WO2012086544A1 - Procédé de préparation de silicium et appareil de préparation, tranche de silicium, et panneau de cellules solaires - Google Patents

Procédé de préparation de silicium et appareil de préparation, tranche de silicium, et panneau de cellules solaires Download PDF

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WO2012086544A1
WO2012086544A1 PCT/JP2011/079189 JP2011079189W WO2012086544A1 WO 2012086544 A1 WO2012086544 A1 WO 2012086544A1 JP 2011079189 W JP2011079189 W JP 2011079189W WO 2012086544 A1 WO2012086544 A1 WO 2012086544A1
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silicon
molten salt
molten
impurities
condensate
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PCT/JP2011/079189
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English (en)
Japanese (ja)
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有田　陽二
幸博 宮元
圭二 山原
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三菱化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/037—Purification

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  • the present invention relates to a silicon manufacturing method and a manufacturing apparatus used as a material for manufacturing a solar cell panel, for example.
  • Polysilicon solar cells generally use high-purity metallic silicon having a specific resistance of 0.5 to 1.5 ⁇ ⁇ cm or more and a purity of 99.9999% (6N) or more.
  • the high-purity metal silicon is most preferable as an industrial method, since the raw material unit price is low, and the impurities are purified and removed from the source metal silicon containing a relatively large amount of impurities.
  • iron, aluminum, titanium and calcium are removed to the silicon liquid phase side by solidifying and segregating molten silicon (silicon obtained by melting the raw metal silicon containing impurities). Can do. Calcium and the like can be removed by evaporating molten silicon in a vacuum of about 1.3 ⁇ 10 ⁇ 2 to 10 ⁇ 4 Pa (10 ⁇ 4 to 10 ⁇ 6 Torr).
  • boron and phosphorus are very difficult to remove, and boron is particularly difficult to remove.
  • oxygen or carbon dioxide, or water vapor is added to inert argon and blown into the silicon to be gasified and removed as a compound of boron, oxygen, or hydrogen.
  • slag mainly composed of silicon dioxide in raw metal silicon
  • slag mainly composed of silicon dioxide in raw metal silicon
  • this is used for component adjustment when removing impurities
  • Patent Document 3 a technique for recovering silicon
  • slag since it is an oxide, usable containers are limited to oxide refractory materials such as silica or alumina, and there is a problem that the apparatus becomes expensive.
  • Patent Document 4 20 g of raw material metal silicon powder is pulverized, mixed with NaF having the same particle size at a mass ratio of 1: 1, and heated at 1300 ° C. to melt solid silicon with NaF. Contacting, second sample heated at 1450 ° C. for 10 minutes to melt NaF and raw metal silicon, cooling these samples (NaF and silicon) to room temperature, aqueous elution and subsequent decantation And the process of separating silicon from NaF in each sample by filtering.
  • Patent Document 4 merely describes that silicon is purified by separating silicon from solids containing NaF and raw metal silicon using filtration or the like.
  • the work of separating silicon is not easy.
  • the vapor pressure of NaF is high, and when a mixture of Si and NaF is heated, NaF evaporates while the temperature is increased by heating. There was a problem that.
  • the present invention solves the problems in the prior art described above and efficiently removes impurities such as boron (B), aluminum (Al), and calcium (Ca) from the raw metal silicon in the same process in a short time. It is an object of the present invention to provide a method for producing silicon that can be removed to obtain high-purity metallic silicon.
  • silicon obtained by melting raw material metal silicon containing impurities and a molten salt are contacted in a container. And reacting impurities such as boron (B), aluminum (Al), and calcium (Ca) in the silicon with a molten salt to dissolve a volatile compound containing the impurities in the molten salt, or It has been found that the impurities can be evaporated out of the system by evaporating into the gas phase.
  • the present invention has been accomplished based on these findings.
  • the present invention is as follows. 1. Removing the impurities from the molten silicon by bringing the molten silicon containing impurities into contact with the molten salt, evaporating the molten salt containing the impurities into an evaporant, A method for producing silicon, characterized in that the evaporant is condensed by a condensing means into a condensate. 2. 2. The method for producing silicon according to item 1, wherein the condensate is used as a molten salt. 3. 3. The method for producing silicon according to item 1 or 2, wherein the condensate is dropped from the condensing means, and the molten salt in the condensate is brought into contact with molten silicon. 4). 4.
  • 9. The method for producing silicon according to any one of items 1 to 8, wherein an inert gas is blown into the molten silicon. 10.
  • the molten salt contains at least one compound selected from the group consisting of a composite salt containing an alkali metal and a halogen, and a composite salt containing an alkaline earth metal and a halogen.
  • a method for producing silicon according to claim 1. 12 The molten salt is lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), rubidium fluoride (RbF), cesium fluoride (CsF), sodium silicofluoride (Na 2 SiF 6 ).
  • cryolite Na 3 AlF 6
  • a mixture of sodium fluoride and barium fluoride a mixture of sodium fluoride, barium fluoride and barium chloride, and a mixture thereof 12.
  • 13. 13 The method for producing silicon according to any one of items 1 to 12, wherein the amount of the molten salt is 5% by mass or more and 300% by mass or less with respect to the molten silicon.
  • An apparatus for producing silicon wherein a molten silicon containing impurities is brought into contact with a molten salt to remove the impurities from the molten silicon by evaporating the molten salt containing impurities into an evaporated product,
  • a container having a bottom, a side, and an upper opening, and filled with molten silicon containing the impurities and the molten salt; Heating means for heating the molten silicon containing the impurities and the molten salt;
  • a condensing means provided above the upper opening of the container, condensing the evaporate to form a condensate, and a discharging means for discharging the impurities removed from the molten silicon by reaction with the molten salt;
  • a silicon manufacturing apparatus 15.
  • the silicon manufacturing apparatus further comprising suction means for sucking the evaporated material. 25. 25.
  • a solar cell panel comprising silicon obtained by the method for producing silicon according to any one of items 1 to 13.
