JP5220935B1 - Silicon for solar cell, polycrystalline silicon material, polycrystalline silicon solar cell, and method for producing silicon for solar cell - Google Patents

Abstract

Provided are a silicon for solar cells, a polycrystalline silicon material, a polycrystalline silicon solar cell, and a method for producing silicon for solar cells, which can produce a solar cell containing both boron and phosphorus and having good conversion efficiency. To do.
Solar silicon having a boron concentration of 0.04 ppmw to 0.32 ppmw, a phosphorus concentration of 0.06 ppmw to 0.4 ppmw, and an aluminum concentration of 1.2 ppmw to 4.5 ppmw. , And a polycrystalline silicon material, a polycrystalline silicon solar cell, and a method for producing solar cell silicon produced using the same.
[Selection] Figure 1

Description

  The present invention relates to silicon for solar cells, polycrystalline silicon materials, polycrystalline silicon solar cells, and a method for producing silicon for solar cells.

  The use of natural energy is attracting attention as an alternative to oil, which is causing various problems in the global environment. Among them, the solar cell does not require a large facility and does not generate noise during operation, and thus has been particularly actively introduced in Japan and Europe.

  Solar cells using compound semiconductors such as cadmium tellurium have also been put into practical use. However, solar cells using crystalline silicon substrates are the most popular from the standpoints of the safety of the materials themselves, past achievements, and cost performance. Solar cells using a polycrystalline silicon substrate (polycrystalline silicon solar cells) occupy a large share.

  A polycrystalline silicon wafer widely used as a substrate for a polycrystalline silicon solar cell is manufactured as follows.

  First, a polycrystalline silicon ingot is obtained by a casting method in which a silicon melt obtained by melting silicon for solar cells is unidirectionally solidified from below in a crucible or an electromagnetic casting method in which a silicon-free melt is continuously grown in a bottomless crucible. Is made.

  Next, the polycrystalline silicon ingot obtained as described above is processed into a prismatic polycrystalline silicon block. Thereafter, the polycrystalline silicon wafer is obtained by slicing the polycrystalline silicon block with a wire saw or the like.

  A polycrystalline silicon solar cell can be obtained by putting the polycrystalline silicon wafer obtained as described above into a solar cell manufacturing process. A polycrystalline silicon solar cell module can be obtained by connecting and laminating a plurality of polycrystalline silicon solar cells.

  It is known that the impurity concentration in the silicon for solar cells has a great influence on the efficiency of the polycrystalline silicon solar cell as the final product (for example, Patent Documents 1 to 3).

  For example, Patent Document 1 discloses that for silicon for solar cells containing at least boron and carbon and / or oxygen, the sum of the impurity concentrations of iron, aluminum, titanium, and calcium and the mutual relationship between boron, phosphorus, carbon, and oxygen. Considering the action, conditions for silicon for solar cells having excellent conversion efficiency are shown.

  Further, Patent Document 2 contains 0.3 to 5.0 ppma boron, 0.5 to 3.0 ppma phosphorus, less than 50 ppma metal element, and less than 100 ppma carbon. Is disclosed.

  Furthermore, Patent Document 3 discloses a polycrystal containing a dopant that determines the conductivity type of a semiconductor and at least one element selected from the group consisting of aluminum, calcium, strontium, copper, and nickel as impurities other than the dopant. Silicon is disclosed. Moreover, the Example of patent document 3 discloses p-type polycrystalline silicon containing boron as a dopant and at least one element included in the above group.

  Moreover, as a method of manufacturing silicon for solar cells from metal silicon using a metallurgical method, for example, methods described in Patent Documents 1, 2, and 4 have been proposed. In the following, “de-P process” means a process of mainly removing phosphorus using a vacuum method, for example, and “de-B process” means a process of mainly removing boron, for example, using a slag method or the like. Shall.

  Patent Document 1 discloses a process in which a de-P process, a unidirectional solidification (metal impurity removal), a de-B process, and a unidirectional solidification (metal impurity removal) are performed in this order. Patent Document 1 also describes that the final unidirectional solidified product is cut into a wafer or remelted and solidified as necessary to form a wafer.

  Patent Document 2 discloses a silicon feedstock manufacturing method in which a de-B process, coagulation, at least one leaching process with an acid leaching solution, and directional solidification are performed in this order.

  Further, Patent Document 4 discloses a silicon purification method in which, for example, a de-B process, a leaching process, a de-P process, and a solidification segregation process are performed in this order. The “leaching step” means a step of leaching impurities from a raw material silicon into an acid or alkali solution by crushing the raw material silicon and immersing it in an acid or alkali solution.

JP-A-10-251010 Japanese Patent No. 4580939 JP 2006-1000033 A JP 2010-173911 A

  In the method of Patent Document 1, studies are made on silicon for solar cells containing at least boron and carbon and / or oxygen. Here, the effects of iron, aluminum, titanium and calcium impurities on the solar cell properties all appear in the form of [Mi] / [C + O], and the interaction between these metal impurities and carbon and / or oxygen. Suggest that is working. Here, [Mi] is the concentration of Fe + Al + Ti + Ca in silicon, and [C + O] is the concentration of C + O in silicon.

