JP4817761B2 - Method for manufacturing semiconductor ingot and solar cell element - Google Patents

Description

  The present invention relates to a method for manufacturing a semiconductor ingot and a solar cell element.

  Solar cells convert incident light energy into electrical energy, and crystalline silicon solar cells are the mainstream.

  This crystalline silicon solar cell is further classified into a single crystal type and a polycrystalline type, and a polycrystalline silicon substrate used for the polycrystalline silicon solar cell is generally manufactured by a method called a casting method.

  This casting method is a method of forming a silicon ingot by cooling and solidifying a silicon melt in a mold made of quartz or the like coated with a release material. The ends of the silicon ingot are removed, cut into a desired size, and the cut out ingot is sliced to a desired thickness to obtain a polycrystalline silicon substrate for forming a solar cell.

  A method for manufacturing a polycrystalline silicon substrate will be described below using a general casting apparatus.

  A melting crucible for melting the silicon raw material is disposed in the upper part of the casting apparatus while being held by the holding crucible, and a pouring port for pouring the silicon melt by inclining the melting crucible is provided at the upper edge of the melting crucible. It is done. A heating means is disposed around the melting crucible and holding crucible, and a mold into which a silicon melt is poured is disposed below the melting crucible and holding crucible. The melting crucible is made of, for example, high-purity quartz in consideration of heat resistance and the fact that impurities do not diffuse into the silicon melt. The holding crucible is used to hold a melting crucible made of quartz or the like because the melting crucible is softened at a high temperature in the vicinity of the silicon melt and cannot keep its shape, and the material is graphite or the like. As the heating means, for example, a resistance heating type heater or an induction heating type coil is used.

  The mold placed in the lower part of the melting crucible and holding crucible is made of quartz, graphite or the like, and is used by applying a release material mainly composed of silicon nitride, silicon oxide or the like to the inside thereof. Further, a mold heat insulating material is installed around the mold to suppress heat removal. As the mold heat insulating material, a carbon-based material is generally used in consideration of heat resistance, heat insulating properties, and the like. In some cases, a cooling plate for cooling and solidifying the poured silicon melt is installed below the mold.

  In the above apparatus, the silicon raw material is charged into the melting crucible, the silicon raw material in the melting crucible is melted by the heating means, and after all the silicon raw material in the melting crucible is dissolved, the crucible is tilted to The silicon melt is poured from the pouring port at the edge to the mold installed at the bottom.

  After pouring, the silicon in the mold is cooled from the bottom and solidified in one direction, and then slowly cooled while controlling the temperature to a temperature at which it can be taken out of the furnace. Finally, the silicon is taken out of the furnace and casting is completed.

  In general, in order to improve the quality of polycrystalline silicon substrates for solar cells, it is ideal to solidify completely in one direction in order to prevent structural defects such as thermal stress induced dislocations occurring in the mold. Has been. In order to perform such unidirectional solidification, a method is used in which the side of the mold is insulated and the top is heated with a heater to a high temperature and the bottom is cooled to a low temperature by a cooling plate.

The silicon melt filled in the mold maintained in such a temperature environment begins to solidify from the bottom where the supercooling condition is reached, and then the heat of the melt is deprived through the solidified layer. The phase changes from the liquid phase to the solid phase at the interface of the liquid phase (hereinafter referred to as the solid-liquid interface), and the solid-liquid interface gradually moves above the mold and the solidification process proceeds.
Japanese Patent Laid-Open No. 11-180711

  At this time, since the temperature distribution on the surface perpendicular to the solid-liquid interface traveling direction is substantially uniform, there is no difference in thermal shrinkage between the mold side surface and the solidified body, and as a result, only a small thermal stress is generated.

  However, as a result of measurement of the residual stress distribution within the solidified body (see FIG. 4B) by the present inventor, it was found that there are the following problems.

  In FIG.4 (b), a continuous line shows the residual-stress measurement result of a solidified body horizontal direction on the solidified body central axis parallel to a solid-liquid interface advancing direction. The other points show the residual stress measurement results in the horizontal direction of the solidified body at 4 points selected from the plane perpendicular to the solid-liquid interface traveling direction.

