TW201229332A - Container for producing silicon ingot and method for producing silicon ingot - Google Patents

Abstract

A container for producing silicon ingots and a method for producing silicon ingots are provided, which are designed such that grown silicon ingots can be easily taken out from the container and also such that the yield of silicon ingots can be increased. The container for producing silicon ingots has a cylindrical shape with an open top surface and a closed bottom and is used for growing polycrystalline silicon therein by solidifying silicon melt, wherein the sidewalls of the container comprise: a side surface lower part which is formed in the vertical direction; a side surface middle part which is inclined and extends from the side surface lower part so as to widen toward the top surface opening section at a predetermined taper angle (θ ) with respect to the vertical direction; and a side surface upper part which extends from the side surface middle part in the vertical direction. A silicon source material is placed in the silicon ingot forming container in a manner such that the surface of silicon melt is positioned at the inclined sections, and polycrystalline silicon is grown by means of the Kyropoulos method while a seed crystal is lifted out at very low speed.

Description

201229332 VI. Description of the Invention: [Technical Field] The present invention relates to a container for producing a bismuth ingot for producing a solar battery grade bismuth ingot and a method for producing the bismuth ingot. [Prior Art] A conventionally known method for producing a niobium ingot used in a solar cell is a casting method in which a crucible is accommodated in a container such as a crucible or a mold, and the crucible is solidified from below to grow polycrystalline crucible ( For example, Patent Documents 1 to 5). According to this casting method, when the crucible melt solidifies, the direction in which the crystal grows is aligned, so that it is possible to prevent the grain boundary from increasing the resistivity and to produce a high-quality wafer. The ingot can be produced in large quantities by the casting method. Generally, a release member is formed on the inner surface of the container used by the casting method. When the crucible is produced by the casting method, when the crucible melts in the container and the crucible reacts with the container, the crucible crystals are fixed to the container and it is difficult to take out the crucible. Therefore, by forming a release member on the inner surface of the container, the ruthenium crystal is not in direct contact with the container. Since the tantalum melt has a density of 2.5 g/cm3 and a solid density of 2.3 3 g/cm3, the volume of the tantalum melt expands by about 7% when it solidifies in the container. Further, as the volume expansion causes stress on the container, it becomes difficult to take out the bismuth ingot from the container, and sometimes the release member formed on the container is damaged. When the mold release member is damaged, the ruthenium crystal is fixed to the container, so that the detachment property of the ruthenium ingot is further deteriorated. Therefore, there is a need for a technique for mitigating the stress generated by volume expansion 201229332 when solidifying the tantalum melt. For example, a technique has been proposed (for example, Patent Document 1). By tilting the opening of the container from the vertical direction to the outside, the vertical stress component is relaxed on the side of the container, so that the ruthenium crystal does not easily intrude into the container. Patent Document 1 discloses a container having an inclined portion which is inclined by 3 in the direction of expansion toward the opening of the container. the above. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. 3-22907 (Patent Document 3) [Patent Document 4] Japanese Patent Application Publication No. 2010-503596 (Patent Document 5) [Problems to be Solved by the Invention] In the case of a container having an inclined portion, if the inclination angle of the side surface of the container is too small, the effect of dispersing the stress accompanying the volume expansion at the time of solidification of the crucible cannot be obtained, so that the crucible is not easily taken out from the container and the release member is allowed to be removed. The problem of damage is not eliminated. When the inclination angle of the side surface of the container is too large, the loss at the time of cutting the outer peripheral portion of the bismuth ingot is increased. The yield (raw material take-up rate) is lowered, so that it is not suitable (refer to Fig. 5). When the bismuth ingot is produced by the casting method, due to the volume from which the release member is formed