  It is unclear to which part the impurity concentration range in the silicon for solar cells disclosed in Patent Document 1 is, but the conventionally required impurity concentration is 6N or more except for C and O ( From paragraph [0002] of Patent Document 1, it can be understood that “silicon for solar cells” is “raw silicon for a polycrystalline silicon ingot for cutting a wafer used as a substrate for a polycrystalline silicon solar cell”.

  However, according to our experimental results, the oxygen concentration in the polycrystalline silicon ingot obtained by melting and unidirectionally solidifying solar cell silicon was not correlated with the oxygen concentration in the solar cell silicon used as a raw material. It seems that it is determined by the oxygen concentration in the atmosphere during unidirectional solidification, elution from silica normally used as a crucible, silicon oxide contained in the mold release material, and the like.

  Similarly to the above, the carbon concentration in the polycrystalline silicon ingot obtained by melting and unidirectionally solidifying the silicon for solar cells is not correlated with the carbon concentration in the silicon for solar cells as a raw material. The carbon in the polycrystalline silicon ingot is caused by the fact that the SiO gas evaporated from the silicon melt in the crucible reacts with a carbon member such as a graphite heater in the apparatus to become CO gas and is taken into the silicon melt again. Mostly. This is because the probability that the CO gas is taken into the silicon melt can be appropriately changed depending on the gas flow in the apparatus, the degree of vacuum, the structure of the furnace, and the like.

  From our experimental results on oxygen and carbon, it is unlikely that [C + O] in silicon for solar cells is directly correlated with the conversion efficiency of solar cells.

  Patent Document 1 suggests that Fe, Al, Ti, and Ca similarly affect the conversion efficiency of the solar cell. However, according to our experimental results, at least with respect to Fe and Al, the influence on the conversion efficiency of the solar cell is completely different, and as described above, [Mi] is a good parameter correlated with the conversion efficiency of the solar cell. Is unthinkable.

  Also, the silicon feedstock of Patent Document 2 is unlikely to correlate with the conversion efficiency of the solar cell, at least for the metal element concentration and the carbon concentration, as in Patent Document 1 described above.

  There is also a problem with respect to the boron concentration and phosphorus concentration of the silicon feedstock of Patent Document 2. When the boron concentration and phosphorus concentration of the silicon feedstock of Patent Document 2 are converted to ppmw units, the boron concentration is 0.115 ≦ [B] ≦ 1.92 ppmw, and the phosphorus concentration is 0.55 ≦ [P] ≦ 3. 86 ppmw.

  According to our experimental results, in a relatively high phosphorus concentration region of [P] ≧ 0.55 ppmw, there is a problem that phosphorus itself becomes a minority carrier trap and deteriorates solar cell characteristics. In addition, in the concentration range of [B]> 0.32 ppmw, when the produced solar cell is irradiated with light, a complex center in which boron and oxygen become minority carrier traps are formed, resulting in significant photodegradation. Arise.

  Moreover, in the Example of patent document 3, how the conversion efficiency of a solar cell changes with each density | concentration change of Al, Ca, Sr, Cu, and Ni in p-type polycrystalline silicon doped with boron. I'm researching. However, in particular, when producing a polycrystalline silicon ingot using a silicon raw material refined by a metallurgical method, since not only boron but also phosphorus is included, each silicon raw material containing both boron and phosphorus It is not obvious how the impurities affect the conversion efficiency of the solar cell.

  Moreover, in the manufacturing method of the silicon for solar cells described in Patent Document 2 and Patent Document 4, a metal removal process such as a leaching process, a directional solidification process, a leaching process or a solidification segregation process is performed twice or more, and a high-cost process is performed. It has become.

  Patent Document 1 also discloses a process in which the metal removal process is performed only once (de-P process, unidirectional solidification (metal impurity removal), de-B process). However, in this case, although the number of processes is reduced, in the de-B process after removing the metal impurities in the unidirectional solidification (metal impurity removal) process of the second process, the metal impurities, boron, phosphorus, etc. There is always a risk of contamination by impurities such as dopant elements. Examples of impurities that are likely to be mixed include a crucible material or a device forming material.

  In view of the above circumstances, an object of the present invention is to provide a solar cell silicon, a polycrystalline silicon material, and a polycrystalline silicon solar cell that can produce a solar cell that includes both boron and phosphorus and has good conversion efficiency. And it is providing the manufacturing method of the silicon for solar cells.

  The present invention includes boron, phosphorus, and aluminum, the boron concentration is 0.04 ppmw to 0.32 ppmw, the phosphorus concentration is 0.06 ppmw to 0.4 ppmw, and the aluminum concentration is It is silicon for solar cells which is 1.2 ppmw or more and 4.5 ppmw or less.

  Here, in the silicon for solar cells of the present invention, the aluminum concentration is preferably 2 ppmw or more and 3.5 ppmw or less.

  Moreover, in the silicon | silicone for solar cells of this invention, it is preferable that the density | concentration of iron is 1 ppmw or less.

