TW201231392A - Manufacturing method and apparatus of silicon, silicon wafer, and panel for solar cell - Google Patents

Abstract

The present invention provides a method for manufacturing silicon, which can remove impurities, such as boron (B), aluminum (Al) and calcium (Ca), from metallic silicon as a raw material efficiently in a short time by a single process and thereby manufacture metallic silicon of high purity. The present invention resides in a method for manufacturing silicon, which comprises: bringing molten silicon containing impurities and a molten salt into contact with each other; vaporizing the molten salt containing the impurities to form a vaporized product and thereby remove the impurities from the molten silicon; and condensing the vaporized product by condensing means to form a condensed product.

Description

[Technical Field] The present invention relates to a manufacturing method and a manufacturing apparatus for a crucible used as a material for manufacturing a panel for a solar cell, for example. [Prior Art] In the Ju Shi Xi solar cell, a high-purity metal crucible having a specific resistance value of 0.5 to 1.5 Ω·cm or more and a purity of 99.9999% (6N) or more is generally used. The high-purity metal lanthanum raw material is inexpensive, and industrially, it is preferable to manufacture and purify impurities by removing and removing impurities from a raw material metal ruthenium containing a large amount of impurities. Among the impurities contained in the raw material ruthenium, iron, aluminum, titanium, and calcium can be removed to the liquid phase side by solidification by melting the ruthenium (a ruthenium in which the raw material metal ruthenium containing impurities is melted). Further, calcium or the like can be removed by evaporating the molten crucible in a vacuum of about 1.3 χΗΤ 2 to 10 _ 4 Pa (1 (T4 to 10 -6 Torr). However, among the impurities, boron and phosphorus are very difficult to remove, especially boron. It is particularly difficult to remove. For example, in a molten crucible, an oxidation treatment is carried out by adding oxygen or carbon dioxide or water vapor to an inert argon and blowing it into a compound of boron, oxygen or hydrogen (refer to the patent). Document 1 and Patent Document 2) In the above method, it is time consuming to oxidize boron (B) in the raw material metal ruthenium using steam or the like to form BO gas, and at the same time, ruthenium is also oxidized. The loss is large. In particular, if water vapor is sucked into the glazed stone, a large amount of hydrogen is generated due to a side reaction, which causes problems in safety. 100147271 4 201231392 In addition, 'as a method of refining ruthenium using a halogenated base' The proposal is to make slag from the sludge of the raw material metal bismuth (the slag containing cerium oxide as the main component in the raw material cerium), and to adjust the composition for removing impurities to recover the sand. (Refer to Patent Document 3), but this does not necessarily result in a crush of satisfactory purity. Moreover, - in the case of melting, since it is an oxide, the container used is limited to oxides such as cerium oxide or aluminum oxide. It is a refractory material, and there is a problem with the installation. In addition, in the case of induction heating, it is necessary to heat the graphite rod or the like in the container until the crucible is melted, which complicates the process. Further, in the slag method, it is necessary to carry out In the process of separating the ruthenium from the molten slag, there is a problem that the process is complicated. Further, Patent Document 4 describes a step of pulverizing 20 g of the raw material metal ruthenium powder and NaF of the same particle diameter. a step of mixing at a mass ratio of 1:1; a step of contacting the solid stone with molten NaF at 1300 ° C; and a step of melting the second sample according to 1450 t: heating for 10 minutes to melt the NaF and the raw material metal ruthenium The step of cooling the sample (NaF and hydrazine) to room temperature, and separating the ruthenium from NaF in each sample by aqueous dissolution and subsequent decantation and filtering. however In the method described in Patent Document 4, since the ruthenium is separated from the solid matter containing NaF and the raw material metal ruthenium by filtration or the like, the ruthenium is not only purified, but the purification effect is insufficient, and the separation operation is difficult. In the case of the 'constant problem', the vapor pressure of NaF is high near the melting point of Shi Xi (Si), 100147271 5 201231392 If the mixture of Si and NaF is heated, there is a period during which the temperature is raised by heating. The problem of the evaporation of the NaF is disclosed in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. JP-A-62-502319 SUMMARY OF INVENTION Technical Problem An object of the present invention is to provide a method for manufacturing a crucible, which solves the problems of the above-described conventional techniques, and can be made of a raw material metal crucible. Impurities such as boron (B), aluminum (AI) and calcium (Ca) are efficiently removed in a short time and in the same process, and are used as high-purity metal stones. (Means for Solving the Problems) The present invention has been subjected to various reviews in order to solve the above problems. As a result, it has been found that "the ruthenium (hereinafter referred to as "melt enthalpy") which melts the metal ruthenium containing the impurity, and the molten salt are brought into contact with the inside of the container. The impurities such as boron (B), aluminum (A1) and l(Ca) in the crucible are reacted with the molten salt, whereby the volatile compound containing the impurity is dissolved in the molten salt and evaporated into the vapor phase. Therefore, the impurities can be removed outside the system. The present invention has been formed based on these findings. That is, the present invention is as follows. A method for producing a crucible, characterized in that a molten crucible containing an impurity is brought into contact with a molten salt, and a molten salt containing the impurity is evaporated to be an evaporate, and the impurity is removed from the molten crucible by 100147271 6 201231392; The evaporant is condensed into cold by means of condensation; 2. The method for producing ruthenium according to the above item 1, wherein s is the above-mentioned cold; molten salt is used. The product is manufactured according to the above item 1 or 2, and the above-mentioned "eighth" is caused to fall by the condensation means, so that the molten condensate in the condensate is screamed and melted; 4. The method for producing a shovel according to any one of the above items 1 to 3, wherein the condensate attached to the condensing means is condensed by a condensing hand & 5. as in the above items i to 4. The manufacturing method according to any one of the preceding claims, wherein the condensate adhering to the condensing means is removed by the condensing means by exchanging the condensing means. 6. The method for producing a shovel according to any one of the items 1 to 5, wherein the condensing means cools the evaporant to be condensed and is cooled in an upper portion of the system. means. 7. The method for producing a crucible according to any one of the preceding claims, wherein the temperature of the condensate is set to be a solidified product by setting it to a melting point or lower of the molten salt. 8. The method for producing a crucible according to any one of the items 1 to 7 above, wherein, after the impurities are removed from the molten crucible, the molten salt is evaporated and removed to the outside of the system. A method of producing the method, wherein an inert gas is blown into the molten crucible. The method for producing a crucible according to any one of the items 1 to 9, wherein the impurities include boron. The method for producing a crucible according to any one of the items 1 to 10, wherein the molten W salt comprises a composite salt containing a metal and a metal salt, and a composite salt containing an alkaline earth metal and a halogen. At least one compound selected from the group. The method for producing a crucible according to any one of the items 1 to 5, wherein the molten salt comprises lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), and Dunhua. a mixture of RbF), cesium fluoride (CsF), fluorinated sodium fluoride (Na2siF6), cryolite (Na3A1F6), sodium fluoride and cesium fluoride, and a mixture of sodium fluoride and cesium fluoride and bismuth gasification And at least one compound of the group consisting of such mixtures. 13. The method for producing a shovel of the above-mentioned item 1 to 12, wherein the amount of the molten salt is 5% by mass or more and 30% by mass or less based on the amount of the lanthanum. A slave manufacturing apparatus for contacting a marsha (4) containing impurities with a molten salt to evaporate the impurity-containing salt into an evaporate, thereby removing the impurity by the smelting, which has: a container having a bottom a side portion and an upper opening portion filled with the molten strontium and the molten salt; and a heating means for heating the molten enthalpy containing the temporary temporary λ and the molten salt; 100147271 8 201231392 condensing means, The upper opening of the container is further above, and the evaporating substance is condensed into condensate; and the discharging means discharges the impurities removed by the molten enthalpy by reaction with the molten salt. 15. The manufacturing apparatus according to the above item 14, further comprising means for adding a molten salt to the container. 16. The manufacturing apparatus according to the above item 14 or 15, wherein the condensate is further reused as a molten salt. The manufacturing apparatus according to any one of the items 14 to 16, further comprising means for removing the condensate adhering to the condensation means from the condensation section. The manufacturing apparatus according to any one of the preceding claims, wherein the condensing means has a side wall extending in a downward direction of the system, and a hollow cylindrical body having an upper portion and a lower portion formed as an opening portion. 19. The manufacturing apparatus according to the above item 18, wherein the partition member is provided inside the cylindrical body. The manufacturing apparatus according to any one of the preceding claims, wherein the condensing means has a side wall extending in a downward direction in the system, and a cylindrical body having a lower portion formed as an opening and closed at an upper portion. The manufacturing apparatus according to any one of the preceding claims, wherein the condensing means is a plate-like body extending in a direction intersecting the upper and lower sides of the system. 100147271 9 201231392 A documented manufacturing apparatus 'where, as a cooling element, as in the previous paragraphs 14 to 21 of the cup, the above condensation hand (four) is used to cool the condensate. 23. The apparatus according to any one of the preceding paragraphs 14 to 22, wherein the container is made of graphite or bismuth telluride. ‘, 24. As in the manufacturing equipment of Shi Xi, which you recorded in the preceding paragraph , to 23, the step-by-step method has the attraction means for attracting the cut evaporation. 25. The manufacturing apparatus according to any one of the items 14 to 24, wherein the step further comprises means for recovering the evaporant. 26. The manufacturing apparatus according to the above item 25, wherein the recovery means is any one of a cyclone, a bag state, or a wet trapping means. 27. A wafer wafer comprising the crucible obtained by the method of manufacturing according to any one of clauses 1 to 13 above. A panel for a solar cell, which comprises the crucible obtained by the manufacturing method described in any one of the items 1 to 13. (Effect of the Invention) According to the present invention, the molten cerium containing impurities such as boron (B), aluminum (A1), and calcium (Ca) can be brought into contact with the molten salt in the system to form the liquid phase and the molten salt. The interface of the liquid phase, through which the impurities in the crucible react with the molten salt, can efficiently remove the impurities. That is, according to the present invention, it is possible to provide a process for producing a crucible which can efficiently remove impurities contained in the molten crucible in a short time and in the same process, and to form a high-purity metal crucible. 