  From this figure, in the solidified body with a height of 300 mm, the residual stress in the horizontal direction of the solidified body on the central axis of the solidified body parallel to the solid-liquid interface traveling direction remains large tensile stress at the bottom surface, and conversely above 25 mm It was found that a large compressive stress remained and gradually changed from the compressive stress region to the tensile stress region upward.

  In addition, on the plane perpendicular to the solid-liquid interface traveling direction, the stress value was almost the same as the stress value on the central axis of the solidified body parallel to the solid-liquid interface traveling direction.

  Regarding this experimental result, the following mechanism can be considered.

  That is, FIG. 4 (a) shows the shape that the solidified body is about to deform immediately after the silicon is completely solidified in the mold, and the bottom surface of the solidified body is closest to the mold in contact with the cooling plate, so Although it is cooled, the cooling rate is reduced as a result of cooling through a silicon solid phase having a low thermal conductivity above 25 mm, and the amount of temperature drop in the bottom surface layer part and the solid phase above the solidified body that has entered from the bottom surface layer part inside There is a difference in the amount of temperature decrease. As a result, there is a problem that a large tensile stress remains in the bottom surface layer portion, and a large compressive stress remains in a balanced manner.

  Such a tendency becomes more prominent as the cooling ability is improved and the solidified body bottom surface temperature is quickly lowered to shorten the solidification time in order to improve productivity.

  On the other hand, it is also conceivable to apply heat treatment such as quenching, annealing and tempering performed to improve the material properties of the steel material to the silicon ingot.

  However, in the case of steel materials, it is known that these heat treatments are applied to the entire material for the purpose of improving the properties of the entire material. However, for steel materials, phase transformation, dislocation hardening, microcrystallization, etc. Since the material itself is cured and used, it is possible to quench the entire solidified body, whereas silicon is a very typical brittle material, and heat treatment such as steel is performed on the entire silicon material. If applied, the same method cannot be used because the solidified body is easily destroyed.

  That is, the fracture stress of polycrystalline silicon is known to be a low value of about several tens of MPa, although it varies significantly depending on the nature of the grain boundaries, the size of adjacent crystal grains, and the plane orientation. Therefore, even if the residual stress value is about the same as the measured stress value this time, even if it is not broken (that is, there is no bottom crack when the solidified body is cooled), the solidified part is cut with a cutting device such as an inner peripheral blade. In particular, the tensile stress remaining on the surface at the moment of cutting off the bottom material of the solidified body disappears, and the internally balanced compressive stress is instantly released in the tensile direction (residual stress is restored). Arrangement), a huge relocation stress is generated, which induces a bottom crack in the silicon solidified body.

  The present invention has been made in view of such conventional problems, and an object of the present invention is to provide a semiconductor ingot capable of suppressing the occurrence of cracks during processing.

The method of manufacturing a semiconductor ingot of the present invention is intended for unidirectional solidification the semiconductor melt inside the mold, have a annealing step of Yakinamasu only solidification starting end portion of the obtained solidified body by the unidirectional solidification In the annealing step, the solidification start end is heated to reach an upper limit temperature of 1400 ° C., and the solidification start end after the heating step is maintained at 10 ° C./min. And the heating step is performed after a preliminary cooling step of cooling the solidified body obtained by the unidirectional solidification under a condition of 10 ° C./min or more. It is characterized by.

  The solidification start end is a region of 1/3 or less of the whole solidified body.

  The annealing step includes heating the solidification start end to 1400 ° C. as an upper limit temperature, and maintaining the temperature for 30 minutes or more, and setting the solidification start end after the heating step to 10 ° C. / and a cooling step for cooling under a condition of less than min. In particular, the heating step is performed after a precooling step of cooling the solidified body obtained by the unidirectional solidification under a condition of 10 ° C./min or more.

  Further, the annealing step is performed at 660 Pa to 0.1 MPa and in an inert air stream or an atmosphere in the air.

  The annealing process as described above is performed in a state where the solidified body is in the mold, and in this case, the heating process is performed using a heating unit disposed below the mold. It is preferable. Alternatively, the annealing step is performed in a state where the solidified body is taken out of the mold, and in that case, the heating step is performed by placing the solidified body on a heating member. Is preferred.