  In the silicon for solar cells of the present invention, the ratio of the phosphorus concentration to the boron concentration is preferably 1.33 or less.

  In addition, the present invention is a polycrystalline silicon material produced by melting and solidifying the above silicon for solar cells.

  Moreover, this invention is a polycrystalline silicon solar cell produced from said polycrystalline silicon material.

  The present invention is also a method for producing the above silicon for solar cells, comprising a step of preparing raw silicon containing boron, phosphorus and aluminum, and a step of removing impurities from the raw silicon. As a process of removing impurities from the silicon for solar cells, only the three processes of removing boron, removing phosphorus, and solidification segregation process are performed, and the last of the three processes is a solidification segregation process. It is a manufacturing method.

  In the method for producing silicon for solar cells of the present invention, the solidification segregation step is preferably a step by a rotational segregation method.

  Furthermore, the present invention is a method for producing the above silicon for solar cells, comprising a step of preparing raw silicon containing boron, phosphorus and aluminum, and a step of removing impurities from the raw silicon, As the process of removing impurities from the process, only the three processes of removing boron, removing phosphorus, and solidification segregation process are performed, and the last of the three processes is the solidification segregation process. It is a manufacturing method of the silicon for solar cells further including the process of mixing the silicon obtained at the process to perform, and the silicon obtained at another process.

  Here, in the method for producing silicon for solar cells of the present invention, the solidification segregation step is preferably a step by a rotational segregation method.

  According to the present invention, silicon for solar cells, polycrystalline silicon material, polycrystalline silicon solar cells, and production of silicon for solar cells capable of producing a solar cell having both boron and phosphorus and good conversion efficiency A method can be provided.

(A)-(c) is typical sectional drawing illustrated about an example of the manufacturing method of the silicon for solar cells of this invention. It is a typical block diagram of an example of the manufacturing apparatus of the polycrystalline-silicon material of this invention. It is a graph which shows the relationship between Al concentration and the high rank rate in Experimental example 1. It is a graph which shows the relationship between the Fe density | concentration in Experimental example 2, and a high rank rate.

  Embodiments of the present invention will be described below. In the drawings of the present invention, the same reference numerals represent the same or corresponding parts.

<Silicon for solar cells>
As a result of intensive studies, the present inventors have found that the above problems can be solved, and have completed the present invention. That is, the silicon for solar cells of the present invention contains boron (B), phosphorus (P), and aluminum (Al), the B concentration is 0.04 ppmw or more and 0.32 ppmw or less, and the P concentration is 0.00. It is 06 ppmw or more and 0.4 ppmw or less, and Al concentration is 1.2 ppmw or more and 4.5 ppmw or less.

  Regarding the B concentration, the high concentration side is restricted from the viewpoint of suppressing the light deterioration of the solar cell and the reverse leakage current at the time of non-irradiation, and the low concentration side is restricted from the viewpoint of improving the conversion efficiency of the solar cell. That is, when the B concentration of the silicon for solar cells is too low, the open voltage of the solar cells does not increase and good characteristics cannot be obtained.

  Accordingly, the B concentration is set to 0.04 ppmw or more and 0.32 ppmw or less from the viewpoint of suppressing the photodegradation of the solar cell and the reverse leakage current at the time of non-irradiation and improving the conversion efficiency of the solar cell, preferably 0. It is set to 1 ppmw or more and 0.2 ppmw or less.

  Similarly, when the Al concentration was examined, when P was present in the solar cell silicon, an interaction between P and Al was observed. Compared with Patent Document 3, the conversion efficiency of the solar cell was confirmed. However, it has been found that the Al concentration range having a good deviation greatly shifts to the high concentration side.

  Specifically, when the P concentration is in the range of 0.06 ppmw to 0.4 ppmw, preferably 0.06 ppmw to 0.25 ppmw, the Al concentration is 1.2 ppmw to 4.5 ppmw. In this case, the conversion efficiency of the solar cell becomes good, and particularly when the Al concentration is 2 ppmw or more and 3.5 ppmw or less, the conversion efficiency of the solar cell becomes even better.

  Furthermore, as a result of examining silicon for solar cells containing B, P, and Al, iron (Fe) becomes a recombination center of minority carriers even when P is contained, and therefore the Fe concentration may be 1 ppmw or less. It turned out to be preferable.

  In addition, in this specification, "ppmw" means the weight percent (Parts Per Million Weight) with respect to the weight of the whole silicon | silicone for solar cells.

<Method for producing silicon for solar cell>
A method for producing solar cell silicon according to the present invention is a method for producing any one of the above solar cell silicon, the step of preparing raw silicon containing B, P and Al, and impurities from the raw silicon. A step of removing impurities from the raw material silicon, and performing only three steps of removing B, removing P, and solidification segregation step, and the last of the three steps Is a solidification segregation process.