100147271 10 201231392 For a (four) at the θ interface, the impurities in Shi Xizhong are reacted with the secret salt, and the resulting reactants, which are partially removed, are partially dissolved in (4) salts. Here, since the (iv) salt has a tendency to evaporate while reacting with the shirt and the impurities, it is preferable to use the salt of the molten salt to be treated. Record the towel to participate in the reaction. In particular, in the present invention, the base material containing the molten salt is condensed into a condensate by means of condensation in the reaction system, and (4) the condensate is used as the (iv) salt, thereby circulating the molten salt in the reaction system, and therefore, Waste the enthalpy and participate in the reaction. Further, the towel of the present invention fills and cuts the condensate entangled + segment yarn attached to the condensing means, and the entanglement of the contact condensed in the condensing means. That is, according to the present invention, it is possible to provide a method for producing a crucible which further improves the efficiency of purifying a high-purity metal crucible. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail, and the description of the components described in (4) is only an example (representative example) of the embodiment of the present invention, and the present invention is not limited to the premise of not exceeding the gist thereof. In the following content. In the present specification, the term "in-system" means evaporation of impurities, reaction of a molten salt, evaporation of a molten salt, condensation of an evaporate containing a molten salt, and condensate by reaction of molten enthalpy with a molten salt, reaction with a molten salt. The place where the fall occurred. For example, in a casing having a discharge port, a heating means or a container is housed, and the inside of the casing is purified, and the impurities are evaporated and removed through the discharge port, so that the inside of the casing can be regarded as a system. On the other hand, the term "system 100147271 11 201231392" refers to the case where the evaporating substance of the salt is removed (4) and contains the scent. • Refined place. For example, the outside of the frame can be regarded as a manufacturing method of the system. :::: The method is characterized in that the TM has impurities (4). The salt of the impurity (IV) is evaporated into an evaporate, a borrowing. Hereinafter, the evaporating material #condensing means is condensed into condensation by *1 impurity. That is, the manufacturing method of the present invention is divided into steps to explain. The method for manufacturing the melting stone Xilin salt (four) t includes: making the impurity containing impurities as the evaporating material, # this = internal contact, evaporating the molten salt containing the impurity and including: removing the impurity by melting the stone (Steps are called S2). In the present invention, the step of condensing the facial hair into condensate (step S2. 'It is preferred to carry out step S1 and step 1.1. step si miscellaneous TM in the system, so that the impurity containing the shaking is reacted with the molten salt. The resulting reactants are partially removed from the filaments to the outside of (10), and partially dissolved in the dazzle. The dissolved (10) impurities of the molten salt can be removed together when the salt is removed by evaporation. In the case of the molten salt, the metal ruthenium which is a raw material is melted. The raw material ruthenium contains at least boron (B) as an impurity, and may further contain, for example, phosphorus (p). Iron (Fe), aluminum (A1), calcium (Ca) or titanium (Ti), etc. In the present invention, among these impurities, boron (B), aluminum (A1) and calcium (Ca) are particularly suitable for removal. The total concentration of impurities in the raw material metal ruthenium is preferably from 1 〇 to 50 ppm, more preferably from 10 to 3 〇 PPm. The raw material metal enamel belonging to such a concentration range can be easily replaced by arc carbon or the like. It is preferable to obtain a low temperature, so that the molten salt is melted at the melting temperature of the raw material metal ruthenium. And contacting the molten crucible containing impurities to form an interface between the liquid phase of the crucible and the molten salt, thereby reacting with impurities such as boron (B), aluminum (A1) or calcium (Ca) in the molten crucible. a compound which can evaporate impurities into a gas phase, or a compound which dissolves impurities in the molten salt itself and which can be evaporated from impurities, and is not particularly limited. The smelting salt can be added to the system in a solid state in the system. It may be melted in the inside, and may be, for example, at least one compound selected from the group consisting of a complex salt containing an alkali metal and a halogen, and a complex salt containing an alkaline earth metal and a cerium. Lithium (LiF), sodium fluoride (NaF), potassium fluoride (KF), cesium fluoride (RbF), fluorinated planer (CsF), sodium strontium fluoride (NajiFj, cryolite (NaAlF6), fluorinated a mixture of sodium and cesium fluoride, and a mixture of sodium fluoride and a mixture of cesium fluoride and cesium chloride, or a mixture of such a mixture. Among these, a large amount of molten salt is inhibited from being inhibited by strontium. In the case of ingredients, and 100147271 13 201231392 In the case of the component, it is preferred that the τ is easily purified, and it is preferably a fluoride of an alkali metal, and particularly preferably NaF. In the case where the raw material metal ruthenium is dissolved, an oxide film is formed, but in the present invention, The oxide can be dissolved in the above molten salt. Further, if the above molten salt is used, ordinary graphite can be used as the container, which is also preferable from the viewpoint of economy = point. When it is formed in the liquid phase of the molten crucible, a molten salt having a density smaller than cerium (Si) can be used. As the molten salt, for example, an alkali metal fluoride salt having an atomic number of less than Cs can be used. The lower the impurity content in the molten salt, the lower the impurity content in the molten salt. Good, but even if the molten salt contains impurities 'the impurities are mostly fluorinated', most of them are evaporated at the treatment temperature, which does not cause any problem. This can be used as a dazzling salt. Here, the treatment temperature means the melting temperature of the raw material metal ruthenium. The amount of the molten salt used is preferably 5% by mass or more, more preferably #% or more, still more preferably 2% by mass, more preferably 30% by mass or more, based on the raw material cerium (melting enthalpy). Further, it is preferably 3% by mass or less, more preferably 5% by mass or less, still more preferably 70% by mass or less, and particularly preferably 5 (% by mass or less). When the amount of the molten salt used is 5% by mass or more, a sufficient purification effect can be obtained. Further, in the method for producing a material according to the present invention, the step of condensing the evaporant in the system by condensation means as a condensate by the step S2' described later, and using the condensate as a molten salt, can be reduced. The smelting salt makes 100147271 14 201231392 dosage. The shape of the raw material metal gamma (10) which is formed at the liquid phase interface between the smelting stone and the molten salt is simultaneously heated and melted = the form in which only the molten metal salt is heated and melted as a raw material. ~, in the case of the raw material metal stone 愈 炫 炫 趟 趟 . θ θ θ θ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The condensate is condensed by the condensing means as a condensing / #w degree down to the melting enthalpy', and the condensate can be used as a melt rider to suppress the loss of the scented salt. In addition, the molten salt can also be used as needed: / buckle σ is heated and melted and then cooled; The temperature at which the metal metal and the molten salt are heated and dazzled is preferably a melting point of Shi Xi, 2000 Ϊ / above 145 ° ° C. Further, the upper limit of the temperature is preferably 2000 C or less, more preferably 17 F (vrc or less): Here, by contacting the molten stone with the molten salt, the interface of the shixi liquid phase without melting...the night phase can be formed. The interface between the liquid phase and the liquid phase of the molten liquid can react the impurity amalgam in the molten metal, and the impurity can be evaporated to the gas phase or the private line to the molten salt. The interface with the liquid phase of the smelting and melting salt causes the pores of the decomposition product formed by the partial decomposition of the molten salt or the composite compound to the stone eve, thereby making the impurity in the molten stone Reacts with the molten salt. The reaction time, that is, the contact time between the smelting and the smelting salt, is usually better than 100147271 201231392 (more than u hours, better than 25 hours, more than μ hours). It is preferably 12 hours or shorter, more preferably 6 hours or shorter, and particularly preferably 2 hours or shorter. The longer the reaction treatment time, the more effective the reduction of impurities is, but from the viewpoint of process cost, it is preferably shorter. The impurities contained in the interface between money and bribes The chemical substance, that is, the reactant which reacts the impurities in the stone stalk with the smelting salt, is evaporated or partially dissolved in the human hetero-salt salt, and the salt can be recorded and evaporated to be removed by evaporation. Decompression degree) If it is atmospheric, it is better to use Pa as the case may be. In addition, when evaporating and removing, 1 inert argon and the like are inhaled and mixed (4) as a rhyme gas, and the 敎 domain is removed, so it is compared with /j- Flow, which can further promote the reaction of impurities. In order to increase the melting (4) relative to (4), it can also be heated by, for example, electromagnetic induction. The moving speed is changed by the flow of molten/wormite relative to the molten salt. The large-scale reaction-promoting reaction is caused by the fact that the boundary layer of the function of the reaction site is relatively thin near the interface between the material phase and the salt-making phase. Limiting force of movement:: The two cuts make the boundary m more than (four)% and (4) the salt becomes Ronghan wrong. In addition, the method of the following «10) can also be further advanced. The reaction of molten salt. Into the impurity and 100147271 201231392 (1) A method of blowing an inert gas into a liquid phase. (II) Using a 冋 frequency sense The method of inductively stirring the Shixi liquid phase in the furnace (III) The method of mechanically detaining the Shangyu Xuan (5) salt to the lower layer of the stone layer. The mechanical beneficiary refers to the use of mechanical means. For example, a concave mold made of graphite is used to push the molten salt into the lower layer of the stone layer. The garment - (iv) a method of stirring the liquid phase using a rotor. W. blowing the powder of the molten salt together with the inert gas The method in the liquid phase of the Shixi. After the impurities and the salt are removed by evaporation, if necessary, the residual molten salt can be removed by vacuum evacuating the inside of the container and can be cured by curing the crucible.冋 ( (4). In the case of (four), the so-called unidirectional solidification can be used to remove the residual impurities by segregation, and a higher purity can be obtained. When the metal is removed, it can be made into a higher purity stone eve. The removal of the metal can be carried out by a known general method. For example, it can be easily removed by (4) etc. by the true line scale. The specific example of the step S1, its function, and the like will be described in more detail below. (a) In the case of using sodium fluoride (NaF) as a molten salt. The proportion under 50〇t is about! 8, lighter than Shi Xi (about 2.6) light. Therefore, in the system, the interface between the lower layer of the liquid phase and the upper layer of the liquid phase is formed. In this case, it is considered that the following reaction occurs through the interface: boron (B) which is miscellaneous in the molten crucible is evaporated as a reactant to the gas phase, and a part of the solution is dissolved and transferred to the molten salt. 4NaF + B = 3Na + NaBF4, or 3NaF + B = 3Na + BF3 In addition, aluminum (A1), which is an impurity in the molten crucible, also reacts as follows. Unlike boron, the product has a low vapor pressure, so in this case it dissolves in the molten salt and is removed together when the molten salt is removed by evaporation. A1 + 6NaF = Na3AlF6 + 3Na In order for the reaction to proceed rapidly, it is important to remove the reactants quickly. The removal of the reactant is preferably carried out by blowing a carrier gas such as argon gas into the molten crucible in the system, and removing the reactant together with the carrier gas to the outside of the system. On the other hand, although a part of Na in NaF is ingested into the molten stone, it can be removed by the above-described alkali removal treatment.