  Moreover, the manufacturing method of the solar cell element of this invention comprises the process of cut | disconnecting the semiconductor ingot obtained by the manufacturing method of the above semiconductor ingots, and obtaining the semiconductor substrate for solar cell elements.

  The method for producing a semiconductor ingot of the present invention solidifies a semiconductor melt unidirectionally inside a mold, and has an annealing step of annealing only a solidification start end portion of a solidified body obtained by the unidirectional solidification. Therefore, it is possible to suppress the occurrence of cracks during processing by effectively reducing the stress remaining in the solidified body.

  Further, since only the solidification start end portion needs to be annealed, the residual stress can be reduced in an extremely short time compared to the case where the entire solidified body is annealed.

  In particular, it is effective to anneal a region of 1/3 or less of the entire solidified body, which is a portion having a large residual stress.

  In the annealing process of the present invention, the solidification start end is heated at 1400 ° C. as an upper limit temperature, and the solidification start end after the heating process is maintained at 10 ° C. It is preferable to set so as to include a cooling step of cooling under a condition of less than / min.

  Here, the heating step is preferably performed after a precooling step of cooling the solidified body obtained by the unidirectional solidification under a condition of 10 ° C./min or more. The total cooling time from formation to obtaining a semiconductor ingot with reduced residual stress can be made extremely short.

  The annealing step is preferably performed at 660 Pa to 0.1 MPa and in an inert air current or an atmosphere in the atmosphere, thereby having a relatively simple apparatus configuration that does not use a high vacuum apparatus or a pressure apparatus. It becomes possible to carry out.

  If the solidified body is in the mold, the annealing process can be simplified because there is no need for a separate annealing apparatus, and the time for carrying out to another apparatus can be shortened. it can. In this case, it is preferable that the heating step is performed using a heating unit disposed below the mold.

  On the other hand, the annealing step may be performed with the solidified body taken out of the mold, and in that case, the heating step is performed by placing the solidified body on a heating member. Is preferred.

  In addition, the method for manufacturing a solar cell element of the present invention includes a step of obtaining a semiconductor substrate for a solar cell element by cutting the semiconductor ingot obtained by the method for manufacturing a semiconductor ingot as described above. By reducing the residual stress as described above, it is possible to effectively suppress the occurrence of cracks due to the force applied to the semiconductor substrate when manufacturing the solar cell element.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

≪Semiconductor ingot manufacturing method≫
<First embodiment>
FIG. 1 is a schematic cross-sectional view showing a casting apparatus used in a method for producing a semiconductor ingot according to the present invention, wherein (a) shows a crucible and (b) shows a mold. 1 is a crucible (1a is a melting crucible, 1b is a holding crucible), 2 is a pouring port, 3 is a heating means, 4 is a silicon melt, 5 is a mold, 6 is a mold release material, 7 is a mold heat insulating material, and 8 is a cooling plate , 9 indicates a mold upper part heating means. These are arranged in a casting furnace (not shown).

  First, in the crucible 1, the silicon raw material is melted by heating using a heating means 3 such as a resistance heating type heater or an induction heating type coil to obtain a silicon melt.

  Here, for the melting crucible 1a, high-purity quartz or the like is used in consideration of heat resistance and the fact that impurities do not diffuse into the silicon melt. The holding crucible 1b is for holding the melting crucible 1a made of quartz or the like because the melting crucible 1a is softened at a high temperature in the vicinity of the silicon melt and cannot keep its shape, and the material is graphite or the like. .

  Next, the crucible 1 is tilted, and the silicon melt is supplied from the pouring port 2 of the crucible 1 to the lower mold 5.

  Here, the mold 5 is made of, for example, quartz or graphite, and a mold release material 6 mainly composed of silicon nitride, silicon oxide or the like is applied to the inner wall thereof.

  Next, by cooling the lower part of the mold 5 while keeping the upper part of the mold 5 at a high temperature, the supplied silicon melt is solidified in one direction from below to form a solidified body.