The bottom of the S-6-201229332 crystal grows, so it is difficult to reduce the crystal grain boundaries. As a result, the loss of the crystal quality due to the loss of the carrier or the decrease in the yield due to the growth of the crystal grain boundary may result. In order to solve the above problems, an object of the present invention is to provide a container for producing a ruthenium ingot and a method for producing the ruthenium ingot, which can easily take out the ruthenium ingot to be incubated from the container and improve the yield of the ruthenium ingot. [Means for Solving the Problem] The invention according to claim 1 is a bottomed cylindrical ingot manufacturing container for opening, which is used for solidifying a crucible melt to grow polycrystalline crucible; a lower portion of the side surface formed vertically, and a side portion of the side surface which is connected to the lower portion of the side surface and which is inclined to extend toward the upper opening portion at a predetermined inclination angle 0 with respect to the vertical direction, and an upper portion of the side surface which is vertically connected to the middle portion of the side surface . According to the invention of claim 2, in the container for producing an ingot, the inclination angle 0 is 10 to 8 inches. . According to the invention of claim 3, in the container for manufacturing an ingot, the inclination angle 0 is 15 to 6 inches. The invention according to claim 4, wherein the above-mentioned inclination angle 0 is 20 to 7 〇». The invention of claim 5, wherein the inclination angle 0 is 20 to 45 in the container for producing an ingot. . According to the invention of claim 6, the container for manufacturing a sand ingot according to any one of claims 1 to 5 is a material composed of any one of quartz, Si3N4' SiC, graphite, and oxygen 201229332. A combination of the above materials. The invention according to any one of claims 1 to 6, wherein the crucible raw material is placed so that the surface of the crucible melt is located in the inclined portion, and the crucible melt is solidified to cause polycrystalline crucible growing up. According to the invention of the present invention, in the method of producing the bismuth ingot according to the seventh aspect, the seed crystal is brought into contact with the surface of the ruthenium melt, and the ruthenium melt is solidified from the surface while the seed crystal is pulled up. Polycrystalline growth. According to the invention of claim 9, in the method for producing an antimony ingot according to claim 8, the seed crystal is pulled up in accordance with the speed of the volume expansion when the crucible melt is solidified. The following is a description of the originality of the present invention. Conventionally, as a crystal growth method, a Kyropulos method has been known in which a seed crystal is brought into contact with a surface of a molten metal, and crystal growth is progressed from a molten surface toward a lower side. In the bubble generation method, since crystal growth is caused from a molten metal surface having a small foreign matter, it is expected that a higher quality tantalum crystal is formed than the casting method. The present inventors have intensively determined a method of producing a ruthenium ingot by a bubble generation method instead of a casting method in which crystals are grown from the bottom of a container in which a release member is formed. First, when the bismuth ingot is produced by the bubble generation method, the method is to pull up the growth crystal at a very low speed to alleviate the longitudinal stress accompanying the volume expansion when the sand is solidified. However, in the case where the ingot is produced by this method, the release member formed on the inner surface of the container has a large number of surface-like disappearances, and it is difficult to take out the crucible ingot. Observe the container after the manufacture of the ingot for the sake of investigation, and understand