  Hereinafter, an example of the manufacturing method of the silicon for solar cells of this invention is demonstrated. First, a step of preparing raw material silicon containing B, P, and Al is performed. Here, the B concentration, the P concentration, and the Al concentration in the raw material silicon are not particularly limited, respectively, but the B concentration, the P concentration, and the Al in the solar cell silicon manufactured by the method for manufacturing a solar cell silicon of the present invention are not limited. It is preferable that the concentration is within the above range. However, depending on the ratio of the B concentration and the P concentration, the conductivity type of the semiconductor changes from p-type to n-type as it solidifies in the region that can be used as silicon for solar cells. Since this may lead to a decrease in the yield of silicon for solar cells, from the viewpoint of suppressing such a decrease in yield, the ratio of the P concentration to the B concentration of solar cell silicon is 1.33 or less ((P concentration / B concentration) ≦ 1.33) seems to be preferred.

  As the raw material silicon, for example, chemical industrial grade metal silicon can be used. As chemical-grade metal silicon, for example, silica sand manufactured by a method of reducing silica with carbon in an electric furnace, having a purity of about 98 to 99.5% can be used. Chemical industrial grade metal silicon contains, for example, B and P as impurities in a concentration of about 5 ppmw to 30 ppmw, respectively, and metal impurities such as Fe, Al, and calcium (Ca) are about 1000 ppmw to 5000 ppmw. Often included in the concentration of.

  Next, a process of removing B from the raw silicon is performed. The step of removing B is not particularly limited as long as it is a method capable of removing B from raw silicon, but it is preferable to use a slag method.

  In the slag method, the addition of the flux to the molten silicon obtained by melting the raw material silicon and the removal of the noro generated by the flux incorporating B in the molten silicon are each performed at least once. This is a method of removing B contained in.

  Specifically, first, for example, as shown in the schematic cross-sectional view of FIG. 1A, the raw material silicon prepared as described above is accommodated in a crucible 3 in an open processing chamber 1 under atmospheric pressure. The raw silicon is heated and melted by the heating device 2 to produce the molten silicon 4.

  Next, molten slag 5 is generated by adding a flux such as silicon oxide and / or alkali metal carbonate to molten silicon 4, and molten silicon 4 and molten slag 5 are reacted. By this reaction, boron oxide (B oxide) is generated and taken into the molten slag 5, and B can be removed from the molten silicon 4.

  The molten slag 5 incorporating B oxide or the like is called Noro and floats on the surface of the molten silicon 4. When the B concentration increases in the floating shell, the reaction efficiency between the molten slag 5 and B decreases. Therefore, scrapes are scraped out from the crucible provided on the upper part of the crucible 3, and new flux is added to the crucible 3 again.

  The B concentration in the raw silicon can be reduced by performing such flux addition and scraping at least once. In this way, when the B concentration in the molten silicon 4 becomes 0.04 ppmw or more and 0.32 ppmw or less, preferably 0.1 ppmw or more and 0.2 ppmw or less, the crucible 3 is tilted and the molten silicon 4 is used as a mold. Take out the hot water and let it cool under atmospheric pressure to obtain a silicon lump. By setting the B concentration in the raw material silicon after the step of removing B to the above content, the B concentration in the solar cell silicon finally obtained can be within the above range.

  Next, a step of removing P from the raw silicon is performed. The step of removing P is not particularly limited as long as it is a method capable of removing P from raw silicon, but it is preferable to use a vacuum method.

  The vacuum method is a method of removing an impurity element having a higher vapor pressure than silicon by holding molten silicon obtained by melting raw material silicon in a reduced-pressure atmosphere. Such impurity elements include arsenic (As), antimony (Sb), and sodium (Na) in addition to P.

  Specifically, for example, as shown in the schematic cross-sectional view of FIG. 1B, first, raw silicon after the step of removing B is accommodated in a crucible 8 in a closed processing chamber 6 and heated by a heating device 7. The raw silicon is heated and melted to produce the molten silicon 4.

  Next, the inside of the closed processing chamber 6 is set to a reduced pressure atmosphere, and the molten silicon 4 in the crucible 8 is held in the reduced pressure atmosphere. Thereby, P can be removed from the molten silicon 4. Thus, when the content of P in the molten silicon 4 is in the range of 0.06 ppmw to 0.4 ppmw, preferably in the range of 0.06 ppmw to 0.25 ppmw, the crucible 8 is tilted. Then, the molten silicon 4 is poured out into a mold and allowed to cool in a vacuum atmosphere to obtain a silicon lump.

  In addition, as a process of removing phosphorus other than the vacuum method, for example, silicon held in a reaction vessel such as a water-cooled copper crucible is irradiated with an electron beam under vacuum to form a high-temperature molten region, thereby removing impurities from silicon. A vacuum refining method that evaporates from the gas can also be used.

Next, a solidification segregation process is performed. The solidification segregation step is a method of segregating impurities by utilizing the difference in solubility between the liquid phase and the solid phase of the impurity element contained in the raw material silicon. When the raw material silicon is solidified, impurities are discharged (segregated) from the solid phase to the liquid phase due to the segregation effect. The degree of segregation is indicated by the equilibrium segregation coefficient K ₀ , and Fe and Al have a small equilibrium segregation coefficient K ₀ , which are about 6.4 × 10 ⁻⁶ (Fe) and 2.8 × 10 ⁻³ (Al), respectively. Therefore, it is known that the removal efficiency by solidification segregation is large.