  The solidified body is formed by a mold heat insulating material 7 made of a carbon-based material or the like provided around the mold 5 and a silicon melt provided under the mold 5 for cooling and solidifying the melt. The cooling plate 8 is controlled to be solidified in one direction from below to above.

  In the above process, the solid material may be formed in the mold 5 as it is after the silicon raw material is dissolved in the mold 5 without using the crucible 1.

  Next, the solidified body formed as described above is annealed through a preliminary cooling step, a heating step, and a cooling step. In the present embodiment, the annealing process is performed without removing the solidified body from the mold 5 in the casting furnace.

  FIG. 2 is a schematic cross-sectional view for explaining a method for producing a semiconductor ingot according to the present invention, in particular, an annealing process in a casting apparatus. 11 is a solidified body (silicon), 8 is a cooling plate, 9 is a mold upper heating means for heating the solidified body head, 10 is a mold lower heating means, and 21 (22, 23) are thermocouples for controlling the bottom heat treatment. It is.

  First, in the preliminary cooling step, the solidification start end of the solidified body is rapidly cooled at a cooling rate of 10 ° C./min or more. In this step, the cooling plate 8 used for unidirectional solidification may be used for cooling as it is.

  Here, the temperature and cooling rate of the solidified body are measured using the thermocouple 21 (22, 23) and strictly controlled. The thermocouple 21 is embedded so that a temperature at a predetermined height can be measured from the center of the solidified body bottom surface, and the thermocouple 22 is measured from the center of the solidified body bottom surface. In actual operation, the temperature inside the solidified body is monitored by the thermocouple 23 arranged outside the mold 5, thereby eliminating the trouble of setting the thermocouple in the mold every time casting is performed, and the mold member is consumed and solidified. It is preferable to suppress body defects.

  Next, in the heating step, the solidification start end portion of the precooled solidified body is heated using the mold lower part heating means 10 at 1400 ° C. as the upper limit temperature, and the temperature is maintained for 30 minutes or more. That is, as indicated by the arrow in FIG. 2, the cooling plate 8 used for the preliminary cooling is moved downward, and the mold lower part heating means 10 is inserted into the lower part of the mold 5 to heat the solidified body from the lower part.

  In this way, by heating and holding the solidified body by the mold lower part heating means 10, it is possible to reduce the stress remaining at the solidification start end (bottom) after complete solidification and to suppress the occurrence of cracks during processing.

  Here, it is preferable from the viewpoint of effective reduction of stress and processing time to anneal a region of 1/3 or less of the entire solidified body, which is a portion having a large residual stress.

  Finally, in the cooling step, the cooling plate 8 is raised again toward the bottom of the mold 5 and gradually cooled at a cooling rate of less than 10 ° C./min.

  Such an annealing process is performed at 660 Pa to 0.1 MPa and in an inert air atmosphere or an atmosphere in the atmosphere from the viewpoint of performing with a relatively simple apparatus configuration that does not use a high vacuum apparatus or a pressure apparatus. Are preferred.

  The semiconductor ingot is manufactured by removing the solidified body that has undergone the above steps from the mold.

<Second Embodiment>
A second embodiment will be described with reference to FIG.

  Fig.3 (a) is a schematic sectional drawing for demonstrating the manufacturing process of the semiconductor ingot which concerns on this invention, especially the annealing process outside a casting apparatus (inside a heating container).

  In the following, description of the same configuration as that of the first embodiment described above will be omitted, and only the configuration unique to this embodiment will be described.

  In the present embodiment, the solidified body is taken out of the casting furnace and rapidly cooled in a state of being present in the mold 5, and then carried into the heating container 32 to perform an annealing process.

  Also in this embodiment, by heating and holding the solidified body with the mold lower heating means 10, the stress remaining at the solidification start end (bottom) after complete solidification is reduced, and the occurrence of cracks during processing is suppressed. it can.

  Furthermore, according to the present embodiment, since the solidified body is annealed after being taken out of the casting furnace, it becomes possible to use the casting furnace for new casting without considering the annealing treatment time. The property is greatly improved.

<Third embodiment>
A third embodiment will be described with reference to FIG.