  • the silicon liquid phase and the molten salt liquid are brought into contact.
  • An interface with the phase can be formed, and the impurity can be efficiently removed by reacting the impurity in silicon with the molten salt through the interface. That is, according to the present invention, it is possible to provide a silicon manufacturing method capable of efficiently removing impurities contained in molten silicon in the same process in a short time to obtain high-purity metal silicon.
  • the molten salt may evaporate without contributing to the reaction with impurities, and it is preferable to recover the evaporated molten salt well and add it again into the molten silicon to contribute to the reaction.
  • the molten salt containing molten salt is condensed in the reaction system by the condensing means to be condensed, and the condensed salt is used as the molten salt to circulate the molten salt in the reaction system.
  • the molten salt can be contributed to the reaction without waste.
  • the quantity of the impurity contained in the condensate which contacts molten silicon can be reduced by removing the condensate adhering to this condensing means from a condensing means. That is, according to the present invention, it is possible to provide a method for producing silicon with further improved efficiency in refining high-purity metallic silicon.
  • FIG. 1 is a diagram schematically showing an example of a manufacturing apparatus capable of performing the silicon manufacturing method according to the present invention.
  • FIG. 2 is a diagram schematically showing an example of a manufacturing apparatus capable of performing the silicon manufacturing method according to the present invention.
  • FIG. 3 is a diagram schematically showing an example of a manufacturing apparatus capable of performing the silicon manufacturing method according to the present invention.
  • FIG. 4 is a diagram schematically showing an example of a manufacturing apparatus capable of performing the silicon manufacturing method according to the present invention.
  • FIG. 5 is a graph in which the horizontal axis is plotted as NaF addition amount vs. Si (%), and the vertical axis is plotted as boron (B) remaining rate (%) in silicon after treatment.
  • FIG. 5 is a graph in which the horizontal axis is plotted as NaF addition amount vs. Si (%), and the vertical axis is plotted as boron (B) remaining rate (%) in silicon after treatment.
  • FIG. 5 is a graph in which the horizontal
  • FIG. 6 is a graph in which the horizontal axis is the processing time (hours) and the vertical axis is the boron (B) remaining rate (%) in the silicon after the processing.
  • FIG. 7 is a graph in which the horizontal axis is the processing time (hours) and the vertical axis is the boron (B) remaining rate (%) in the silicon after the processing.
  • in-system means reaction between molten silicon and molten salt, evaporation of impurities due to reaction with molten salt, evaporation of molten salt, condensation of evaporant containing molten salt, and A place that causes a fall.
  • a heating means or container is housed in a housing with a discharge port
  • silicon is purified inside the housing, and impurities are removed by evaporation through the discharge port
  • the inside of the housing is regarded as the system. be able to.
  • “outside the system” means a place where the recovery of impurities removed from the molten silicon and the recovery / purification of the evaporant containing the molten salt are performed.
  • the outside of the housing can be regarded as outside the system.
  • the method for producing silicon according to the present invention removes impurities from the molten silicon by bringing molten silicon containing impurities into contact with a molten salt, evaporating the molten salt containing impurities into an evaporate.
  • the evaporated product is condensed by a condensing means to form a condensed product.
  • the silicon manufacturing method according to the present invention removes impurities from the molten silicon by bringing molten silicon containing impurities into contact with molten salt in the system, evaporating the molten salt containing impurities into an evaporate. And a step (step S2) of condensing the evaporated product by a condensing unit.
  • step S1 and step S2 are performed simultaneously in the system.
  • Step S1 is a step of removing the impurities from the molten silicon by bringing the molten silicon containing the impurities into contact with the molten salt to evaporate the molten salt containing the impurities to form an evaporated product.
  • the reaction product generated by reacting the impurities in the molten silicon with the molten salt has a high vapor pressure, and part of the reactant is evaporated and removed from the system, and part of the reactant is dissolved in the molten salt. Impurities dissolved in the molten salt can be removed together when the molten salt is removed by evaporation outside the system. As a result, only purified silicon can be recovered from the system.
  • Molten silicon is obtained by melting metal silicon as a raw material.
  • the raw metal silicon contains at least boron (B) as an impurity.
  • B boron
  • boron (B), aluminum (Al), and calcium (Ca) can be suitably removed.
  • the total concentration of impurities in the raw metal silicon is preferably 10 to 50 ppm, more preferably 10 to 30 ppm, based on mass.
  • the raw material metal silicon in such a concentration range is preferable because it can be easily obtained by arc carbon reduction or the like and the cost can be kept low.
  • the molten salt melts at the melting temperature of the raw metal silicon and contacts with the molten silicon containing impurities, for example, by forming an interface between the silicon liquid phase and the molten salt liquid phase, boron (B) in the molten silicon, aluminum
  • the compound is not particularly limited as long as it is a compound capable of reacting with impurities such as (Al) or calcium (Ca) and evaporating the impurities into the gas phase, or a compound capable of dissolving the impurities in the molten salt itself and evaporating with the impurities.
  • the molten salt may be added to the system in a solid state and melted in the system.
  • lithium fluoride LiF
  • sodium fluoride NaF
  • potassium fluoride KF
  • rubidium fluoride RbF
  • cesium fluoride CsF
  • sodium silicofluoride Na 2 SiF 6
  • cryolite Na 3 AlF 6
  • a mixture of sodium fluoride and barium fluoride and a mixture of sodium fluoride, barium fluoride and barium chloride, or a mixture thereof, at least one kind selected from the group consisting of It is preferable to include a compound.
  • alkali metal fluorides are preferable, and NaF is particularly preferable from the viewpoint that a large amount of molten salt component is taken into silicon and can be easily purified even when taken in. preferable.
  • an oxide film may be formed.
  • the oxide can be dissolved in the above-described molten salt.
  • a normal graphite can be used as a container and it is preferable also from an economical viewpoint.
  • molten salt when forming the liquid phase of molten salt on the liquid phase of molten silicon, it is good to use molten salt with a density smaller than silicon (Si).