S -8- 201229332 The top edge of the bismuth ingot, that is, the portion corresponding to the fused portion of the bismuth melt, and the top periphery of the planar part of the release member, which has a high convex portion formed in the circumferential direction. On the other hand, in the part corresponding to the top of the bismuth ingot by the casting method, the demolding is caused by the crystallization growth method, but the stress accompanying the volume expansion when 矽, when it is solidified The stress associated with volume expansion. On the other hand, when solidifying near the surface of the crucible melt, the mold release member is peeled off by invading the mold release (especially the convex portion of the top peripheral edge) and pulling it up. Further, it has been found that, by focusing on the shape of the good container of the bismuth melt, it is possible to effectively disperse the volume expansion which is entangled in the transverse direction, and the take-up property and yield of the bismuth ingot are taken out from the container. [Effect of the invention] According to the present invention, the stress generated on the container which is generated when the crucible is solidified is alleviated, so that the mold release member which can be effectively formed is damaged. The container is then allowed to be removed and can be easily removed. On the other hand, in the container for producing an ingot, the portion which becomes a large stress due to the coagulation is solidified as the vicinity of the surface of the inclined portion, and the crystal disappears. On the other hand, it was confirmed that the ingot was in the range of 0·1 to 0.5 mm, and the piece disappeared. Therefore, the solidified part near the surface of the molten metal should be solidified more than the other parts, and the solidified part which is expanded in the transverse direction by the bubble method, in this state, the volume expansion when it is modified by the half-surface position (especially The stress can thereby complete the present invention at the same time. The volume expansion is accompanied by the production place to prevent the volume of the bismuth ingot which is shaped in the inner surface of the container from being fixed at the time of solidification, and the part -9 having less stress - 201229332 (the lower part of the side) is formed vertically, so the machining loss when the outer peripheral portion of the bismuth ingot is cut is reduced. Therefore, the yield of the bismuth ingot can be improved. [Embodiment] - The following is based on the drawing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The first embodiment is a cross-sectional view of a container for manufacturing a bismuth ingot according to the present invention. The container for producing a bismuth ingot (hereinafter referred to as a container) 11 shown in Fig. 1 is, for example, a quartz material. A bottomed cylindrical or rectangular tubular container having an open upper surface. The side wall of the container 1 is divided into a vertically lower side surface (hereinafter referred to as a straight body portion) 1 1 C and a side lower portion 1 1 C company It is inclined so as to be inclined at an inclination angle (inclination angle with respect to the vertical direction) 侧面 a side surface middle portion (hereinafter referred to as an inclined portion) lib which is expanded toward the upper opening portion, and a side surface upper portion 1 which is vertically connected to the inclined portion 1 1 b 1 a. Here, as shown in Fig. 6(a), when the thickness of the side wall na and the bottom wall lid of the container 11 is T1, the thickness T1 is preferably about 5 to 20 mm. If it is less than 5 mm, there is a container material. On the other hand, if it is larger than 20 mm, it cannot be ignored because of the influence of the increase in the heat insulation of the container, and the melting time of the crucible increases, so that the productivity is lowered due to the increase in the lead time or the cost of electricity. For the same reason, the thickness T2 of the side lower portion 11c is desirably about 5 to 30 mm. Although the length Lc' of the side lower portion 11c is not particularly limited, when the raw material is melted in the container, the length L a above the lower portion of the side surface 1 a The ratio (L + Lb ) / Lc of + L b to the length Lc of the side lower portion 1 1 c is preferably "2" or more.

S -10 - 201229332 The density of the solid is less than the liquid, so in order to make the position of the melt surface at least to the position of Lc (the uppermost end of the straight portion 11c), it is necessary to fill the material to a height of at least twice the Lc in the container. s position. Although the degree of filling of the container differs depending on the shape of the raw material, it is practically sufficient as long as it is the above-described dimensional ratio. The thickness or length of the container 11 is not limited to the case of a rectangular tubular container. The same is true for the cylindrical container. As shown in Fig. 6(a), the internal dimensions of the upper and lower portions of the container 11 are respectively ml. In the case of m2, the difference (ml - m2) between the two is preferably 2 to 50 mm, preferably 1 to 20 mm. When it is less than 2 mm, it is impossible to prevent the ruthenium in the growth of crystal from intruding into the release member and the container. When the thickness is more than 50 mm, the heat insulating property of the inclined portion on the side of the container and the thick portion of the lower portion of the side of the container is increased. Therefore, the melting time of the crucible is increased as compared with the case of 50 mm or less, and the productivity is lowered due to an increase in the lead time or the electric power cost. . Further, for example, in the case of obtaining a mortar of, for example, 150 to 270 kg from a rectangular or cylindrical container, for example, m2 is 600 mm, and ml is 602 to 650 mm', preferably 610 mm to 620 mm. When the crucible is accommodated in the container 11 and the crucible melt is solidified to grow the polycrystalline crucible, the stress accompanying the volume expansion at the time of solidification of the crucible melt located in the inclined portion 1 1 b is dispersed in the inclined portion 1 1 b vertical component and parallel component. For example, by setting the inclination angle 0 to 3 ° or more and less than 90 °, the stress accompanying the volume expansion can be dispersed to such an extent that the release member is not peeled off. According to experiments, it has been confirmed that when the inclination angle is less than 3, the cultured ingot will invade the release member and the release member is damaged. Therefore, -11 - 201229332 expects the tilt angle 0 to be 3° or more. Fig. 2 is a view showing an example of a crystal growth apparatus using the container 11. In the crystal growth apparatus 1 shown in Fig. 2, a crucible ingot is produced by a Kyropulos method, and the container 11 to be used is a release member 12 in which an Si3N4 calcined body or the like is formed on the inner surface. In the crystal growth apparatus 1, the container 11 is supported by a socket 13 made of graphite, and a heater 14 is disposed on the outer circumference of the socket 13. A crystal pulling shaft 15 is disposed at the center of the container 11, and a seed crystal 16 made of single crystal Si (or polycrystalline Si) is attached to the tip end. When the ruthenium ingot is produced by the bubble growth method using the crystal growth apparatus 1, a ruthenium raw material (e.g., ruthenium melt) is introduced into the vessel 1 1 so that the surface of the ruthenium melt 17 is located at the inclined portion lib. Then, the seed crystal 16 is brought into contact with the surface of the crucible melt 17, and the crucible melt 17 is solidified from the surface to grow the polycrystalline crucible. At this time, by growing the polycrystalline silicon while pulling the seed crystal 16 at an extremely low speed, the longitudinal stress accompanying the volume expansion at the time of solidification of the crucible can be alleviated. That is, the pulling speed of the seed crystal 16 is set in accordance with the volume expansion in the longitudinal direction when the crucible melt 17 is solidified. Since the surface of the crucible melt 17 is located at the inclined portion 1 1 b of the container 1 1 , the volume expansion at the time of solidification near the surface of the melt is accompanied by the lateral stress generated in the container 11 being dispersed. In other words, the stress component perpendicular to the inclined portion 1 1 b is made smaller in accordance with the magnitude of the inclination 0, so that the ruthenium crystal can be prevented from intruding into the release member 12. Therefore, during the growth of the polycrystalline crucible, the release member 12 is not damaged, so the cultured ingot is not fixed to the container, and