  FIG.3 (b) is a schematic sectional drawing for demonstrating the manufacturing process of the semiconductor ingot which concerns on this invention, especially the annealing process outside a casting apparatus (outside a casting_mold | template).

  In the following, description of the same configuration as that of the first embodiment described above will be omitted, and only the configuration unique to this embodiment will be described.

  In this embodiment, the solidified body is taken out from the casting furnace and the mold 5 and cooled to room temperature, and then the annealing process is performed in a state where the solidified body is placed on the hot plate 30 and the heating element 31.

  Also in this embodiment, the stress remaining at the solidification start end (bottom) after complete solidification is reduced by heating and holding the solidified body using the hot plate 30 and the heating element 31 instead of the mold lower part heating means 10. It is possible to suppress the occurrence of cracks during processing.

  Furthermore, according to the present embodiment, since the solidified body is annealed after being taken out of the casting furnace, it becomes possible to use the casting furnace for new casting without considering the annealing treatment time. The property is greatly improved.

≪Method for manufacturing solar cell element≫
Hereinafter, the manufacturing method of a solar cell element is demonstrated using figures.

  FIG. 5: is a schematic sectional drawing which shows the solar cell element formed using this invention, (a) is schematic sectional drawing, (b) is the top view seen from upper direction, (c) is seen from the downward direction It is a bottom view.

  In the figure, 41 is a semiconductor substrate, 42 is a reverse conductivity type diffusion region, 43 is an antireflection film, 44 is a surface electrode, 44a is a front side bus bar electrode, 44b is a front side finger electrode, 45 is a back electrode, Reference numeral 45a denotes a back-side extraction electrode, 45b denotes a back-side collecting electrode, and 46 denotes a back-surface electric field region.

  The semiconductor ingot obtained by the method of each of the above embodiments is cut into a size of about 10 cm × 10 cm or 15 cm × 15 cm by removing a side surface of the semiconductor ingot with a band saw device or the like. Then, a plurality of semiconductor substrates 41 are formed by slicing to a predetermined thickness, for example, 300 μm or less, using a wire saw device or the like. In order to clean the mechanically damaged layer or the contaminated layer on the surface that has been cut or sliced, it is desirable that the surface is etched by a very small amount with NaOH, KOH, hydrofluoric acid, or hydrofluoric acid.

  Next, it is desirable to form minute protrusions on the surface of the semiconductor substrate 41 using a dry etching method or a wet etching method.

Thereafter, the semiconductor substrate 41 is placed in a diffusion furnace and heat-treated in a gas containing an impurity element such as phosphorus oxychloride (POCl ₃ ), thereby diffusing phosphorus atoms in the outer surface portion of the semiconductor substrate 41 and n A reverse conductivity type diffusion region 42 having a conductivity type of the mold is formed.

  Then, other portions are removed except for the reverse conductivity type diffusion region 42 on the light receiving surface side of the semiconductor substrate 41, and then washed with pure water. As this removal method, for example, a film having resistance to hydrofluoric acid is applied to the surface side of the semiconductor substrate 41, and a reverse conductivity type diffusion other than the light receiving surface side of the semiconductor substrate 41 is performed using a mixed solution of hydrofluoric acid and nitric acid. After removing the region by etching, a film having resistance to hydrofluoric acid may be removed.

Next, an antireflection film 43 is formed on the light receiving surface side of the semiconductor substrate 41. The anti-reflection film 43 is a silicon nitride film, a silicon oxide film or the like, for example, a silicon nitride film is deposited by plasma in a mixed gas glow discharge decomposition of silane and (SiH ₄₎ and ammonia (NH ₃₎ plasma It is formed by a CVD method or the like. The antireflection film 43 is formed so as to have a refractive index of about 1.8 to 2.3 in consideration of a refractive index difference with the semiconductor substrate 41, and is formed to a thickness of about 500 to 1200 mm. . When the silicon nitride film is formed in the presence of hydrogen plasma in this way, it has a passivation effect at the same time, so that it has an effect of improving the electric characteristics of the solar cell in addition to the antireflection function.