  • molten salt include alkali metal fluoride salts having an atomic number smaller than that of Cs.
  • the processing temperature refers to the melting temperature of the raw metal silicon.
  • the amount of molten salt used is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass or more with respect to the raw metal silicon (molten silicon). Moreover, 300 mass% or less is preferable, less than 100 mass% is more preferable, 70 mass% or less is more preferable, and 50 mass% or less is especially preferable. By setting the amount of molten salt used to 5% by mass or more, a sufficient purification effect can be obtained.
  • the silicon production method according to the present invention includes a step of using the condensate as a molten salt by condensing the evaporate in the system by a condensing means in step S2 to be described later.
  • the amount of molten salt used can be reduced.
  • the form of forming the liquid phase interface between the molten silicon and the molten salt may be, for example, a form in which the raw metal silicon and the molten salt are mixed and then heated and melted simultaneously. After the molten silicon is formed, the molten salt may be added thereto.
  • the molten salt evaporates and becomes an evaporate until the silicon is melted.
  • the evaporate is condensed by means of step S2 described later. By condensing into a condensate, it can be dropped again into the molten silicon, and the loss of the molten salt can be suppressed by using the condensate as a molten salt.
  • the molten salt may be mixed as necessary, cooled after heating and melting, and converted into a flux.
  • the temperature at which the raw metal silicon and molten salt are heated and melted is preferably the melting point of silicon (1410 ° C.) or higher, more preferably 1450 ° C. or higher.
  • the upper limit of the temperature is preferably 2000 ° C. or lower, and more preferably 1700 ° C. or lower.
  • the interface between the silicon liquid phase and the molten salt liquid phase can be formed by bringing the molten silicon and the molten salt into contact with each other.
  • the impurities in the molten silicon and the molten salt can be reacted via the interface between the silicon liquid phase and the molten salt liquid phase, and the impurities can be evaporated into the gas phase or transferred to the molten salt.
  • the gas in which the molten salt has evaporated or the gas of the decomposition product formed by partial decomposition of the composite compound is allowed to act on the silicon, thereby The impurities can be reacted with the molten salt.
  • the reaction treatment time that is, the contact time between the molten silicon and the molten salt is usually preferably 0.1 hours or more, more preferably 0.25 hours or more, and particularly preferably 0.5 hours or more. Moreover, 12 hours or less are preferable normally, 6 hours or less are more preferable, and 2 hours or less are especially preferable. The longer the reaction treatment time, the more effective the reduction of impurities, but a shorter one is desirable from the viewpoint of process cost.
  • the compound containing impurities generated at the interface between the molten silicon and the molten salt that is, the reaction product obtained by reacting the impurities in the silicon with the molten salt evaporates or partially dissolves in the molten salt. And can be removed by evaporation.
  • the pressure at the time of evaporation removal (pressure reduction degree) is sufficient if it is atmospheric pressure, but it is preferable to reduce the pressure to about 10 ⁇ 4 Pa in some cases.
  • the reaction between the impurities and the molten salt can be further promoted by stirring and flowing the molten silicon.
  • heating may be performed by electromagnetic induction stirring.
  • the reason why the reaction is promoted by increasing the flow rate of the molten silicon with respect to the molten salt is that the boundary layer functioning as a reaction field formed near the interface between the silicon liquid phase and the molten salt layer is made relatively thin. This is thought to be possible. Since the boundary layer serves as a resistance for movement of each molecule when the molten silicon and the molten salt are in contact with each other, it is estimated that the boundary layer is thinned so that the molten silicon and the molten salt are easily in contact with each other.
  • the method according to the following (i) to (v) can further promote the reaction between the impurities and the molten salt.
  • (I) A method of blowing an inert gas into the silicon liquid phase.
  • (Ii) A method of induction stirring the silicon liquid phase using a high frequency induction furnace.
  • (Iii) A method of mechanically pushing the molten salt in the upper layer into the lower silicon layer. The mechanical pushing means that the molten salt in the upper layer is pushed into the lower silicon layer using a mechanical means such as a concave jig made of graphite.
  • (Iv) A method of stirring the liquid phase using a rotor.
  • (V) A method of blowing molten salt powder together with an inert gas into a silicon liquid phase.
  • the inside of the container is evacuated to remove the remaining molten salt and solidify the silicon to obtain high-purity silicon. Further, when silicon is solidified, so-called unidirectional solidification is performed, and remaining impurities are removed by segregation, whereby silicon with higher purity can be obtained.
  • the alkali metal is further removed to obtain higher-purity silicon.
  • the alkali metal can be removed by a commonly used method known per se. For example, it is easily removed by a process such as vacuum processing or unidirectional solidification.
  • step S1 A specific example of step S1 will be described in more detail, including its action and the like.
  • Al Al
  • Al + 6NaF Na 3 AlF 6 + 3Na
  • the reactant is preferably removed by blowing a carrier gas such as argon gas into the molten silicon in the system and removing the reactant together with the carrier gas.
  • a carrier gas such as argon gas
  • Aluminum (Al) or calcium (Ca) will be removed from the molten silicon in a similar process.
  • Aluminum (Al) or calcium (Ca) reacts with NaF to form Na 3 AlF 6 and NaCaF 5 and dissolves in the molten salt, respectively, and is removed in the process of removing the molten salt.
  • NaF and Si may react to produce SiF 4 , and gaseous SiF 4 may react with impurities, but in any case, the impurities are fluorides with high vapor pressure. Can be removed.
  • (B) can also be used as a molten salt complex compounds NaF and SiF 4 (Na 2 SiF 6) If complex compounds NaF and SiF 4 as the molten salt using a (Na 2 SiF 6). In this case, Na 2 SiF 6 partially decomposes before becoming a liquid phase, and becomes NaF and SiF 4 .
  • SiF 4 is a gas
  • the reaction between NaF and liquid phase silicon (Si) is suppressed, there is an advantage that the yield of silicon to be purified is improved.
  • Process S2 The method for producing silicon according to the present invention is characterized in that it includes step S2 in addition to step S1 described above.