S -12- 201229332 It is easy to remove it. By appropriately setting the size of the container 11 (the inner diameter of the straight body portion llc, the inclination angle 0, etc.) or the amount of the raw material to be poured (the surface position of the crucible melt 17) can also be determined by the seed crystal 16 The pulling operation is such that the top periphery of the crucible is not in contact with the inner surface of the container 11 (inclined portion 11b). For example, consider that 'when solidified near the surface of the crucible melt located in the inclined portion 11b', considering the case where the crystal formed on the liquid surface is pulled up from the seed crystal 16 to the straight portion of the container, before and after the pulling up The diameter of the surface of the melt will increase to 2Ltan Θ. Then, if the volume expansion amount (2Ltan 0 ) is larger than the volume expansion in the lateral direction at the time of solidification, the top edge of the crucible ingot does not come into contact with the inner surface of the container 11 (inclined portion lib). The tantalum melt is known to expand in the lateral direction by about 1 mm when solidified, and it has been determined by experiments by the inventors of the present invention that a convex portion having a height α (about 0.1 to 0.5 mm) is formed on the top periphery of the tantalum ingot. By setting the pulling amount L of the seed crystal 16 and the tilt angle 0 such that the diameter expansion amount (2Ltane) is larger than (1.+ α ) ', the top circumference of the bismuth ingot can be made not to correspond to the container 1 1 (inclined portion lib). Inside contact. For example, L = 10.5 (mm) · α = 0.1 (mm), 0 2 3 °. In the container 11, the portion of the large stress generated by the volume expansion at the time of solidification of the crucible is used as the inclined portion 1 1 b, and the lower portion 1 1 C of the side surface having a small stress is formed vertically, so that the outer peripheral portion of the crucible ingot is cut. The loss when machining into a cylindrical shape or a square column is small. As a result, the yield of the bismuth ingot can be improved. In other words, as shown in Fig. 5, if the entire side of the container is inclined -13 - 201229332, the stress accompanying the volume expansion during solidification of the crucible can be dispersed, but the bottom outer diameter of the ingot is Since the difference from the upper outer diameter becomes large, the loss when the tantalum ingot is processed into a cylindrical shape or a square column shape becomes large. For example, in the case of a crucible having a bottom diameter of 1 〇° and a total of a side diameter of 90 mm, a height of 1 10 m, and a top diameter of 128 mm, the loss volume is 56% of the total. Similarly, in order to produce a bismuth ingot having a bottom diameter of 90 mm and a height of 11 Omm, and the inclination angle is 20°, 30°, 45°, and 70°, the outer diameter of the upper portion of the rectangular tubular container and the bismuth ingot is significantly increased. The furnace was enlarged, and the loss rate of the bismuth ingot on the bottom surface of the container was calculated to be 70%, 79%, 87%, and 97%, respectively. In this manner, in the case of a conventional method of inclining the entire side surface of the container and applying an inclination angle, the yield of the square columnar ingot is remarkably lowered. If you want to increase the yield slightly, there will be a disadvantage of increasing the number of cuts. On the other hand, in the case of using the container 1 of the embodiment of the present invention, the inclined portion is provided only on the upper side of the top side of the bismuth ingot, and the other side and the face are straight portions, so that the volume loss rate is 36% even if it is inclined. The angle was changed to 10°, 20°, 30°, 45°, 70°, and the loss volume rate was still 36%. When the bismuth ingot is produced by the bubble generation method, the polycrystalline enamel is grown while the seed crystal is pulled up. Therefore, by appropriately adjusting the pulling speed, the top peripheral edge of the bismuth ingot can be brought into contact with the release member 12. Maintain and continue to grow. Therefore, it is possible to more effectively prevent the ingot from intruding into the demolding member 12, and it is not because