  As such a solidification segregation step, for example, a method performed by a unidirectional solidification method or a method performed by a rotation segregation method can be exemplified, and among them, a method performed by a rotation segregation method is preferable. The rotational segregation method is advantageous for cost reduction because it can increase the segregation efficiency, the solidification rate and the raw material utilization efficiency as compared with the unidirectional solidification method usually used for removing metal impurities.

  As described above, during solidification segregation, impurities are discharged from the solid phase to the liquid phase side, so if the stirring on the liquid phase side is not sufficient, the impurity concentration on the solid-liquid interface liquid phase side becomes locally high, There is a problem that the segregation coefficient becomes large. The rotational segregation method can avoid such a situation by actively stirring the liquid phase, and can expect a good segregation effect even if the solidification rate is high. In the rotational segregation method, since the impurity element remains in the molten silicon, the step of cutting the impurity-containing region as in the unidirectional solidification method can be omitted.

  Specifically, first, as shown in the schematic cross-sectional view of FIG. 1C, for example, the raw silicon after the process of removing P is accommodated in the crucible 14 in the closed processing chamber 9, and the heating apparatus 10 is used. The raw silicon is heated and melted to produce the molten silicon 4.

  Next, the stirring rod 13 made of carbon provided with a cooling mechanism inside is immersed in the molten silicon 4 and rotated by the rotating device 12 attached to the upper portion of the processing chamber 9 via the connecting portion 11 for rotating device, The molten silicon 4 is stirred. Then, the surface temperature of the stirring bar 13 is lowered by the cooling mechanism of the stirring bar 13 to solidify and segregate silicon on the surface of the stirring bar 13.

  Thus, the silicon concentration for solar cells of the present invention can be segregated on the surface of the stirring bar 13 by reducing the Al concentration and the Fe concentration. The solidification segregation step is performed so that the Al concentration in the solar cell silicon of the present invention segregated on the surface of the stirring bar 13 is 1.2 ppmw to 4.5 ppmw, preferably 2 ppmw to 3.5 ppmw. . The solidification segregation step is performed so that the Fe concentration in the silicon for solar cells of the present invention segregated on the surface of the stirring bar 13 is 1 ppmw or less.

  In the above description, the process of removing impurities from the raw material silicon has been described in the order of the process of removing B, the process of removing P, and the solidification segregation process. However, the process of removing P and B is removed. It is also possible to perform in order of the process and the solidification segregation process.

  In the method for producing silicon for solar cells of the present invention, the steps of removing impurities from the raw material silicon containing B, P and Al include a de-B step, a de-P step, and a solidification segregation step (metal impurity removal). Only the process is performed, and the last of the three processes is a solidification segregation process.

  Thereby, the metal impurity removal step can be performed only once and the number of steps can be made the same as the method of Patent Document 1, and the last step is a solidification segregation step which is a metal impurity removal step. The risk of contamination by impurities in the process can be avoided.

  Further, the method described in Patent Document 4 includes a leaching step in addition to the above three steps. Since the leaching process is effective not only for reducing the Fe concentration but also for reducing the Al concentration, the present inventor recognizes that the lower the Al concentration, the better the conversion efficiency of the solar cell. The leaching process was performed in order to suppress the above.

  However, as a result of the subsequent diligent studies by the present inventors, it was found that there is an optimum value for the Al concentration, and when the leaching process was omitted in order to increase the Al concentration, the Al concentration was reduced simultaneously with the cost reduction due to the omission of the process. It has been found that it is possible to make the concentration range of the silicon for solar cells of the present invention.

  Further, the method may further include a step of mixing silicon obtained in the step of removing impurities consisting of only the above three steps and silicon obtained in a separate step. Here, the silicon obtained in the separate process is not particularly limited. For example, the polysilicon obtained by the Siemens method, the polysilicon obtained by the fluidized bed method, the end material of the single crystal silicon ingot, the single crystal silicon. Examples thereof include a block, a single crystal silicon wafer, a mill end of a polycrystalline silicon ingot, a polycrystalline silicon block, a polycrystalline silicon wafer, or a purified product thereof.

<Polycrystalline silicon material>
The polycrystalline silicon material of the present invention is produced by melting and solidifying the above silicon for solar cells.

  In FIG. 2, the typical block diagram of an example of the manufacturing apparatus of the polycrystalline-silicon material of this invention is shown. The polycrystalline silicon material manufacturing apparatus of the present invention shown in FIG. 2 surrounds the crucible 21, the outer crucible 22 that accommodates the crucible 21, and the outer crucible 22 inside a chamber 27 that has a heat insulating material 213 on the inner wall. And a resistance heating body 28 made of a graphite heater.

  The outer crucible 22 is supported by a crucible base 23. The crucible base 23 is provided with a cooling tank 211 for flowing a coolant for cooling the crucible 21 and the outer crucible 22, and for raising and lowering the crucible 21 and the outer crucible 22. An elevating drive mechanism 212 is attached.