  • Step S2 is a step of condensing the evaporated product obtained by evaporating the molten salt containing impurities by the condensing means in the system.
  • step S1 when performing step S1, most of the molten salt evaporates without contributing to the reaction with the impurities in the molten silicon.
  • step S2 the evaporant is not discharged out of the system, but is condensed in the system by the condensing means to form a condensate.
  • the condensate contains molten salt and impurities in the molten silicon.
  • the silicon production method according to the present invention preferably includes a step of bringing the condensate into molten silicon and bringing the molten salt in the condensate into contact with the molten silicon. That is, in the method for producing silicon according to the present invention, the condensate is used as a molten salt in the system.
  • the condensing means is preferably provided in the upper part of the system, and more preferably is a cooling means that condenses by cooling the evaporate to form a condensate.
  • the upper part in the system means a position above the molten silicon or molten salt and facing the liquid phase interface of the molten silicon and molten salt.
  • the temperature of the condensate is solidified below the melting point of the molten salt and the solidified product is dropped onto the molten silicon.
  • the solidified material has a high density, and can fall naturally in the system and easily reach the molten silicon.
  • the condensate adhering to the condensing means is converted into molten silicon by a method such as giving vibration to the condensate or scraping the condensate with a J-shaped rod or the like. It is preferable to drop.
  • step S2 is performed together with step S1. That is, in step S2, the molten salt evaporated in step S1 is condensed by a condensing means to form a condensate, and then the condensate is dropped into molten silicon and used again as a molten salt.
  • the interface between the molten salt and the molten salt is always properly formed.
  • the molten salt can be reused in the reaction system, whereby the molten salt can be contributed to the reaction without waste.
  • impurities in the molten silicon are removed by the steps S1 and S2.
  • the molten salt is preferably removed by evaporation. Further, when it is desired to further increase the purity, it is preferable to newly add molten salt after evaporation removal of the molten salt and repeat steps S1 and S2 again.
  • the molten salt removed by evaporation can be used again as a molten salt in the next and subsequent silicon purification. In some cases, it may be used after purification by a known method.
  • the molten salt condensed in the system by the condensing means in step S2 and the molten salt newly added from outside the system may be properly used.
  • the condensate is used as a molten salt in the system by the condensing means in step S2
  • the latter half of the process in which the impurity concentration in the molten silicon is low for example, When 80% or more of the total purification time has elapsed, or when the boron concentration in the molten silicon is 1 ppm or less on the mass basis), once the molten salt in the system is removed, A molten salt (an unused molten salt or a refined molten salt) may be added and then steps S1 and S2 may be performed.
  • step S2 the condensate containing impurities adheres to the condensing means, and after a certain period of time, the amount of impurities contained in the condensate increases, and the contact with the molten silicon in the lower part of the system due to natural fall or the like The amount of impurities contained in the condensate will also increase.
  • the method for producing silicon according to the present invention further includes a step of removing the condensate adhering to the condensing means from the condensing means, so that the condensate with a large content of impurities is removed, The amount of impurities contained in the condensate in contact with the molten silicon in the lower part can be reduced.
  • condensing by condensing means with a condensate adhering to a condensing means with no condensate adhering or condensing by condensate removing means
  • the method of removing the condensate adhering to a means is mentioned.
  • Specific examples of the means for removing the condensate include means for imparting vibration to the condensate, means for scraping the condensate (for example, a J-shaped bar, etc.), and the like.
  • the reaction between the impurities and the molten salt is hindered by the generation of silica, and there is a possibility that the impurities cannot be removed efficiently.
  • the oxide is described as being dissolved in the molten salt.
  • the formation of silica may be prevented by including the following steps.
  • a gas that does not contain oxygen in the system includes a step of removing oxygen from the inside of the system to the outside of the system, and the molten silicon containing impurities and the molten salt are brought into contact with each other in the system.
  • a silicon production method including a step of reacting impurities in silicon with molten salt and removing the impurities out of the system, oxygen in the system is removed, resulting in generation of silica. Can be suppressed.
  • a gas not containing oxygen may be circulated in the system by blowing a gas not containing oxygen into the liquid phase of the molten silicon.
  • oxygen in the molten silicon can also be driven out of the system, and generation of silica can be further suppressed.
  • argon gas is preferable.
  • the gas when a gas not containing oxygen is circulated in the system, the gas can be used as a carrier gas. That is, impurities removed by evaporation from molten silicon can be removed out of the system using a gas that does not contain oxygen as a carrier gas. Thereby, oxygen removal and impurity removal can be performed simultaneously.
  • the loss of the molten salt can be suppressed, and there is no need to prepare a new molten salt.
  • the molten silicon can be purified in a short time and efficiently.
  • the said form is a concept contrary to above-described process S2.
  • it may be applied at the time of evaporating and removing the molten salt after completion of silicon purification.
  • a method for producing silicon including a step of introducing a purified product into the system and bringing it into contact with molten silicon containing impurities, so that a molten salt (gaseous, liquid, Or powder form) can be recovered.
  • the suction port or the flow channel is made more than the melting point of the molten salt. It is preferable to set the temperature to be high.
  • the suction port may be installed near the liquid surface of the molten salt or molten silicon. Thereby, the temperature at the suction port can be easily set to a temperature equal to or higher than the melting point of the molten salt, and the evaporated molten salt can be efficiently sucked.
  • a purification method for example, fume is collected, condensed and recovered as a condensate, and the condensate can be purified by melting at a temperature equal to or higher than the melting point of the molten salt.
  • fume can be condensed by a cyclone or bag filter and recovered as a condensate.
  • fumes can be collected in a solvent by wet collection to form a slurry, and the slurry can be dried to be recovered as a massive condensate.
  • water is preferably used as the solvent.
  • the following effects are also show
  • agglomerated aggregates can be melted and purified more easily than powders. This is considered to be because the voids are reduced and the density is increased by becoming a lump, resulting in an increase in thermal conductivity, and heat can be easily conducted to the inside. Thereby, the aggregate can be easily melted, and impurities existing inside can be efficiently removed and purified.