I Intrusion situation to hinder the pulling operation of growth crystallization. However, the seed crystal 16 is pulled up in response to the volume expansion at the time of solidification of the crucible, and the longitudinal stress accompanying the volume expansion is alleviated, so

S •14- 201229332 does not produce a defect due to the compression of the melt. By setting the inclination angle 0 to 3° or more and less than 90°, the stress accompanying the expansion of the volume of the coagulation is dispersed to the extent that the release member 12 is damaged, but if the inclination angle 0 is too small, the volume is expanded. As the dispersion effect of the generated stress is small, there is still the possibility of damage due to the undesired release member. When the inclination angle 0 is too large, in order to maintain the height of the inclined portion 1 1 b, the inclined portion 1 1 b is largely extended laterally, which may cause an increase in size of the device, which may cause an increase in loss, and the inclined surface and the straight body In the curved portion of the boundary, the release member is easily cracked and there is a possibility that the bismuth ingot cannot be easily taken out. From this viewpoint, the inclination ′ is desirably set in the range of 10° to 80°, preferably 20° to 70°, or 15°·, more preferably 20° to 45°. [Examples] In Examples 1 to 4, a ruthenium ingot was produced by using a bubble of the crystal growth apparatus 1. The container 11 has a cylindrical shape, and the inner diameter (ml) of the opening portion of the straight body portion 11 is 146 mm, the bottom diameter (m2) of the straight body portion 11c is 125 mm, and the height Lc of the straight body portion 11c is 30 mm + Lb. It is 60 mm. The height Lb of the inclined portion 1 lb is when the inclination angle is 0 = , 30°, 45. 70. At the time, they are 29 mm, 18 mm, and 10 mm, respectively. ο First, the liquid to which boron (concentration: l.〇xl〇16 at〇m/cm3) is added flows into the cylindrical container 11, and the crucible is kept: The surface is located at the middle point of the inclined portion 1 1 b (the condition from the boundary with the straight body portion 1 1 c does not depend on the condition, and is open, angle 0, 60. Inside the birth method a, La = 20. The 4mm 矽 melting table starts from -15-201229332 5.25111111), the temperature gradient in the depth direction is 1〇^:/(:111. Then the crystal orientation is <100> and the 3.5mm square Si single crystal is formed. The seed crystal 16' is in contact with the surface of the crucible melt, and the polycrystalline crucible is grown by manually pulling the seed crystal 16 at 1 mm/h. At this time, the container 11 and the seed crystal 16 are rotated at 5 rpm to seed The polycrystalline silicon is grown into a concentric shape with the crystal 16 as the center. The crucible melt is completely solidified by the growth of 3 hours, and the crucible ingot of the embodiment is obtained. The temperature at the bottom of the vessel 11 will become the freezing point of the crucible, that is, 14 The time point of 10 ° C is regarded as the end point of crystal growth. The results are not shown in Table 1. [Table 1]