Although NaBF4 and BF3 are considered to be the first to dissolve in NaF, their vapor pressure

It is also relatively common, and most of it evaporates during the process. Even if impurities are dissolved in NaF, NaF can be removed by evaporation together with impurities by increasing the temperature in the latter half of the process or by evaporating under reduced pressure. Aluminum (A1) or calcium (Ca) is also removed from the molten crucible by the same process. The aluminum (A1) or calcium (Ca) system reacts with NaF to form Na3A1F6 and NaCaF5, respectively, and dissolves in the smelting salt, which is removed in the process of removing the sulphate salt. Further, it is also considered that NaF reacts with si to form siF4, and gas SiF4 reacts with impurities, and any impurity can be used as a high vapor pressure fluoride. 100147271 18 201231392 is removed. (b) A composite compound of NaF and SiF4 (Na2SiF6) is used as a smelting enthalpy. A composite compound having a resistance to ton can also be used. At this time, the part of Na2S!F6 decomposes before it becomes a liquid phase, and becomes NaF and SiF4. Since SlF4 is a gas, it is preferable that the gas reacts with impurities in the melt if the (four) sand is mechanically pushed into the molten stone. Further, since the reaction between the secret and the liquid phase dream (Si) is suppressed, the superiority of the yield of the refined slave is enhanced. * These reactions are usually preferably carried out at a pressure of 5 to 2 Torr, and it is economically preferable to use a large gas sealed by an inert gas such as argon. Even at atmospheric pressure, the molten salt is almost evaporated. Furthermore, in the case of complete removal, it is preferably set to a vacuum of about 13 〇 _ _ (1 〜 1 (^) to evaporate. Thus, it becomes only a stone eve in the melt, by casting a person to It can be easily recovered in the mold. 1.2. Step S2 The method for producing the sand of the present invention has the feature of the above step W, step S2. Step S2 is in the system mr ^ ^ λ, so that 3 has the melting of the miscellaneous _ The cold things in the cold section of the cold goods "as a step of condensate. Two two = ΓΤ" most of the - not involved in the molten condensate = condensation in the system by condensation means condensate. Cold 3 has molten salt and melting 矽The method of the present invention has a step of contacting the molten salt in the condensate with the molten crucible by lowering the condensate 100147271 201231392 to the molten crucible. In the manufacturing method, the condensate is used as a molten salt in the system. The condensing means in the y-heart S2 is preferably provided in the upper part of the system, and more preferably, the condensate is cooled and condensed as a condensate. Cooling means. The so-called system, σ ρ above the gram, refers to the melting stone eve The position above the smelting salt relative to the liquid phase interface of the smelting stone and the molten salt. Thereby, the condensate condensed in the condensing means is dropped to the smelt by, for example, the self-secreting τ, the descending airflow Shi Xi' and participate in the reaction. The specific form of the condensing means (4) will be described later. It is better to make the temperature of the condensate below the melting point of the smelting salt to solidify it and make the condensed product fall to the smelt 14 By solidifying the condensate, it is possible to suppress the impurities from being dissolved in the coagulum. Moreover, the density of the coagulum is high, and it can naturally flow down in the system and easily reach the molten crucible.