  • silicon can be manufactured in an air atmosphere, silicon can be manufactured efficiently. Moreover, if it can manufacture in an air atmosphere, manufacturing cost can also be suppressed.
  • the process includes a step of bringing molten silicon containing an impurity into contact with a molten salt in a system containing oxygen, reacting the impurity in the molten silicon with the molten salt, and removing the impurity out of the system.
  • the oxide generated on the liquid surface of the molten silicon it is preferable to create a portion where no oxide exists in the liquid surface portion and / or inside of the molten silicon.
  • the form of moving the oxide in a certain direction by inducing and stirring the molten silicon by induction heating and inducing flow, or plasma It may be a form in which the oxide is moved or removed by treatment or the like.
  • the molten salt may be supplied to a portion where no oxide exists in the molten silicon by pushing the molten salt into the molten silicon.
  • impurities can be efficiently removed from molten silicon containing impurities such as boron (B), aluminum (Al), and calcium (Ca) in a short time in the same process.
  • Silicon Manufacturing Apparatus A manufacturing apparatus capable of performing the silicon manufacturing method according to the present invention will be described.
  • molten silicon containing impurities and molten salt are brought into contact in the system, the impurities and molten salt in the molten silicon are reacted, and the impurities are removed from the system.
  • a silicon manufacturing apparatus that removes impurities from the molten silicon by bringing the molten silicon containing impurities into contact with the molten salt and evaporating the molten salt containing the impurities to form an evaporated product.
  • a container having a bottom portion, a side portion, and an upper opening and filled with molten silicon containing the impurity and the molten salt.
  • Means Condensing means provided above the upper opening of the container to condense the evaporate into a condensate (4)
  • the container, the heating means, and the condensing means in a housing such as a chamber, the inside of the housing can be made “inside the system” and the outside of the housing can be made “outside the system”.
  • a discharge port as a discharge means in a part of the housing, impurities can be evaporated and removed from the system to the outside through the discharge port during the purification of the molten silicon.
  • the container is filled with molten silicon and molten salt.
  • the impurities in the molten silicon react with the molten salt.
  • the impurities are removed from the molten silicon to the outside through the upper opening and the discharge means by evaporating into the gas phase or by dissolving in the molten salt and evaporating into the gas phase together with the molten salt.
  • the material of the container is not particularly limited as long as the silicon production method according to the present invention can be carried out, but it is preferable to use a container made of graphite or silicon carbide.
  • the shape and size of the container may be appropriately determined according to the scale of the purification process (scale of the heating means).
  • Heating means is not particularly limited as long as it can heat the molten silicon and the molten salt filled in the container.
  • Condensing means The condensing means is not particularly limited as long as it is provided above the upper opening of the container and can condense the evaporated product obtained by evaporating the molten salt containing the impurities into a condensed product. It is not a thing.
  • the condensing means is preferably a cooling means for condensing the evaporated product by cooling it.
  • the condensing means can be a hollow cylindrical body having side walls extending in the vertical direction in the system and having upper and lower openings.
  • a temperature distribution exists, and the temperature decreases as the distance from the container side increases. That is, the evaporated molten salt is cooled as it rises inside the cylindrical body and eventually condenses.
  • the silicon production apparatus preferably further comprises means for reusing the condensate as a molten salt.
  • a means for reusing the condensate as a molten salt for example, a means for dropping from the upper opening of the container onto the molten silicon can be mentioned.
  • Specific examples of means for dropping into the molten silicon from the upper opening of the container include, for example, means for applying vibration to the condensate, means for scraping off the condensate (for example, a J-shaped bar, etc.), etc. Is mentioned.
  • the density of the condensed molten salt increases and contributes to the reaction by coming into contact with the molten silicon from the inside of the cylindrical body to the upper opening of the container, for example, by natural fall or downdraft.
  • the vaporized impurities have a high vapor pressure, the impurities rise without being condensed inside the cylindrical body and are discharged out of the system. This makes it possible to supply the condensed molten salt into the molten silicon again while removing impurities.
  • the evaporated molten salt may be cooled and condensed in the hollow space of the cylindrical body, or may be adhered to the inner side wall of the cylindrical body and condensed. Even the condensate adhering to the inner side wall can be naturally dropped into the upper opening of the container by peeling off from the side wall or flowing down from the side wall. In this case, it is preferable to provide a means for applying vibration to the cylindrical body, which facilitates the fall of the molten salt.
  • the shape and size of the cylindrical body are not particularly limited. Any structure may be used as long as the molten salt is cooled and condensed and freely falls.
  • the molten salt has a mouth (hollow part) of the same size as the upper opening of the container and extends upward from the container. It can be set as a cylindrical body.
  • the material of the cylindrical body is not particularly limited as long as it can withstand the temperature in the system and does not easily react with the evaporated salt.
  • it can be made of the same material as the container.
  • a heat insulating material such as ceramic may be attached around the cylindrical body for temperature control.
  • a filter may be attached to the opening of the cylindrical body with carbon felt or the like so as to allow only gas to escape.
  • a partition member may be provided inside the cylindrical body.
  • the partition member can increase the surface area inside the cylindrical body. It is also possible to control the rise of evaporated molten salt.
  • the shape and material of the partition member are not particularly limited.
  • the upper part of the cylindrical body may be closed.
  • the evaporated molten salt can be appropriately captured and condensed.
  • the condensing means may be a plate-like body extending in a direction intersecting with the vertical direction in the system. Even in such a form, the evaporated salt melt can be condensed near the container-side surface of the plate-like body. In particular, a water-cooled surface plate is preferable. This is because the evaporated molten salt can be condensed more appropriately.
  • the material of the plate-like body may be the same as that of the cylindrical body. Further, the shape and size of the plate-like body may be appropriately determined in consideration of the size of the container. In the case of a plate-like body, it is preferable to provide a gap or a hole as a escape path for impurities removed by evaporation between the plate-like body and the container or in a part of the plate-like body.