Tilt angle 0 [. Intrusion release of the container Example 1 20 Μ j\w 〇 Example 2 30 Μ j»\\ 〇 Example 3 45 Μ /»\N 〇 Example 4 70 Μ 〇 Comparative Example 1 2 Having X comparison Example 2 8 Δ Comparative Example 3 85 X Comparative Example 4 0 X was produced by the bismuth ingots of Examples 1 to 4' As shown in Fig. 3, during the growth process, no polycrystalline germanium 18 was invaded. The release member 12 prevents the pulling operation. That is to say, the use of the container 11 having the inclined portion 1 1 b is formed, and the polycrystalline crucible is formed by pulling the seed crystal 16 while pulling, whereby the compressive stress generated in the crucible melt 17 can be effectively alleviated. Moreover, the produced bismuth ingot can be easily taken out from the container 11. And it won't -16 -

S 201229332 The container 1 1 and the top window of the bismuth ingot have been produced, and there has been no problem in the shape of the bismuth ingot. Further, in the obtained niobium ingot, the grain boundary was neat and compared with the niobium ingot produced by the casting method, and the grain boundary quality confirmed the effectiveness by the bubble method using the container 11 of the embodiment. In the first to fourth embodiments, the case where the inclined portion 1 is 20°, 30°', 45°, and 70° is shown, and the inclination angle 0 j can obtain the same result. When the tilt angle 0 was changed from 10 to 80 points, the results of the experiment were compared. It was confirmed that: in the case of 15 to 60°, the yield of the bismuth ingot taken out from the container was 0 to 45°, and the yield was the highest. Excellent. [Comparative Example] Fig. 4 is a view showing a crystal formed in Comparative Example 4. In Fig. 4, the 20-crystal growth apparatus 2 is added to the constituent element which is the same as or corresponding to the solid-length apparatus 1, and the crystal growth apparatus of the embodiment is a general straight-type container 21. In Comparative Examples 1 to 4, a ruthenium ingot was produced using the crystal growth apparatus 2. In the cylindrical container 21, a container having an inner diameter is used. The examples in which the amount of the raw material to be poured and the polycrystalline germanium are the same are the same. The weld of the circumference. The actual direction of the ingot splitting is more vertical. In the case where the inclination angle 0 of the crystal growth 1 b is 60°, the range of ° is also slightly higher at the inclination angle 0, and the slanting device is crystallized into a pattern number. The difference in the knot 1 is the growth condition of 125 mm by the bubble method, etc., and -17-201229332. In Comparative Example 1, the container is caught in the crystal pulling up, and the volume continues to grow in this state, the volume The expansion stress concentrates on the bottom of the container and destroys the container. On the other hand, in the container 21 after the ingot was taken out, the mold release member 22 was not peeled off in the large half of the bottom surface and the side surface of the container 21, but there were many areas of the release member in the portion corresponding to the top of the crucible ingot. 22 disappeared in a face. This should be that when the vicinity of the surface of the crucible melt 27 is solidified, the polycrystalline crucible 28 which expands in the lateral direction intrudes into the demolding member 22 because the release member 22 is peeled off by the half-stretching in this state, and the polycrystalline compact is removed. It is placed on the container 21, so it is difficult to take out the bismuth ingot. In the case where the inclination angle of Comparative Example 2 is 8°, when the crystal is pulled up by the bubble generation method, although the crystal is not stuck to the container, the friction between the top side of the crucible ingot and the release member is severe, and it becomes difficult to take out. result. In the case of Comparative Example 3, the release member was cracked at the inclined portion of the container and the bent portion of the straight portion, so that the ingot was welded to the container at this portion, and it was difficult to take out the ingot. It should be that in the bent portion, the embrittled release member cannot withstand the volume expansion stress. In the production of the niobium ingot prepared in Comparative Example 4, as shown in Fig. 4, the polycrystalline crucible 28 invaded the mold release member 22 during the growth process to hinder the pulling operation. Further, the movement of the growth crystal upward is restricted (the pulling speed is lowered), and as a result, the stress caused by the volume expansion at the time of solidification is not moderated, and the crucible melt is compressed, and the melt is spattered from the center of the container and splashed. The phenomenon of going out of the container (the squirting of the melt). Due to the spouting process during the growth process, good crystal growth is hindered and expensive device components are damaged.