  A crucible lower thermocouple 25 and an outer crucible lower thermocouple 26 are respectively attached to the lower part of the crucible 21 and the outer crucible 22, and the lower crucible thermocouple 25 and the outer crucible lower thermocouple 26 are connected to the controller 29. It is connected. Further, the control device 29 can control the heating temperature of the resistance heating body 28 based on the respective temperature information of the crucible 21 and the outer crucible 22 transmitted from the crucible lower thermocouple 25 and the outer crucible lower thermocouple 26. Connected to resistance heater 28 so that it can.

  The polycrystalline silicon material of the present invention can be manufactured, for example, as follows. First, the silicon for solar cells of the present invention produced as described above is accommodated in the crucible 21 and heated by the resistance heater 28. Thereby, the silicon for solar cells of the present invention inside the crucible 21 is melted to produce a molten silicon 24.

  Next, the molten silicon 24 is sequentially solidified by causing the coolant to flow from the cooling tank 211 and moving the crucible 21 downward by the elevating drive mechanism 212 while cooling the molten silicon 24 inside the crucible 21. Go. Thereby, the polycrystalline silicon ingot which is an example of the polycrystalline silicon material of this invention can be obtained.

  A polycrystalline silicon block can be obtained by cutting the polycrystalline silicon ingot obtained as described above into a desired shape and size such as a prismatic shape using a known apparatus such as a band saw.

  A polycrystalline silicon wafer can be obtained by slicing the polycrystalline silicon block obtained as described above using a known apparatus such as a multi-wire saw.

  In this specification, “polycrystalline silicon material” is a concept including a polycrystalline silicon ingot, a polycrystalline silicon block, and a polycrystalline silicon wafer.

<Polycrystalline silicon solar cell>
The polycrystalline silicon solar cell of the present invention is a solar cell produced from the polycrystalline silicon material (polycrystalline silicon wafer) of the present invention. In this specification, “solar battery” is a concept including a solar battery cell and a solar battery module, and “polycrystalline silicon solar battery” means a polycrystalline silicon solar battery cell and a polycrystalline silicon solar battery. It is a concept that includes modules.

  The polycrystalline silicon solar cell of the present invention can be manufactured by a known solar cell process using, for example, a polycrystalline silicon wafer that is the polycrystalline silicon material of the present invention.

  For example, in the case of a polycrystalline silicon wafer doped with p-type impurities, a pn junction is formed by doping an n-type impurity to form an n-type layer using a known material and a known method. Then, a polycrystalline silicon solar battery cell can be manufactured by forming a front electrode and a back electrode.

  In the case of a polycrystalline silicon wafer doped with n-type impurities, a pn junction is formed by forming p-type layers by doping p-type impurities using known materials and known methods. Then, a polycrystalline silicon solar battery cell can be manufactured by forming a front electrode and a back electrode.

  Moreover, the polycrystalline silicon solar cell of the present invention is not limited to the one using the pn junction inside the polycrystalline silicon wafer as described above, for example, by depositing a metal with a thin insulating layer interposed therebetween. There are formed MIS type solar cells, solar cells using p-type and n-type silicon heterojunctions having different structures by forming an amorphous silicon thin film having a conductivity type opposite to that of a polycrystalline silicon wafer. Moreover, a polycrystalline silicon solar cell module can be manufactured by electrically connecting the plurality.

<Experimental example 1>
Using the manufacturing apparatus shown in FIG. 2, each of the sample Nos. 1 to 11 polycrystalline silicon ingots were produced. And sample No. manufactured as mentioned above is carried out. The impurity concentrations of 1 to 11 polycrystalline silicon ingots were measured by ICP (Inductively Coupled Plasma) emission analysis.

  Next, sample No. manufactured as described above was used. A polycrystalline silicon wafer is prepared from each of the 1 to 11 polycrystalline silicon ingots, and each of these polycrystalline silicon wafers is put into a normal solar cell process. 1 to 11 solar cells were produced. In addition, about 15,000 polycrystalline silicon wafers were obtained from one 400 kg polycrystalline silicon ingot, and solar cells were respectively produced from all these polycrystalline silicon wafers.

  And sample No. produced as mentioned above was carried out. The conversion efficiency of each of the solar cells 1 to 11 was measured, and the correlation between the Al concentration of the polycrystalline silicon ingot and the conversion efficiency of the solar cells was examined. The results are shown in Table 1.

  In addition, the high rank rate (%) of Table 1 was made into the ratio of the photovoltaic cell whose conversion efficiency is higher than a threshold value by making predetermined conversion efficiency of a photovoltaic cell into a threshold value. Moreover, the notation of “0.0 ppmw” of the Al concentration in Table 1 means that it is below the detection limit (0.04 ppmw) in the ICP emission analysis method.

  FIG. 3 shows a graph with the Al concentration shown in Table 1 as the horizontal axis and the high rank ratio as the vertical axis.

  As shown in FIG. When the Al concentration of the 1 to 11 polycrystalline silicon ingots was in the range of 1.2 ppmw to 4.5 ppmw, the high rank ratio was a good value.