  • the installation position of the plate-shaped body may be above the upper opening of the container.
  • it is preferably provided at a position filled with the molten salt vapor in the system.
  • the condensing means the effect of dropping the molten salt can be expected if the evaporated molten salt is condensed below the melting point.
  • the condensing means is preferably means for cooling the evaporated molten salt to below the freezing point.
  • the condensing means is preferably provided outside (above) the heating means.
  • the heating furnace is an induction furnace, it is preferable to use a cylindrical body having a side wall extending upward from the coil, or a plate-like body provided above the coil.
  • the silicon production apparatus preferably further comprises means for removing the condensate adhering to the condensing means from the condensing means.
  • means for removing the condensate adhering to the condensing means from the condensing means By further providing a means for removing the condensate adhering to the condensing means from the condensing means, the condensate having a high impurity content is removed from the condensing means, and the amount of impurities contained in the condensate used as the molten salt is reduced. Can be reduced.
  • Examples of means for removing the condensate adhering to the condensing means include means for dropping the condensate into molten silicon and contributing to the reaction, and means for removing the condensate outside the system. Specifically, for example, means for applying vibration to the condensate, means for scraping the condensate (for example, a J-shaped bar), means for discharging the condensate to a high temperature, A discharge port provided so as to communicate with the outside of the system. These means may be used alone or in combination.
  • Discharging means discharges impurities removed from the molten silicon by reaction with the molten salt, an evaporated product obtained by evaporating the molten salt containing impurities, or a condensed product obtained by condensing the evaporated product by the condensing unit. It is means to do.
  • the silicon manufacturing apparatus of the present invention may include a plurality of discharging means.
  • discharge means discharge from the inside of the system to the outside of the system. That is, as the discharging means, for example, a discharge port provided so as to communicate the inside and outside of the system can be mentioned. As described above, the discharge port can be provided in a part of a housing such as a chamber. In particular, it is preferably provided on the top of the housing.
  • the discharging means may be a suction means for sucking an evaporated material obtained by evaporating a molten salt containing impurities. Thereby, it can be made to condense without missing molten salt.
  • the impurities removed by evaporation by the suction means are also attracted.
  • the impurities removed by evaporation have a high vapor pressure, so they are removed out of the system by gas, or outside the system. Since the temperature is low, it is also condensed and recovered together with the molten salt.
  • the silicon production apparatus may further include a recovery means for recovering the evaporated material.
  • the recovery means is preferably provided outside the system of the manufacturing apparatus.
  • the molten salt when the molten salt is removed by evaporation after the purification of silicon is completed, if the molten salt evaporated and removed by the recovery means is recovered outside the system, it can be reused again as the molten salt at the next silicon purification. Can do.
  • the collecting means either a cyclone, a bag filter or a wet collecting means is preferable.
  • the cooling means is not allowed to function (for example, change the direction of the cylindrical body or plate-like body, or remove the cylindrical body or plate-like body. Remove from inside the system to outside the system). Thereby, molten salt can be smoothly evaporated and removed.
  • the silicon production apparatus of the present invention may include means for adding a molten salt to the container.
  • a liquid molten salt may be added and the molten salt made into solid may be added.
  • it can be added to the container through the raw material input port (input pipe), or may be added directly to the container from a bucket containing molten salt.
  • the powdered molten salt may be added, or the molten salt formed into a rod shape may be inserted into the container and brought into contact with silicon. .
  • FIG. 1 schematically shows a silicon manufacturing apparatus 100 according to an embodiment of the present invention.
  • the manufacturing apparatus 100 includes a chamber 7 that can be sealed or a casing 7 that can be sealed with an inert gas such as argon, a container (crucible) 3 such as graphite disposed therein, a coil 4 for induction heating, a heat insulating material 8 It comprises a support base 10 for supporting the crucible 3 and a mold 9 for casting silicon.
  • the molten silicon 1 and the molten salt 2 are filled in the crucible 3 in the form of liquid phase separation.
  • a gas introduction port 11, an exhaust port 12, a raw material input port 6, and the like are attached to the housing 7.
  • the inside of the chamber can be controlled to a pressure range of about 0.01 to 2 ⁇ 10 5 Pa (vacuum to 2 atm), but it is usually inactive such as Ar. It is more economical to use a gas seal housing.
  • the induction heating coil 4, the heat insulating material 8, and the crucible 3 can be tilted together, and the processed molten silicon 1 is poured into the mold 9.
  • FIG. 1 first, a space above the crucible 3 or between the cylinder 13 and the crucible 3 with the top portion is opened, and powder or granular molten salt is supplied from the raw material inlet 6 to the surface of the molten silicon. After a certain amount has been charged, the cylinder 13 is placed again above the crucible 3.
  • the molten salt that has been charged evaporates after being heated and melted, but when the vapor rises in the cylinder 13, it cools and condenses, becomes liquid or solid, and naturally drops again into the crucible 3 because of its high density. Cycle through.
  • the tube 13 is moved away from the crucible 3 and the remaining molten salt is evaporated.
  • the molten silicon is also purified by this process.
  • the evaporated material is exhausted from the exhaust port 12 to the outside of the system. If necessary, the molten silicon 1 is highly purified by repeating these processes.
  • an oxide or nitride for example, silica or silicon nitride
  • an oxide or nitride for example, silica or silicon nitride
  • high purity silica or silicon nitride particles may be coated. By coating in this way, the sticking of NaF can be easily prevented.
  • FIG. 2 schematically shows a silicon manufacturing apparatus 200 according to an embodiment of the present invention.
  • the manufacturing apparatus 200 of FIG. 2 in view of the fact that moving the interface between the two liquid phases is advantageous for impurity treatment, argon or the like, which is an inert gas, is blown into the liquid phase through the gas blowing pipe 25.
  • impurity treatment argon or the like, which is an inert gas
  • the contact state at the interface between the two liquid phases can be improved.