Further, when the condensate is fixed to the condensing means, it is preferable to cause the condensate adhering to the condensing means to fall into the melting enthalpy by, for example, imparting vibration to the A condensate and condensing the condensate by the word (4). . Thus, in the manufacturing method of the present invention, the step S2 is performed in step S1. That is, the molten salt evaporated in step S1 is condensed into condensate by means of condensation in step S2, and then the condensate is dropped into the amalgam and used as a nucleus (four), thereby passing the tis local shape _ The interface with the molten enthalpy. In the present invention, the molten salt can be reused in the reaction, whereby the molten salt can be used for the reaction without waste. 100147271 20 201231392 S2, in the manufacturing method of the money heart, the material is processed by the above steps S1 and Then, after the removal of the miscellaneous f, it can be removed. In addition, when the purity is desired, the molten salt can be re-added after the melting, and the steps S1 and S2 are repeated again. : can be = the molten salt removed by evaporation, and then the salt will be melted after the next Shi Xijing system. As the case may be, in the method of manufacturing the other method of the invention, Step S2 can be used to condense the salt in the money and to re-add the dissolved salt to the outside of (4). For example, the impurity concentration in the molten stone is higher, and the refining process is half-step. S2 uses the condensing means to use the condensate molten salt in the system. When the second half of the process with a low degree of heterogeneity in the Hyun (four) towel is more than 80% of the total replacement time, the concentration of the butterfly in the New (four) becomes the mass basis. After lppm or less), after removing the dazzling salt in the system, The new molten salt (unused molten salt or refined molten salt) is introduced into the system, followed by steps S1 and S2. In step S2, if the condensate containing impurities adheres to the condensing means, after a certain period of time, the condensate When the amount of impurities contained therein is increased, the amount of impurities contained in the condensate which is in contact with the molten crucible in the lower portion of the system by natural dropping is also increased. Therefore, the method for producing the crucible of the present invention is to be attached by further containing The step of removing the condensate from the condensing means by the condensing means, so that the condensate removal of the impurity content 100147271 21 201231392 can reduce the amount of impurities contained in the condensate which is contacted by the natural drop and the like. The lower portion and the melt are used as a means for condensing the condensate adhering to the condensing means, for example, by condensing a hand attached to the condensed hand of the condensate or not 2 = or by removing the condensate The method of removing the condensate by the condensing means. As the section I for removing the condensate, for example, means for imparting vibration to the condensate, and means for the object (for example) Such as j-shaped model and so on), etc. Called each other 2. Other forms are contained in the Qing Dynasty (8) and the purchase of impurities such as impurities, the impurity = time and the same process - efficient removal of the point of view, You can set up the manufacturing method of Shi Xi with the following steps. 2.1· The form of removing yttrium from the system ^There is oxygen in the system (4), the oxygen bribe _ saki 1 = it is dioxotomy. Dioxide (4) According to the solid form at the interface of the two less / dish 'sometimes, the interface between the molten salt and the molten stone is reduced.

That is, since the formation of (4) by the dioxins A does not hinder the reaction of the impurities with the thixotropic salt, it dissolves (4). In the above, the formation of the oxide is described. The solitary 'but can also be prevented by the following steps to prevent the oxidation of 100147271, p hunting due to the circulation of oxygen-free gas in the system, and the removal of oxygen from the system 22 201231392 to the outside of the system The melting enthalpy of the impurity is contacted with the molten solute in the jt to cause the impurity in the smear (4) to react with the molten salt, and the manufacturing method of the step (4) of removing the impurity to the outside of the system removes oxygen in the system, and the result is Inhibit the formation of trioxane. At this time, it is also possible to charge a gas containing no oxygen by blowing a gas containing no oxygen into the liquid phase of the molten stone. Thereby, the oxygen in the molten stone can also be driven out of the system, and the formation of the dioxane can be inhibited step by step. As the oxygen-free gas, argon is preferred. Alternatively, when an oxygen-free gas is circulated in the system, the gas may be used as the carrier ILw. That is, impurities removed by evaporation (four) can be removed to the outside of the system by using a gas other than 3 oxygen as a carrier gas. Thereby, oxygen removal and impurity removal can be performed simultaneously. 2.2. In the case where the melting (4) is efficiently recovered, the above description will explain that the molten salt evaporated in the system is condensed and dropped, but the evaporated salt can be recovered outside the system. For example, the dazzling salt can be efficiently recycled by the method of manufacturing the stone. It can suppress (4) the loss of salt salt. It is not necessary to prepare a new molten salt. As a result, it is widely and efficiently refined (4). Wherein, the shape _ 1 is reversed when the _ state is added to the present invention, and the shoulder is applied to the evaporation removal of the molten salt after the completion of the refining of the stone. There is a manufacturing method in which Hr contains the following step (4), which can be used to melt the salt (gas, liquid or powder) when it is effectively smashed outside the system: the salt containing the salt of 100147271 23 201231392 is contacted in the system, The step of removing the path by removing the path of the molten salt from the molten salt by removing the molten salt from the molten salt by the molten enthalpy, and performing the stepping; At the time of listening, it is a step of refining the recovered flue gas as a refined product; the step of the κ to the system, the step of bringing the blood, the 4 product, and the 3 mixed impurities into contact with the system. . Also, doubt! It can be used to prevent the evaporation of the salt from the suction port without causing U to solidify, and to prevent the (four) salt in the circulation path, the best rule π or the circulation path is set to be a bribery view. high temperature. In addition, for example, when the flue gas is high with the thief gas, the wind speed (m · S·1) in the circulation path is set to 5 or more and 3 (u, love; brother 'by suppressing the circulation path The adhesion of the molten salt in the 'can prevent the flow of the second' can also be used, or the 'in the case of the material' can also be (4) the mouth is placed near the (four) salt or liquid surface. Fine this can easily set the temperature of the attraction σ to (four) salt At the temperature above the melting point, the molten salt evaporated by the bow can be efficiently sucked. In addition, the molten salt can be recovered after refining. As a refining method, for example, the trap can be checked to make it cold and cold. The condensate is purified by melting at a temperature above the melting point of the molten salt. For example, the flue gas can be condensed by a cyclone or a bag filter and recovered as a condensate. The wet trap captures the flue gas into the solvent to form a polymer. 100147271 24 201231392 The slurry is used as a solvent in the form of a condensate of block granules. The following effect: the trapping of the aggregate in the form of a block, that is, the block The agglomerate can be more easily smelted and refined than the powder. The basin is considered to be a block-like shape, and the voids are reduced and the density is increased. As a result, the thermal conductivity is still high, so that the heat is easily expected to be caused by (4). The agglomerates are easy to remove and refine the impurities present in (4). 2.3. The form in which the crucible is produced in an atmospheric environment has been described in terms of cutting under the circulation of an inert gas. In the case of a large-scale (4) manufacturing process, it is difficult to completely become an inert gas environment in the system. From this point of view, it is considered that if it can be manufactured in the atmosphere, it can be efficiently manufactured. If it can be manufactured in an atmospheric environment, the manufacturing cost can also be suppressed. However, as described above, in the atmospheric environment, there is a problem that the oxygen dioxide is reacted with the stone to form a oxidized ash, and the reaction interface is reduced. It is solved by the following manufacturing method. That is, by the following method of manufacturing the stone, the molten stone can be appropriately contacted with the molten salt, and the molten crucible containing the impurity and the molten salt are contained. a contact in the oxygen system to cause an impurity in the azalea to react with the (iv) salt, to remove the impurity to the outside of the system, and to supply the molten salt to the liquid portion and/or the portion belonging to the molten crucible, and Oxygen produced in the reaction with oxygen and does not exist in oxygen. 100147271 25 201231392 The part of the compound can be moved to the liquid surface of the fused sun worm by moving the generated oxide to the liquid surface of the scent Partially and / or internally, the part where the oxide is not present. Regarding the oxide cut, in addition to the shape of the movement of the tool or the prop, the induction of the molten stone by induction heating causes the grip to be triggered. a form in which the oxide is moved to a predetermined direction; or a form in which the oxide is removed by electric t treatment, etc. Further, the molten salt may be impregnated into the interior of the smelting stone. The molten salt is supplied to the portion of the inside of the -11 where no oxide is present. With the above form, it is possible to remove impurities by efficiently containing the impurities such as boron (B), aluminum (A1) and calcium (Ca) in the same process. A manufacturing apparatus for cutting a manufacturing method. In the present invention, the "melting enthalpy with impurities and the molten salt are inscribed in the system: the externally fused" impurities are reacted with _ to remove the impurities:: ..., 9 3 melted impurities with impurities contact with the molten bees There is the impurity reading shirt 7 =, so that the (four) building device 'is characterized by being provided in the system; =) except the impurity (1) has a bottom portion and a side portion and an upper opening portion, filled: b). The melting enthalpy and the above-mentioned molten salt are contained in the above-mentioned upper part of the above-mentioned container. Further, a condensing means for condensing the evaporant to serve as a condensate (4) a discharge means for discharging the impurities removed by the above-described squeezing frequency by a reaction with the salt of the above (4), for example, by a frame such as a chamber The inside of the container and the heating means condensing means can be set to "inside the system", and the outside of the frame is set to "outside the system" 1 and then "the outlet is provided as a discharge means by the frame" When the county slaves are refined, the impurities can be removed from the system by the system. 3.1. Container-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- In the molten salt, the liquid is melted into the gas phase, whereby the opening and the discharge hand are removed from the system by the melt. In particular, if r::f' is a manufacturing method in which the present invention can be carried out, the capacity of the graphite or the carbonaceous stone is not determined as appropriate, and can be appropriately adjusted in accordance with the refined form _ (feeding scale). Means 100147271 27 201231392 The heating means is not particularly limited as long as it can be filled in the container <line fusion; In particular, if induction heating is used, the molten salt is melted and the molten salt is inductively stirred to promote the 3.3. condensing means in each unit. The condensing means is provided on the opening of the upper portion of the container. The evaporating material obtained by evaporating the molten salt of the impurities is preferably cold-containing. Preferably, the condensing means is a cooling means for condensing by cooling the steam to be cold/suspect. For example, the condensation means may be provided with a side wall facing the inside of the system, and the upper portion and the lower portion are formed as a middle portion of the opening portion: the inner portion (hollow portion) of the direction extending body exists, and the temperature distribution exists. , % scorpion. This kind of tube is kept away from it and is lowered. That is, the degree of evaporation is cooled as it rises from the inside of the container side, and is finally condensed. The attacker is in the cylindrical body. The manufacturing apparatus of the present invention is preferably a means for recycling the bovine as a molten salt. The means for using the above-mentioned condensation for the cold suspect V is exemplified by, for example, a means for making a molten salt from the upper part of the container. Specifically, for example, a means for lowering the upper portion of the container from the lower portion to the melting portion, for example, a means for imparting a vibration to the condensate to the hand of the molten crucible (for example, a rod such as a J-shaped mold). ' slave used to fall condensation