-18- S 201229332 Combining these results' The inclination angle 0 at which the bismuth ingot can be taken out from the container without any problem is in the range of 10° to 80°. In view of the fact that the release member of the curved portion is easily peeled off, and the volume expansion stress of Si in the lateral direction is 'inferior to the case where the inclination angle 0 is 20° to 70°, more preferably, the inventors have specifically explained what has been done by the inventors according to the embodiment. The invention is not limited to the embodiments described above, and may be modified without departing from the spirit and scope of the invention. For example, in the embodiment, a material composed of quartz, si 3 N 4 , Si C , graphite, or alumina or a combination of two or more types may be used as the case where the container 11 is made of a quartz material. Composition. Further, for example, the container 1 1 disperses the stress caused by the expansion of the volume when the crucible is solidified by the inclined portion 1 1 b, and is therefore effective also when the crucible is produced by the casting method. In the case of producing a bismuth ingot by a casting method, it is only necessary to allow the surface of the sand solution to be located at the inclined portion lib. Even when the shape of the container 11 was changed from a cylindrical shape to a rectangular tube shape, the same results as in the examples 1 to 4 and the comparative examples 1 to 4 were obtained. All of the ideas of the embodiments disclosed herein are examples and are not intended to be limiting. The scope of the present invention is defined by the scope of the claims and the scope of the claims BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a container for manufacturing a bismuth ingot to which the present invention is applied. -19 - 201229332 Fig. 2 is a view showing an example of a crystal growth apparatus using a container for producing an ingot in the present invention. Fig. 3 is a view showing a growth process of polycrystalline silicon when the crystal growth apparatus of the embodiment is used. Fig. 4 is a view showing a crystal growth apparatus using a general straight type ingot manufacturing container. Fig. 5 is a view showing the loss generated when a conventional tilt type container is used. Fig. 6 is a cross-sectional view (a) of a side wall of a container for manufacturing a ruthenium ingot according to an embodiment of the present invention, and an example of a shape of a container when viewed from an upper portion of the container toward a bottom wall surface (square tubular container (b), cylindrical shape) A brief description of the container (c)), and its appropriate thickness or length. [Explanation of main component symbols] 1 : Crystal growth device Π : Container for manufacturing enamel ingot 1 1 a : Side upper portion 1 1 b : Side middle portion (inclined portion) 1 1 c : Side lower portion (straight body portion) 1 2 : Release Item 13: Seat 1 4 : Heater 1 5 : Crystal pull-up shaft 1 6 : Seed crystal

S -20- 201229332 1 7 : 矽 melt 1 8 : polycrystalline sand 0 : tilt angle -21 -

Claims (1)

201229332 VII. Patent application scope: 1. A container for manufacturing an antimony ingot, which is a bottomed cylindrical ingot manufacturing container for opening, which is used for solidifying a crucible ingot to grow polycrystalline crucible: characterized by: The side wall of the container is: a lower portion of the side surface formed vertically; a side portion of the side surface connected to the lower portion of the side surface and inclined to expand toward the upper opening portion at a predetermined inclination angle 0 with respect to the vertical direction; and vertically connected to the middle portion of the side surface The above-mentioned side upper portion constitutes a crucible 2 - a container for manufacturing an antimony ingot according to the first aspect of the patent application, wherein the inclination angle 0 is 10 to 80°. 3- Container for manufacturing an antimony ingot according to item 2 of the patent application, wherein the inclination angle 0 is 1 5 to 60 °. 4. The container for manufacturing an antimony ingot according to the second aspect of the invention, wherein the inclination angle 0 is 20 to 70°. 5. The container for manufacturing an antimony ingot according to the second aspect of the invention, wherein the inclination angle 0 is 20 to 45°. The container for producing an antimony ingot according to any one of claims 1 to 5, which is a material composed of any one of quartz, Si3N4, SiC, graphite, and alumina, or a combination of two or more thereof. Made up of materials. A method for producing a bismuth ingot, which is characterized in that: in the container for manufacturing a bismuth ingot according to any one of claims 1 to 6, the ruthenium raw material is placed on the surface of the sputum-melting liquid at the inclined portion - 22- S 201229332 The above-mentioned cerium melt is solidified to grow polycrystalline germanium. 8. The method for producing a niobium ingot according to claim 7, wherein the seed crystal is brought into contact with the surface of the niobium melt, and the crucible is solidified from the surface while the seed crystal is pulled up to grow the polycrystalline crucible. 9. The method of producing an antimony ingot according to claim 8, wherein the seed crystal is pulled up at a speed corresponding to a volume expansion at which the crucible melt is solidified. -twenty three-