  • the reaction product of impurities at the interface can be efficiently driven out together with the inert gas.
  • the silicon liquid phase is induced and stirred using a high frequency induction furnace, or the stirring plate is rotated in the molten silicon 1 to stir the liquid phase. This method is also effective.
  • induction heating it is preferable to use a power source having a relatively low frequency, for example, about 0.5 to 5 KHz, because an induction current is generated in the silicon melt and a specific stirring phenomenon occurs.
  • the melt can be stirred without mechanical stirring by inserting a stirring plate or the like into the silicon melt, which is preferable from the viewpoint of contamination.
  • FIG. 3 schematically shows a silicon manufacturing apparatus 300 according to an embodiment of the present invention.
  • a plate 33 is provided instead of the cylinder 13 of the silicon manufacturing apparatus 100.
  • the plate 33 is provided so as to intersect with the vertical direction in the system, so that the evaporated salt can be appropriately condensed in the vicinity of the surface of the plate 33 on the crucible 3 side. it can.
  • the above-described silicon manufacturing method according to the present invention can be appropriately implemented by a silicon manufacturing apparatus as exemplified by silicon manufacturing apparatuses 100, 200, and 300.
  • a silicon manufacturing apparatus may be provided.
  • molten silicon containing impurities and molten salt are brought into contact with each other in the system, the molten salt containing impurities is evaporated into an evaporated product, and a fume containing the evaporated product and the impurities is sucked from a suction port.
  • An apparatus for producing silicon to be removed outside a container having a bottom portion, a side portion, and an upper opening in the system, filled with molten silicon containing impurities and molten salt, molten containing impurities
  • a heating means for heating silicon and molten salt, a suction port provided at a position facing the liquid surface of the molten silicon and molten salt, and a flow path connected to the suction port and extending to the outside of the system are provided.
  • the molten silicon is purified by the silicon production apparatus, the evaporated molten salt and impurities are removed from the suction port through the distribution channel. And can be aspirated and removed Kill.
  • the molten salt can be recovered by the recovery means provided outside the system, and the molten salt can be reused.
  • the suction port may be provided at a position facing the liquid surface of the molten silicon and the molten salt and below the upper opening of the container. Further, in order to efficiently suck the evaporated molten salt and impurities, the wind speed (m ⁇ s ⁇ 1 ) at the uppermost end of the container side wall filled with molten silicon and molten salt is set to 0.5 or more. Is preferred.
  • the diameter of the flow path it is preferable to reduce the diameter of the flow path in order to increase the wind speed and prevent the molten salt from adhering to the wall of the path, but if it is too small, the pressure loss increases. For this reason, it is preferable to determine the diameter and air volume of the flow path so that the wind speed (m ⁇ s ⁇ 1 ) of the flow path is 5 or more and 30 or less.
  • a heating means for melting the molten salt may be further provided outside the system. Impurities dissolved and remaining in the molten salt can be removed by heating and melting the recovered molten salt.
  • the form of the collecting means is not particularly limited, and examples thereof include a cyclone, a bag filter, and a wet collecting means.
  • wet collection means it is preferable to use water as the solvent.
  • FIG. 4 schematically shows a silicon manufacturing apparatus 400 according to an embodiment.
  • suction means 40 is provided instead of the cylinder 13 of the silicon manufacturing apparatus 100.
  • the suction means 40 is provided at a position where the suction port faces the liquid surfaces of the molten silicon 1 and the molten salt 2.
  • the suction port is provided inside the crucible 3 (below the upper opening), it is possible to efficiently suck the evaporated salt. Thereby, it is possible to efficiently suck the molten salt without condensing it at the suction port.
  • the impurity concentration of silicon obtained by the method for producing silicon according to the present invention is preferably 2.0 ppm or less, more preferably 1.5 ppm or less, further preferably 1.0 ppm or less, and 0.5 ppm or less for boron (B). Is particularly preferred.
  • Al aluminum
  • Ca calcium
  • 20 ppm or less is preferable normally, 5 ppm or less is more preferable, 2 ppm or less is further more preferable, and 1 ppm or less is especially preferable.
  • the impurity concentration can be made smaller than the above value by repeating the steps S1 and S2 many times.
  • the impurity concentration in silicon can be analyzed by, for example, ICP-MS (Inductively Coupled Plasma Mass Spectrometer).
  • the silicon obtained by the method for producing silicon according to the present invention may be further purified by combining other purification methods.
  • the silicon obtained by the method for producing silicon according to the present invention can be used as, for example, a silicon ingot or a silicon wafer for solar cells by processing by a known method. Alternatively, it can be used as high-purity silicon used as a material for producing solar cell elements and solar cell panels.
  • the impurity concentration (ppm) in silicon is a value (mass standard) analyzed by ICP-MS (Inductively Coupled Plasma Mass Spectrometer).
  • the impurity concentration of the raw material metal silicon used in the examples is boron (B): 11 ppm, phosphorus (P): 13 ppm, iron (Fe): 190 ppm, titanium (Ti): 34 ppm, aluminum (Al): 220 ppm, Calcium (Ca): 4.1 ppm and sodium (Na): 0.4 ppm.
  • Example 1 In the apparatus as shown in FIG. 1, after sealing with argon, the inside of the housing 7 was brought to atmospheric pressure, 3 kg of raw material silicon metal for purification was placed in the graphite crucible 3, and heated and dissolved at about 1450 ° C. Thereafter, the cylinder 13 having the same form as that obtained by inverting the crucible 3 is removed from the upper part of the crucible 3, 0.5 kg of molten salt (NaF) is introduced from the raw material inlet 6, and then the cylinder 13 is again attached. The crucible 3 was put on top and left for 1 hour.
  • molten salt NaF
  • the gas considered to have been generated by reacting with silicon was released from the gap 14 between the crucible 3 and the cylinder 13. Then, the cylinder 13 was removed from the upper part of the crucible 3, and all the molten salt (NaF) was removed by evaporation. In this way, the molten salt was added six times at a rate of 0.5 kg each time, and the same operation as described above was performed. Finally, the crucible 3 was tilted, and silicon was tilted into the mold 9 to be solidified. . When the inside of the cylinder 13 was observed after the experiment, the molten salt (NaF) was hardly adhered except for a portion close to the crucible 3.