D, the inside of the scorpion is increased toward the macro crying department by 'for example, natural falling, lower = _ touch' and participating in the anti-library. On the other hand, and the other side, the impurities removed by evaporation are large because of the evaporation of 100147271 28 201231392. Therefore, the inside of the cylindrical body does not condense and rises directly, and is discharged to the outside of the system. Thereby, the condensed molten salt can be supplied again to the 'J: Rong Rongshi in the evening while removing the impurities. Further, the evaporated molten salt may be cooled or condensed in the hollow space portion of the cylindrical body, or may be attached to the inner side wall of the cylindrical body to be condensed. Even the condensate attached to the inner side wall can be naturally dropped to the upper opening portion of the container by peeling off from the side wall or flowing from the side wall. At this time, it is preferable to provide a means for applying vibration to the cylindrical body to promote the falling of the molten salt. The shape and size of the cylindrical body are not particularly limited. In order to cool and condense the evaporated molten salt and to fall freely, for example, it may be a cylindrical body having a port (hollow portion) having the same size as the opening of the upper portion of the container and extending upward from the container. . The material of the cylindrical body is not particularly limited as long as it can withstand the temperature in the system and is less likely to react with the evaporated molten salt. For example, it can be set to the same material as the above container. Further, for temperature control, a heat insulating material such as ceramic may be provided around the cylindrical body. Further, a filter such as carbon fluff may be provided in the opening of the cylindrical body to allow only gas to escape. Further, when the condensing means is a cylindrical body, a partition member may be provided inside the cylindrical body. By separating the members, the surface area inside the cylindrical body can be increased. Moreover, the rise of the evaporated molten salt can also be suppressed. The shape or material of the partition member is not particularly limited. 100147271 29 201231392 In addition, the upper part of the cylindrical body can also be closed. Thereby, the evaporated molten salt can be appropriately captured. Among them, when the upper portion of the cylindrical body is closed, the detachment path as the impurity to be removed by evaporation is preferably provided with a gap between the cylindrical body and the container or the side wall of the cylindrical body. In this way, it is possible to prevent the circulation of impurities and impurities not only in the system. On the other hand, the condensing means may be a plate-like body extending in a direction intersecting the upper and lower directions in the system. In this form, the evaporated molten salt can be condensed in the vicinity of the container side surface of the plate-like body. The special system is set as a water-cooled plate because it can more appropriately condense the evaporated molten salt. The material of the plate-like body may be the same as the above-mentioned cylindrical body. Further, the shape and size of the plate-shaped body can be appropriately determined in consideration of the size of the container. Further, in the case of a plate-like body, it is preferable to provide a gap or a hole as a detachment path for the impurities to be removed by evaporation between the plate-like body and the container or at a portion of the plate-like body. The plate-like body is disposed above the opening of the upper portion of the container. The special system is installed in the system filled with molten salt vapor. In the condensation means, if the evaporated molten salt is condensed to a melting point or less, the effect of dropping the molten salt can be expected. The condensing means is particularly preferred as means for cooling the evaporated molten salt to below the freezing point. Therefore, the unnecessary temperature rise should be avoided, and the condensing means is preferably disposed on the outer side (upper side) than the heating means. In the example, when the heating furnace is used as an induction furnace, it is preferable to use a cylindrical shape having a side wall extending upward from the coil, or a plate-shaped body provided above the coil. Further, in the manufacturing apparatus of the present invention, it is preferable to further provide means for removing the condensate adhering to the condensation means by the condensation means. Further, by means of a means for removing the condensate falling on the condensing means by the condensing means, the condensate having a large amount of impurities can be removed by the condensing means, and the amount of impurities contained in the condensate used as the molten salt can be reduced. The means for adhering the condensate to the condensing means by the condensing means may, for example, be a means for dropping the condensate to the melting enthalpy, for the reaction, and removing the condensate to the outside of the system. Specifically, for example, means for imparting vibration to the condensate, means for scraping off the condensate (for example, a rod such as a J-shaped mold), means for discharging the condensate to a high temperature and discharging it to the outside of the system, and setting the system and the system Externally connected discharge ports, etc. These means may be used alone or in combination. 3. The discharge means discharge means is an evaporate obtained by evaporating a molten salt by a reaction with a molten salt, evaporating a molten salt containing the impurity, or condensing the evaporated product by condensation means. The condensate is discharged to the outside of the system. The manufacturing apparatus of the present invention may also have a plurality of means for discharging. The term "discharge" as used herein refers to the discharge from the system to the outside of the system. That is, as the discharging means, for example, a discharge port for communicating the outside of the system with the outside of the system can be provided. The above-mentioned "discharge port" may be provided in one of the casings such as the chamber. The special system is located on the upper part of the frame. Further, the means for discharging may be a suction means for attracting the evaporate of 100147271 31 201231392 which is obtained by evaporating a molten salt containing impurities. Thereby, the molten salt can be condensed without being escaping. Moreover, the impurities which are removed by evaporation by the attraction means are also attracted, but since the vapor pressure of the impurities which are evaporated by the above is large, the gas is removed to the outside of the system or the temperature outside the system is low. It is condensed and recovered together with the molten salt. Further, in the manufacturing apparatus of the present invention, the means for recovering the evaporating material may be further provided. Preferably, the means of recovery is external to the system of the manufacturing apparatus. For example, after the completion of the purification of Shi Xi, when the molten salt is removed by evaporation, the evaporated salt removed by evaporation can be recovered outside the system by means of recovery, and can be reused as a molten salt in the next purification of the crucible. Specific examples of the means for recovery are preferably those of a cyclone, a bag filter or a wet trapping means. When the refining of Shi Xi is carried out and the smelting salt is removed by evaporation, the cooling means is not acted upon (for example, changing the direction of the cylindrical body or the plate-like body, or removing the shape or the plate-like body from the system to (4) material). Thereby, the molten salt can be smoothly removed by evaporation. In the manufacturing apparatus of the Shishishi, the molten salt may be added to the above-mentioned Rongjiguang. When the molten salt is added to the container, a molten salt which can be added as a solid can be added. In any case, it can be added to the container, for example, by means of a raw material, or it can be directly added to the container by a person who has a (4) 100147271 32 201231392 salt bucket. When the salt is added to the container, the molten form of the slave may be added as a can. Next, the other constitutions and the like other than the present invention will be described in more detail. Specific examples of the money device of the eve, and the manufacturing device of the above 3.5.1. Fig. 1 is a schematic view showing the system 100 of the invention of the present invention. The manufacturing apparatus 100 is composed of a male body, a sealed body 7 and a horse body 3, and a device for the 4th stone 4 after the induction heating (hanging line SU, heat-dissipating material 8, and ribs). The support of the disaster 3: H), and the mold for the transfer, the 9th tooth of the eve is filled in the form of liquid phase separation in the form of liquid phase separation. _ Frame 7 Anzhen has Weng迸 mouth 6 counted in Weitian U, exhaust port 12, raw material input port 6, etc. For use in straight space, please use 〇!~2xH)5P G, body 7 can control the pressure range from a / air to 2 air pressure in the chamber, but seal the frame with the inert gas of the usual Ar More economical. The body coil 2, the heat-dissipating material 8, and the _ 3 system are formed to be body-tilted, so that the processed molten stone i flows into the mold 9 and is shown in Fig. 1, the first report, n-, k out of the tube above the 坩埚3 or the space above the lid - the smelt salt of powder or granules is injected into the filament surface by the raw material input port, and then placed on the 坩埚3 Above. 100147271 33 201231392 The molten salt to be charged is evaporated by heating and melting, but is cooled and condensed when the vapor rises in the tube 13 to become liquid or solid. 'Because of the high density, it is naturally dropped into the crucible 3. cycle. Thereby, the molten salt which is wastefully evaporated irrespective of the reaction can be reduced. Further, the impurity in the molten crucible 1 reacts with the molten salt 2 to form a gaseous reaction product. The gaseous reaction product is removed from the upper portion of the cylinder 13 or the gap η between the crucible 3 and the cylinder 13 is removed to the outside of the system and refined into a molten stone. Further, in order to discharge the gaseous reaction product more efficiently to the outside of the system, it is effective to open the tube 13 away from the trouble 3 after a small amount of time for the gas to pass through the portion of the tube 13 to make the remaining dazzle At this time, since the molten salt is evaporated, impurities are also slightly dissolved in the molten salt, so that the crucible is also refined. The evaporant is discharged from the exhaust port 12 to the outside of the system. It is necessary to 'by repeating these steps, then (4) (4) 1 is highly purified. In the tube above the time 3, or in the upper part of the tube 1