  In particular, sample no. When the Al concentration of the polycrystalline silicon ingots 1 to 11 was in the range of 2 ppmw or more and 3.5 ppmw or less, the high rank ratio was 80% or more, and thus a further favorable value was obtained.

  Therefore, as shown in FIG. 3, it was confirmed that the high rank rate has a correlation with the Al concentration.

  In addition, this experimental data is the whole data which produced the photovoltaic cell from the whole ingot in which the abundance and abundance ratio of various impurity elements are changing in the height direction of the polycrystalline silicon ingot due to the segregation effect. It's not trivial data.

<Experimental example 2>
In Experimental Example 2, a sample was obtained in the same manner as in Experimental Example 1 except that a plurality of silicon for solar cells containing B, P, Fe, and 2.5 ppmw of Al and having different Fe concentrations were used. No. 12 to 15 polycrystalline silicon ingots were produced and sample Nos. The impurity concentration of 12 to 15 polycrystalline silicon ingots was measured by ICP emission spectrometry.

  Thereafter, in the same manner as in Experimental Example 1, sample no. Polycrystalline silicon wafers are prepared from 12 to 15 polycrystalline silicon ingots, and these polycrystalline silicon wafers are respectively put into a normal solar cell process. 12 to 15 solar cells were produced.

  In the same manner as in Experimental Example 1, sample No. The conversion efficiency of each of 12 to 15 solar cells was measured, and the correlation between the Fe concentration of the polycrystalline silicon ingot and the conversion efficiency of the solar cells was examined. The results are shown in Table 2.

  In addition, the high rank rate (%) of Table 2 was made into the ratio of the photovoltaic cell whose conversion efficiency is higher than a threshold value by making predetermined conversion efficiency of a photovoltaic cell into a threshold value. Moreover, the notation of “0.0 ppmw” of the Fe concentration in Table 2 means that it is below the detection limit (0.04 ppmw) in the ICP emission analysis method.

FIG. 4 shows a graph with the Fe concentration shown in Table 2 on the horizontal axis and the high rank ratio on the vertical axis.
As shown in FIG. It was found that when the Fe concentration of the 12-15 polycrystalline silicon ingot was 1 ppmw or less, the high rank ratio was 80% or more, which was a favorable value.

  Therefore, as shown in FIG. 4, it was confirmed that the high rank rate has a correlation with the Fe concentration.

  This experimental data is also the entire data for producing solar cells from the entire ingot in which the abundances and abundance ratios of various impurity elements change in the height direction of the polycrystalline silicon ingot due to the segregation effect. It's not trivial data.

<Experimental example 3>
In Experimental Example 3, a slag method is used as a process for removing B, a vacuum method is used as a process for removing P, and a rotary segregation method is used as a solidification segregation process for removing metal impurities. A method for producing silicon for a battery will be described.

  First, as the raw material silicon, a silicon having a purity of about so-called metal silicon was prepared. Here, the raw material silicon contained B and P as impurities at a concentration of about 5 ppmw to 30 ppmw, respectively, and metal impurities such as Fe, Al, and Ca were contained at a concentration of about 1000 ppmw to 5000 ppmw. .

  Next, as shown in FIG. 1 (a), the raw material silicon is accommodated in a crucible 3 in an open processing chamber 1 under atmospheric pressure, and the raw material silicon is heated and melted by a heating device 2. Thus, molten silicon 4 was produced.

  Next, a molten slag 5 was generated by adding a flux such as silicon oxide and / or alkali metal carbonate to the molten silicon 4, and the molten silicon 4 and the molten slag 5 were reacted. By this reaction, B oxide was generated and taken into the molten slag 5, and B was removed from the molten silicon 4.

  Next, noro, which is the molten slag 5 incorporating B oxide, was scraped out from a trough provided on the top of the crucible 3, and a new flux was added to the crucible 3 again.

  The B concentration in the raw material silicon was reduced by repeatedly performing such addition of flux and scraping of Noro 20 times. When the desired B concentration was achieved, the melting furnace was tilted to pour molten silicon into a mold and allowed to cool under atmospheric pressure to obtain a silicon lump.

  As described above, B was removed from the raw silicon, and the B concentration in the raw silicon was reduced to 0.1 ppmw to 0.2 ppmw.

  Next, as shown in FIG. 1B, the raw material silicon after the step of removing B is accommodated in a crucible 8 in a closed processing chamber 6, and the raw material silicon is heated and melted by a heating device 7. Thus, molten silicon 4 was produced.

  Next, the pressure in the closed processing chamber 6 was set to about 1 Pa or less, and the temperature of the molten silicon 4 was maintained at 1650 ° C. When the desired B concentration was achieved, the melting furnace was tilted to pour molten silicon into a mold and allowed to cool under atmospheric pressure to obtain a silicon lump.