  • total NaF input is 3 kg
  • boron is reduced to about 10% of the original raw material, both aluminum and calcium are greatly reduced, and the concentration of sodium can be removed in subsequent processes. It was low enough. Furthermore, if this process is continued, it is possible to reduce the boron concentration.
  • Example 2 As shown in FIG. 2, the same as Example 1 except that the gas blowing tube 25 was inserted into the molten silicon and argon gas was blown into the molten silicon, and the addition of the molten salt was performed three times at 0.5 kg each time. The experiment was conducted under conditions. Argon gas was continuously blown at 500 ccm during the experiment.
  • Example 1 when the inside of the cylinder 13 was observed after the experiment, the evaporated salt (NaF) was hardly adhered except for a portion close to the crucible. However, NaF adhered to the portion of the argon blowing tube. This is presumably because NaF was cooled in the portion of the argon blowing tube when the molten salt was removed by evaporation.
  • NaF evaporated salt
  • Comparative Example 1 In FIG. 1, the same experiment was performed with the cylinder 13 not provided above the crucible 3 and the top of the crucible 3 being open. However, in this case, since the molten salt (NaF) evaporates vigorously, the addition of the molten salt was 1 kg, twice as much as that of the example, and was added three times.
  • the molten salt NaF
  • the main impurity concentrations in the obtained silicon are boron (B): 3.3 ppm, phosphorus (P): 14 ppm, iron (Fe): 86 ppm, titanium ( Ti): 41 ppm, Aluminum (Al): 4.4 ppm, Calcium (Ca): 2.1 ppm, Sodium (Na): 33 ppm.
  • B boron
  • P phosphorus
  • Fe iron
  • Ti titanium
  • Al 4.4 ppm
  • Na sodium
  • the impurity concentration of NaF used in this example was boron (B): 0.5 ppm and phosphorus (P): 1.2 ppm.
  • Example 3 to 6 Experiments were performed in the same manner as in Example 1 except that the amount of NaF added to the molten silicon, the number of times of NaF addition, and the processing time (time for holding the cylinder 13) were the conditions shown in Table 1.
  • “condensing means” “present” indicates that the cylinder 13 is provided above the crucible 3.
  • “None” for “removal of condensate from the condensing means” indicates that the same cylinder 13 was used during the process.
  • Examples 7 to 13 Experiments were performed in the same manner as in Example 1 except that the amount of NaF added to the molten silicon, the number of times of NaF addition, and the processing time (time for holding the cylinder 13) were the conditions shown in Table 1.
  • “existing condensate from the condensing means” “present” indicates that the cylinder 13 was replaced with a cylinder 13 to which no condensate adhered during processing.
  • Example 7 500 g of NaF was added 6 times (addition amount was 100% with respect to Si), and each addition was held for 1 hour. In Example 7, the cylinder 13 was replaced after 1 hour from the start of the process.
  • Example 8 the amount of NaF added was 500 g for the first time, and 250 g was added for the second time and thereafter, and each addition was held for 1.5 hours.
  • the cylinder 13 was replaced after an hour had elapsed since the start of processing, as in Example 7.
  • Example 11 to 13 the amount of NaF added was 500 g for the first time, and 200 g was added for the second and subsequent times, and held for 1 hour after each addition.
  • the cylinder 13 was replaced in the same manner as in Example 7 after 1 hour from the start of processing.
  • Comparative Examples 2-4 The experiment was performed in the same manner as in Comparative Example 1 except that the amount of NaF added to the molten silicon, the number of times of NaF addition, and the treatment time were set as shown in Table 1.
  • Table 1 shows the impurity concentration, the boron (B) residual rate, and the yield in silicon of Examples 3 to 13 and Comparative Examples 2 to 4.
  • boron (B) residual ratio indicates the concentration ratio at the time of measurement with respect to the initial concentration of boron.
  • Yield indicates the ratio (%) of the amount of silicon cast (recovered) to the amount of dissolved silicon.
  • the horizontal axis represents NaF addition amount versus Si (%), and the vertical axis represents boron (B) residual rate (%) in silicon after treatment. As shown in FIG.
  • Examples 3 to 13 processed using the condensing means had a lower boron (B) residual ratio in the silicon than Comparative Examples 2 to 4 processed without using the condensing means. It was. Further, in Examples 8 to 13, in which the condensate adhering to the condensing means was removed during the processing, silicon was purified with higher efficiency than in Examples 3 to 6 in which the condensate was not removed from the condensing means. I knew it was possible.
  • Examples 8 to 10 in which the condensate adhering to the condensing means were removed during the processing were higher than Examples 3 to 6 in which the condensate was not removed from the condensing means. It was found that silicon can be purified with efficiency.
  • the silicon obtained by the method for producing silicon according to the present invention can be used as a material for a silicon wafer or a solar cell panel, for example.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Photovoltaic Devices (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un procédé de préparation de silicium avec lequel des impuretés telles que le bore (B), l'aluminium (Al), et le calcium (Ca) peuvent être éliminées d'une matière première de silicium métallique rapidement et efficacement par le même procédé pour obtenir du silicium métallique très pur. La présente invention concerne un procédé de préparation de silicium caractérisé en ce que du silicium fondu contenant des impuretés est mis en contact avec un sel fondu, le sel fondu comprenant les impuretés est évaporé pour éliminer les impuretés du silicium fondu, et le sel fondu évaporé est condensé par des moyens de condensation.
PCT/JP2011/079189 2010-12-20 2011-12-16 Procédé de préparation de silicium et appareil de préparation, tranche de silicium, et panneau de cellules solaires WO2012086544A1 (fr)

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TWI640473B (zh) 2017-12-07 2018-11-11 財團法人工業技術研究院 除硼方法與除硼裝置

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