Preferably, the oxide or nitride is coated, for example, by dioxo or chopping, to the purity of the dioxate or nitrided particles. By means of ..., it is easy to prevent the fixing point of NaF. Nine types of coatings can be used as the manufacturing apparatus 200 of 3.5.2. 图 Figure 2 is a schematic diagram of the present invention. In the manufacturing apparatus and apparatus 200 of Fig. 2 after the manufacture of July, in view of the fact that the transfer surface is favorable for the impurity to describe the two liquid phases. The quality treatment is caused by the inert gas... 100147271 : 34 201231392 The body blowing pipe 25 is blown into the liquid phase, and the field is selected to improve the contact state of the two liquid phase interfaces. Thereby, the interface product can be efficiently discharged together with the inert gas. 〃 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于It is also valid. In the case of induction heating, if a power source having a low frequency, for example, about 0.5 to 5 Torr, is used, an induced current is generated in the sputum, and a characteristic tax drop phenomenon occurs, which is preferable. In this case, since it is not necessary to insert a stirring plate or the like into the mechanical stirring of the Shixi melt, the melt can be stirred, which is preferable in terms of pollution. 3-5.3. Manufacturing apparatus 3 of FIG. 3 is a schematic view showing a manufacturing apparatus 3 of the present invention of the present invention (FIG. 3). The manufacturing apparatus·cylinder 13' is provided with a plate 33. Thus, by arranging the plate 33 in place of the upper and lower directions in the system instead of the tube 13, the surface of the plate 33 can be appropriately placed near the surface of the hanging plate 3 side. The evaporating molten salt is condensed in the ground. The manufacturing method of the above-described enamel of the present invention can be suitably carried out by the manufacturing apparatus of the present invention 100, 200, and 300. The form is prepared from a melting crucible containing impurities such as boron (B), aluminum (A1), and calcium (Ca), and can be efficiently removed in a short period of time and in the same process, and can also be prepared as 100147271 35 201231392. For example, it is a device for manufacturing Shi Xi, which is composed of, for example, a halogen (4) containing the impurity and a molten salt in contact with the system, and the smoke of the impurity "(4)"!= is a new object, and the (four) The device, which is manufactured to the outside of the system (4), has a container of ==:r and a molten salt, and contains impurities. · The liquid surface is opposite to the second: the heating means; it is located in the circulation of the smelting stone and the molten salt. r and bow σ; and connected to the suction port and extended to the system and recycling means · two = = Connected: In addition to the material, the attraction means in the circulation path is attracted by the flow series (4). It can be used to melt the salt, and can be reused. _=Recycling means outside the system can be recycled and can be recycled in the county. The position of the salt liquid is opposite to the position 'and 5 is lower than the upper portion of the upper portion of the container. Further, in order to efficiently attract the evaporated (10)_ or impurity', it is preferable to fill the uppermost end of the side wall of the container of the filling. The wind speed (m·/) is set to 〇5 or more. - = When the path is straight, the wind speed is increased, and it is suppressed to adhere to the wall surface of the path. Therefore, if it is too small, the pressure loss becomes large. According to the wind speed (m · 1) of the flow path, the diameter and the air volume of the flow path are determined to be 5 or more and 3 or less. ^ In this form, since the recovered thaw salt is refined, it is possible to enter a 100147271 36 The impurity in 201231392 goes out of the system and has a heating hand that melts the molten salt. The form of the recovery means is not particularly limited, and may be, for example, a rotator or a wet type (four) means, etc., preferably when a wet type collection means is used; In the manufacturing apparatus 4GG of the embodiment of the present invention, the suction means 40 is provided instead of the cylinder η of the manufacturing apparatus of the sand. The suction port of the suction means 4G is provided at a position facing the liquid surface of the smelting smelt 1 and the molten salt 2. Further, since the suction port is provided inside the (4) 3 (lower than the upper opening), the suction port can be effectively attracted. Evaporated molten salt. Thereby, the molten salt can be efficiently sucked without being condensed at the suction port. According to the manufacturing apparatus described above, the manufacturing method of the crucible of the present invention can be suitably carried out. The impurity concentration of ruthenium obtained by the method for producing ruthenium according to the present invention is preferably 2. 〇 ppm or less, more preferably i 5 ppm or less, still more preferably 1.0 ppm or less, and particularly preferably 5 ppm or less. Further, 'M1' is usually preferably 2 〇ρρηη or less, more preferably iSppm or less, still more preferably 2 ppm or less, and particularly preferably 1 ppm or less. Further, calcium (Ca) is usually preferably 20 ppm or less, more preferably 5 ppm or less, still more preferably 2 ppm or less, and particularly preferably 1 ppm or less. Further, in the manufacturing method of the present invention, the impurity concentration can be made smaller than the above value by repeating the above steps S1, 100147271 37 201231392 S2 '. In the evening, the chromaticity can be analyzed by, for example, ICP-MS (Inductively Coupled Plasma Mass Spectrometer). The hydrazine obtained by the production method of the mash of the present invention can also be improved in purity by further combining other purification methods. 4. Use of the crucible The crucible obtained by the production method of the crucible of the present invention can be processed by a known method and used as, for example, a tantalum ingot or a tantalum wafer for a solar cell. Further, it is also possible to use the southern purity stone used as a solar cell element or a solar cell panel. (Examples) Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not to be construed as limited to Further, in the following examples, the impurity concentration (ppm) in the crucible is a value (mass basis) analyzed by an ICP-MS (Inductively Coupled Plasma Mass Spectrometer). Further, the impurity concentration of the raw material metal ruthenium used in the examples was boron (B): ll ppm, phosphorus (P): 13 ppm, iron (Fe): 190 ppm, titanium (Ti): 34 ppm, and Lu (Al). 220 ppm. , #5(Ca) . 4.1 ppm, nano (Na): 0_4 ppm. (Example 1) In the apparatus shown in Fig. 1, it was sealed with argon, and the inside of the frame 7 was set to 100147271 38 201231392 atmosphere, and 3 kg of the raw material metal crucible for purification was placed in a graphite crucible 3, and dissolved by heating. Up to about 50 baht. Thereafter, the cylinder 13 having the same shape as that of the _3 reversal is taken out from the upper portion of the crucible 3, and the molten salt (NaF) is introduced into the crucible of 5 kg from the raw material input port 6, and then the cylinder 13 is placed over the upper portion of the crucible 3, and placed. Two hours. During the standing period, it is considered that the gas generated by the reaction with the hydrazine is released by the gap 14 between the crucible 3 and the cylinder 13. Thereafter, the canister 13 was taken out from the upper portion of the crucible 3, and all of the molten salt (NaF) was evaporated. In this manner, the addition of the molten salt was carried out 6 times per 〇5 kg, and the same operation as described above was carried out, respectively, and finally the tilting was carried out 3', and the stone was poured into a mold and solidified. After the experiment, the inside of the cartridge 3 was observed, and as a result, the evaporated salt of the molten salt (NaF) was hardly adhered except for the portion close to the disaster. The ruthenium was sampled during the first to sixth experiments, and the main impurity concentrations in the ruthenium obtained were as follows. 2nd time: boron (B): 4.7ppm, structure (P): 19ppm, iron (Fe): 200ppm, titanium (Ti) 34ppm, Ming (Al): 5.5ppm, feed (Ca): 2.5ppm, nano ( Na): 9.4ppm 4th: Boron (B): 2.1ppm, Dendrobium (P): 17ppm, Iron (Fe): 200ppm, Titanium (Ti) 33ppm, | Lu (Al): 2.1ppm, i bow ( Ca) : 1.7ppm, nano (Na): 19ppm 6th: boron (B): l.Oppm, filled (P): 18ppm, iron (Fe): 190ppm, titanium (Ti) 34ppm, |g(Al) : l.Oppm, feed (Ca): 1.2ppm, nano (Na): 100147271 39 201231392 15ppm The sixth time (the total input of NaF is 3kg), the boron is reduced to about 10% of the original raw material, and with aluminum, The calcium is greatly reduced together, and the sodium concentration is also sufficiently reduced to the extent that it can be removed in the subsequent process. Further, if the process is continued, the boron concentration can be lowered. (Example 2) Except that as shown in Fig. 2, the gas injection tube 25 was added to the molten crucible, and the addition of the argon gas "thin salt" was carried out three times per 5 kg. 1 Experiment under the same conditions. The argon gas system was set to be continuously blown in at 500 ccm in the experiment. The same as in Example 1 'The inside of the can 13 was observed after the experiment, and as a result, almost no evaporate of molten salt (NaF) was attached except for the portion close to the crucible. Among them, NaF is attached to a part of the argon blowing pipe. It is believed that NaF is cooled in a portion of the argon blowing tube when the molten salt is removed by evaporation. The third time (the total input of NaF is 1.5kg), the main impurity concentration in the obtained Shixi is boron (B): 1.8ppm, phosphorus (P): 16ppm, iron (Fe): 250ppm, titanium (Ti) 38ppm, Shao (Al): 1.2ppm, mother (Ca): 1.8ppm 'Sodium (Na): 6.2ppm, boron, aluminum, calcium are reduced together, and the sodium concentration is also sufficiently reduced to the extent that it can be removed in the subsequent process. . (Comparative Example 1) In Fig. 1, the tube 13 was not provided above the crucible 3, and the same experiment was carried out in the form of opening above the crucible 3. In this case, since the evaporation of the molten salt (NaF) 100147271 40 201231392 is intense, the addition of the slaked salt is set to twice (lkg) per embodiment and is carried out three times. The third time (the total input of NaF is 3kg), the main impurity concentration in the obtained Shixi is boron (B): 3.3ppm, phosphorus (P): 14ppm, iron (Fe): 86ppm, titanium (Ti) 41ppm Aluminum (Al): 4.4 ppm, calcium (Ca): 2.1 ppm, sodium (Na): 33 ppm. Although aluminum and calcium are reduced, although NaF is added, boron is only reduced to 30 °/ of the original raw material. Left and right, it is not enough. It can be seen that NaF, which does not participate in the reaction and directly evaporates, exists in a large amount. Further, the impurity concentration of NaF used in the present embodiment was boron (B): 0.5 ppm, and filled (P): 1.2 ppm. As is clear from the results of Examples 1 and 2 and Comparative Example, the evaporate obtained by evaporating the molten salt containing impurities is condensed into a condensate by means of condensation, and the condensate can be reused as a molten salt to reduce the amount of the condensate. The amount of molten salt used is effectively purified by hydrazine. (Examples 3 to 6) Experiments were carried out in the same manner as in Example 1 except that the amount of NaF added to the molten crucible, the number of times of addition of NaF, and the treatment time (time of holding the cylinder 13) were set to the conditions shown in Table 1. In Table 1, the "condensation means" is "present", which means that the cylinder 13 is provided above the crucible 3. Further, the phrase "removal of the condensate by the condensing means" means "none", which means that the same cylinder 13 is used for the treatment. (Examples 7 to 13) The same procedure as in Example 1 except that the amount of NaF added to the molten crucible, the number of times of NaF addition, and the time between the treatments of 100147271 41 201231392 (the time of holding the cylinder 13) were as shown in Table 1. conduct experiment. In the table, "removal of condensate by condensation means" means "present" means that the cylinder 13 is exchanged for the tube 13 to which no condensate is attached during the treatment. Regarding Example 7, the 5G () gNaF addition force σ (addition amount is 1% by weight relative to Si) was carried out for 6 times, and was kept for i hours. The exchange of the cartridge 13 in Example 7 was carried out 1 hour after the start of the treatment. In Example 8 to 丨〇, the amount of NaF added in the first time was 5 〇〇g, and after the second time, 25 〇g was added each time, and 丨 was added for 5 hours each time. In the eighth to tenth embodiments, the exchange of the cartridge 13 was the same as in the seventh embodiment, and it was carried out 1 hour after the start of the treatment. In the examples 11 to 13, the amount of NaF added in the first time was 500 g, and 200 g was added each time after the second time, and the addition was maintained for several hours. The exchange of the canister 13 is the same as in the embodiment, and is carried out after a lapse of several hours from the start of the treatment. (Comparative Examples 2 to 4) Experiments were carried out in the same manner as in Comparative Example, except that the amount of NaF added to the molten crucible, the number of times of NaF addition, and the treatment time were as shown in Table 1. The impurity concentration in the crucibles of Examples 3 to 13 and Comparative Examples 2 to 4, the boron (B) residual ratio in the crucible, and the yield are shown in Table 1. Further, in Table 1, "the butterfly (b) residual ratio" refers to the concentration ratio at the time of measurement of the initial concentration of boron. Further, the "yield" means the ratio (%) of the amount of niobium cast (recovered) to the amount of niobium dissolved. 100147271 42 201231392