  The pressure in the processing chamber 6 is not limited to 1 Pa or less, but a lower pressure is preferable because a P removal rate is faster. Further, the temperature of the molten silicon 4 is not limited to 1650 ° C., and may be any temperature not lower than the melting point of silicon. Further, the higher the temperature of the molten silicon 4 is, the faster the removal rate of P is. However, since there are heat-resistant temperatures of members such as an apparatus and a heat insulating material, and elution of crucible material from the crucible (for example, when using a graphite crucible) From the viewpoint of stable operation, the temperature of the molten silicon 4 is most preferably 1600 ° C to 1700 ° C.

  As described above, P was removed from the raw silicon, and the P concentration in the raw silicon was reduced to 0.25 ppmw or less.

  Next, as shown in FIG. 1C, the raw material silicon after the process of removing P is placed in a crucible 14 in a closed processing chamber 9, and the raw material silicon is heated and melted by the heating device 10. Thus, molten silicon 4 was produced.

  Next, the stirring rod 13 made of carbon provided with a cooling mechanism inside is immersed in the molten silicon 4 and rotated by the rotating device 12 attached to the upper portion of the processing chamber 9 via the connecting portion 11 for rotating device, Molten silicon 4 was stirred. Then, the surface temperature of the stirring bar 13 was lowered by the cooling mechanism of the stirring bar 13 to solidify and segregate silicon on the surface of the stirring bar 13.

  In this way, the Al concentration and the Fe concentration were decreased, and the silicon for solar cells was segregated on the surface of the stirring bar 13.

  When the impurity concentration of the silicon for solar cells of Experimental Example 3 obtained through only the above three steps was analyzed by ICP emission analysis, the B concentration was 0.4 ppmw or less, the P concentration was 0.5 ppmw or less, and the Fe concentration was 1 ppmw or less, Al concentration was 1.2 ppmw or more and 4.5 ppmw or less, and the impurity concentration was within the range of the silicon for solar cells of the present invention.

  Therefore, in Experimental Example 3, the B concentration, the P concentration, the Al concentration, and the Fe concentration are converted into solar cells with good conversion efficiency by only the three steps of the step of removing B, the step of removing P, and the solidification segregation step. Since it can be within the concentration range of the silicon for solar cells of the present invention capable of producing a battery, it was confirmed that the leaching step can be omitted and the cost can be reduced as compared with the conventional case.

  Although the embodiments and examples of the present invention have been described above, it is also planned from the beginning to appropriately combine the configurations of the above-described embodiments and examples.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  INDUSTRIAL APPLICABILITY The present invention can be used for a solar cell silicon, a polycrystalline silicon material, a polycrystalline silicon solar cell, and a method for producing solar cell silicon.

  1 processing chamber, 2 heating device, 3 crucible, 4 molten silicon, 5 molten slag, 6 processing chamber, 7 heating device, 8 crucible, 9 processing chamber, 10 heating device, 11 rotating device connection, 12 rotating device, 13 Stirring rod, 21 crucible, 22 outer crucible, 23 crucible base, 24 molten silicon, 25 crucible lower thermocouple, 26 outer crucible lower thermocouple, 27 chamber, 28 resistance heating element, 29 control device, 211 cooling tank, 212 lift drive Mechanism, 213 Insulation.

Claims (10)

Including boron, phosphorus and aluminum,
The boron concentration is 0.04 ppmw or more and 0.32 ppmw or less,
The phosphorus concentration is 0.06 ppmw to 0.4 ppmw,
The silicon for solar cells whose density | concentration of the said aluminum is 1.2 ppmw or more and 4.5 ppmw or less.   The silicon for solar cells of Claim 1 whose density | concentration of the said aluminum is 2 ppmw or more and 3.5 ppmw or less.   The silicon for solar cells of Claim 1 or 2 whose density | concentration of iron is 1 ppmw or less.   The silicon for solar cells according to any one of claims 1 to 3, wherein a ratio of the concentration of phosphorus to the concentration of boron is 1.33 or less.   A polycrystalline silicon material produced by melting and then solidifying the solar cell silicon according to any one of claims 1 to 4.   A polycrystalline silicon solar cell made from the polycrystalline silicon material according to claim 5. A method for producing silicon for solar cells according to any one of claims 1 to 4,
Preparing a raw material silicon containing boron, phosphorus and aluminum;
Removing impurities from the raw silicon,
As the step of removing impurities from the raw silicon, only three steps of removing boron, removing phosphorus, and solidification segregation step are performed, and the last step of the three steps is the solidification segregation step. A method for producing silicon for solar cells.   The manufacturing method of the silicon for solar cells of Claim 7 whose said solidification segregation process is a process by the rotation segregation method. A method for producing silicon for solar cells according to any one of claims 1 to 4,
Preparing a raw material silicon containing boron, phosphorus and aluminum;
Removing impurities from the raw silicon,
As the step of removing impurities from the raw silicon, only three steps of removing boron, removing phosphorus, and solidification segregation step are performed, and the last step of the three steps is the solidification segregation step. Yes,
The manufacturing method of the silicon for solar cells which further includes the process of mixing the silicon obtained at the process of removing the said impurity, and the silicon obtained at another process.   The manufacturing method of the silicon for solar cells of Claim 9 whose said solidification segregation process is a process by the rotation segregation method.

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