The seed crystal of the size m of m is supplied to the fluidized layer of the reduction reaction from the introduction tube by the carrier gas and the seed crystal, and the seed crystal is grown as a core and promotes the formation of the foregoing . 5 17. The reaction device for manufacturing a raw material for solar cells according to claim 1 or 2, further comprising a separator for separating the aforementioned gas from the gas discharged from the reaction furnace And is a cyclone separator that separates the aforementioned crucible by centrifugal force. 18. The reaction apparatus for producing a raw material 10 for a solar cell according to claim 17, wherein the lanthanum separated from the separator is supplied to the reaction furnace. 19. The reaction apparatus for producing a raw material for a solar cell according to claim 17, wherein a heating mechanism is disposed on a side wall of the separator to perform temperature control in the separator. 15 20. The reaction apparatus for manufacturing a raw material for a solar cell according to claim 17, which is provided with a heating mechanism for heating both the separator and the reaction chamber to separate the separator and the foregoing reaction The temperature control is performed indoors, and the heating mechanism is formed in a plurality of temperature zones in which the plurality of temperatures are formed in the longitudinal direction of the reaction chamber. 46