[II α η 夺 , 1 〇Ο — 寸 〇 0.4 0.4 210 S_ 63 4200 63 4200 63 4200 <0.1 450 <0.1 4000 ! <0.1 52 inch · OO 〇CN On Ο Ο^ί m cn ο ;ό(〇PL, Ο 〇〇1-H CS ο ο CO '―'CN 190 220 Ο ο σ\ 00 —CN 110 200 720 1100 720 1100 720 1100 2; s Ο 〇 inch (N Τ—^ ί- Η 140 210 Ο ο m m τ—· CO Ο Ο νο inch—CO ο ο in in ' CN P CN CO cn co CN inchcn co <Ν寸mm cn α\ cn co 〇\ r«H i—l ΓΟ Ο Os in ο vo 〇\ ^Τ) ο σ\ 寸ν〇CN '~H inch α CN CN v〇σ\ cn 〇\ (Ν ΟΟ inchΟΟ (N cn C3 U inch N inch ^ ^ tT) o inch·^―' m \〇寸·一 m ^ cn in csj ^r) m cn CN v〇»—1 r- r- CN rn CO rH οο in i—ί 220 5.1 (N <^><N — O v〇PI〇59 <0.1 v〇O Ό ο ^ ΓΟ ν〇Ο ^ ΓΟ 97 1 260 r^. m rn 卜<N On ^ 2 cn CN Ο -Η CN 240 1.2 *〇 Inch ο ο VO moov〇CN o c5 V〇00 O CN <0.1 <0.1 oq vq ' 〇οο a c5 οο ν〇^Η* Ο inch (N 〇〇 inch v〇〇〇 inch inch O cn 1—η rH ^r Ο卜卜Ο ο (3⁄4 ν〇1—Η rH iH v〇v〇T"H r·^ O inch(T) 〇〇»n 〇s CO 〇> Ό in —0*Ν iT) i〇!λ ?! O CN tH O cn IH i-HO <N - CN 00 ο 〇 \ »-Η CO 1-Η ι—Η PQ οο ^ ΙΤ) ―卜·1—1 CO—inch'<N — CO· ^ 〇On inch v〇d oo m oo οο cn od 00 CO 00 ^ <N inch S in (N inch CN CM »—1 o 〇) — inch ^ cn ^ <Ν 〇oq ' 1-Η Yield (%) II 1 1 II IS 1 ? II 1 1 丨汔II II 丨汔IP I 00 1 οο 1 Γ-It-1 δ 铋卽〇mr—^ O VO §^2 Ο ΟΟ r*H铋& §2 m·!, W τ ο mo ο σ\ 〇22 O v〇o One O inch O v〇O un Ο νο Ο νο NaF added times 1-Η CN mv〇v〇cr\ ν〇 inch Ό rH NaF with respect to Si ▲ addition amount (%) ! 卜 mm 〇〇cn m 卜 P; ο r - Η Ο ! $ if #. 1 1 I condensing means # - Example 3 1 Example 4 Example 5 _i Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Comparative Example 2 Comparative Example 3 Comparative Example 4

ε Inch U3A-00I 201231392 Dan: Ten pairs of real "彳3~13, Comparative Example 2~4" are added to NaF relative to Si (/.) as (4), and after (4) boron (8) residual rate (10) The vertical axis 'means' will be shown in Table 5. ▲ Figure 5 shows that Example 3 to η, which is processed by means of condensation, is compared with the ratio of _ 2 - The residual rate of the stone in the middle of the stone is low. In addition, 'the real off 8~13' which removes the condensate attached to the condensing means during the treatment is compared with the condensate which is not removed by the condensing means. Examples 3 to 6, which can be crushed and purified according to higher efficiency. For Examples 3 to 7, Examples u to 13, and Comparative Examples 2 to 4, the treatment time (hour) was taken as the loose axis to treat the stone. The butterfly in the evening (9) Residual rate (% plotted on the vertical axis ' is shown in Table 6. ... as shown in Figure 6] Examples 3 to 13 treated using condensation means, compared to the method of not using coagulation And the ratio of riding treatment (four) 2 ~ heart can be reduced in the short-term _) residual rate. And 'the condensate attached to the condensation means removed in the treatment Examples 7 to 13 are Examples 3 to 6 which are treated in comparison with the condensate removal by condensation means, which can be carried out with higher efficiency for Examples 3 to 13 and treatment time (hours) as the horizontal axis. The residual ratio (%) of boron (B) in the treated crucible is taken as the vertical axis, and the plotted graph is shown in Table 7. As shown in Fig. 7, it is known that the condensate attached to the condensation means is removed in the treatment. Examples 8 to 1G were compared with Examples 3 to 6 which were not subjected to condensate removal by condensation, and were subjected to hydrazine purification according to higher efficiency. 100147271 44 201231392 From Examples 3 to 13 and comparison As a result of Examples 2 to 4, it is understood that, except for the step of evaporating the molten salt containing impurities into an evaporate and condensing it into a condensate by condensation means, by further passing the condensate attached to the condensing means by condensation means In the step of removing, the enthalpy refining can be carried out according to a higher efficiency. The present invention has been described above by way of the most practical and preferred embodiments, but the present invention is not limited to the embodiment of the present specification. Application The invention may be appropriately changed within the scope of the invention or the scope of the invention as described in the entire specification, and the manufacturing method and the manufacture of the m-day yen and the solar cell panel are also included in the present invention. In the above technical scope, the present invention will be described in detail with reference to specific aspects, but it is known in the art that various modifications can be made in the context of the invention. _ The application for the Japanese special spear application (Special Wish 2_·2 Curry) applied for on December 2nd of the year, the entire contents of which are applied to this. (Industrial Applicability) Manufacturing method of the present invention

It can be used as a material for a panel for MU solar cells, for example. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an example of a manufacturing method of a table_implementation tree. Fig. 2 is a schematic view showing an example in which the present invention can be implemented. The manufacturing apparatus of the manufacturing method of the present invention 100147271 201231392 Fig. 3 is a schematic view showing an example of a manufacturing apparatus capable of implementing the manufacturing method of the present invention. Fig. 4 is a schematic view showing an example of a manufacturing apparatus capable of implementing the manufacturing method of the present invention. Fig. 5 is a graph in which the amount (%) of NaF added to Si is plotted on the horizontal axis and the residual ratio (%) of boron (B) in the treated crucible is plotted on the vertical axis. Fig. 6 is a graph in which the treatment time (hour) is taken as the horizontal axis, and the residual ratio (%) of boron (B) in the treated crucible is plotted on the vertical axis. Fig. 7 is a graph in which the treatment time (hour) is taken as the horizontal axis, and the residual ratio (%) of boron (B) in the treated crucible is plotted on the vertical axis. [Explanation of main component symbols] 1 Melting 矽 2 Molten salt 3 坩埚 4 Coil 6 Raw material input port (input pipe) 7 Frame 8 Heat-dissipating material 9 Mold 10 Support table 11 Gas introduction port 12 Vent port 100147271 46 201231392 13 Tube 14 Gap 25 gas blowing pipe 33 plate 40 suction device 100, 200, 300, 400 矽 manufacturing device 100147271 47

Claims (1)

201231392 VII. Patent application scope: A method for manufacturing a cultivar, which is characterized in that a smelting stone containing a heterofluorene is contacted with a solute and a molten salt containing the impurity is evaporated as an evaporating substance, whereby the melting The enthalpy removes the impurities; the condensate is condensed by condensation means as a condensate. 2. The method of producing a _ 之 之 之 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The manufacturing method according to the first or second aspect of the invention, wherein the condensate is dropped by the condensing means, so that the condensed liquid is melted in contact with the salt. 4. The manufacturing method according to any one of claims 1-3, wherein the condensate attached to the above condensation means is removed by condensation. 5. The manufacturing method according to any one of claims 1 to 4, wherein the condensate adhering to the condensing means is removed by the condensing means by exchanging the above condensing means. 6. The manufacturing method according to any one of claims 1 to 5, wherein the above-mentioned condensing means is condensed by cooling the evaporant as a condensate and is disposed in an upper portion of the system. Cooling means. 7. The manufacturing method according to any one of claims 1 to 6, wherein the temperature of the condensate is set to be less than or equal to the melting point of the molten salt to be solidified. 8. The manufacturing method according to any one of claims 1 to 7, 100147271 48 201231392 to remove the above molten salt, wherein the impurities are removed from the molten enthalpy and then to the outside of the system. And in the case of 9th, the manufacturing method of any of the items 1 to 8 is in the middle, and the inert gas is blown into the melting enthalpy. 10. If you apply for a patent scope! The method of any one of the above-mentioned items, wherein the above-mentioned impurity includes: a manufacturing method according to any one of the claims 1 to 10, wherein the above-mentioned dazzling salt system comprises a metal-containing test and a comparison The composite dish and the mixture of 3 alkaline earth metals and self-complexed salts are selected to a small compound. Xixia 12. If you apply for a patent scope! The method for producing a stone according to any one of the items, wherein the molten salt comprises from lithium fluoride (UF), sodium fluoride (NaF), potassium fluoride (KF), fluoride condensation, and fluorination.铯(CsF) 矽 gasified sodium (NajiF6), cryolite, a mixture of sodium fluoride and cesium fluoride, and a mixture of sodium fluoride and cesium fluoride and gasified ruthenium, and mixtures thereof The method for producing a crucible according to any one of the preceding claims, wherein the amount of the molten salt is 5 masses or more and 300 masses with respect to the melting enthalpy. 〇14. A manufacturing apparatus for a crucible, in which a molten crucible containing impurities is brought into contact with a molten crucible, and a molten salt containing the impurity is evaporated into an evaporate, thereby removing the impurity by reading melt = ,, which is provided : 100147271 49 201231392 Heyi' has a bottom portion, a side portion and an upper opening *, and fills the above-mentioned molten crucible containing impurities and the above molten salt; 'heating means, heating the above-mentioned impurity-containing molten stone and the above-mentioned molten salt Condensing means provided in the above container Above the upper opening portion, the evaporating substance is condensed into condensate; and the discharging means 'discharges the impurities removed by the molten stone by the reaction with the above-mentioned molten salt. 15. Scope of application 帛In the manufacturing apparatus of the 14th item, the manufacturing apparatus of the above-mentioned container is provided with the means for adding the molten salt to the above-mentioned container. The condensate is used as a means of reversing the condensate of the manufacturing equipment of any one of items 14 to 16 in the middle of the condensate. The manufacturing equipment of the “parts of the 17th item” has a side wall extending in the upper and lower directions of the system, and the upper side of the RA is in the form of a hollow cylindrical body. , ^ _ The manufacturing device of the 18th item, in which there is a partition member within the upper (four) shape. 20. If the scope of the patent application is set, the means--the means has the direction === 100147271 201231392 Formed on the side wall and lower part A manufacturing apparatus according to any one of claims 14 to 17, wherein the condensing means extends in a direction intersecting the upper and lower directions of the system. The manufacturing apparatus according to any one of claims 14 to 21, wherein the condensing means is cooled by condensing the evaporant by cooling it A manufacturing apparatus according to any one of claims 14 to 22, wherein the container is made of graphite or tantalum carbide. 24. The manufacturing apparatus according to any one of claims 14 to 23, further comprising a suction means for attracting the evaporating substance. The manufacturing apparatus according to any one of claims 14 to 24, further comprising means for recovering the evaporating material. 26. The manufacturing apparatus of claim 25, wherein the recovery means is any one of a cyclone, a bag filter, or a wet trapping means. 27. A crucible wafer comprising the crucible obtained by the manufacturing method of any one of claims 1 to 13. 28. A panel for a solar cell, which comprises the method of manufacturing according to any one of claims 1 to 13. 100147271 51