  Next, the front electrode 44 and the back electrode 45 are formed. The current collecting electrode 45b on the back surface side constituting the back electrode 45 is mainly composed of a metal made of, for example, aluminum powder, and the organic vehicle and the glass frit are 10 to 30 parts by weight, 0.1 parts by weight per 100 parts by weight of aluminum. An electrode material containing as a main component a first metal added to 5 parts by weight in paste form is used. As a specific shape, for example, as shown in FIG. 5 (c), an opening except for a portion where the extraction electrode 45a on the back surface side is formed is provided so as to be almost the entire surface of the back surface. As a coating method, a known method such as a screen printing method can be used. After the coating, the solvent is evaporated at a predetermined temperature and dried.

  The rear-side extraction electrode 45a constituting the back-side electrode 45 and the front-side bus bar electrode 44a and the finger electrode 44b constituting the front-side electrode 44 are mainly composed of a metal material having better solder wettability than the first metal, such as silver powder. An electrode material mainly composed of a second metal prepared by adding 10 to 30 parts by weight and 0.1 to 5 parts by weight of an organic vehicle and glass frit to 100 parts by weight of silver, respectively, is used.

  As for the surface electrode 44, as shown in FIG. 5 (b), a bus bar electrode 44a for taking out output from the surface as a general solar cell element, and a current collecting electrode provided so as to be orthogonal thereto. What is necessary is just to form in a grid | lattice form by the finger electrode 44b.

  As a coating method, a known method such as a screen printing method can be used, and after coating, the solvent is evaporated at a predetermined temperature and dried.

  The surface electrode 44 and the back electrode 45 coated and dried as described above are baked for about 1 to 30 minutes at a maximum temperature of 600 to 800 ° C., thereby baking the electrodes on the semiconductor substrate 41. Can be formed. Further, at the same time as forming the current collecting electrode 45b on the back surface, the back surface electric field region 46 is formed to prevent aluminum from diffusing into the semiconductor substrate 41 and recombination of carriers generated on the back surface. A portion corresponding to the surface electrode 44 of the antireflection film 43 is etched in advance, and an electrode material (silver paste or the like) containing the second metal as a main component is applied to the portion and baked to form the reverse conductivity type diffusion region 42. Conduction may be taken, or an electrode material (silver paste or the like) containing the second metal as a main component is directly applied onto the antireflection film 43 and fired, and the antireflection film 43 is fired by a so-called fire-through method. May be made to be electrically connected to the reverse conductivity type diffusion region 42.

  Since the solar cell element produced by the above method uses a semiconductor ingot with reduced residual stress as described above, a cutting process for obtaining a semiconductor substrate for a solar cell element or a solar cell element is produced. The generation of cracks due to the force applied to the semiconductor substrate can also be effectively suppressed.

  Examples of the present invention will be described in detail below.

  First, using a conventional method that does not have an annealing step, the bottom of the solidified body when the solidified body is cut as a critical condition when the silicon melt is unidirectionally solidified in the mold and the silicon solidified body is cooled to room temperature. 15 ° C./min, which is a cooling rate at which cracks occur, was determined as a basic cooling rate.

  And the following experiment was conducted regarding 1st embodiment which concerns on the manufacturing method of the semiconductor ingot of this invention.

  First, after performing rapid cooling at the above cooling basic speed as a unidirectional solidification and precooling step, the cooling plate 8 is lowered and separated from the bottom surface of the mold 5 without taking it out of the casting furnace. It was moved horizontally and placed so as to face the bottom of the mold.

  And as a heating process, after changing the output of the casting_mold | template lower part heating means 10 and heating solidified body bottom temperature T1 from 100 degreeC to the ultimate temperature of 1400 degreeC, the time to hold | maintain this ultimate temperature was variously changed.

  As a subsequent cooling step, the output of the mold lower part heating means is lowered, and the cooling rate when the solidified body bottom temperature 21 is cooled to room temperature is 3 conditions of 1.5 ° C./min, 10 ° C./min, and 15 ° C./min. And the presence or absence of cracks after cutting the solidified body was evaluated.

  The above experimental results are shown in FIG.

  As shown in FIGS. 6 (a) and (b), in the heating process, the ultimate temperature of the solidified body bottom temperature is 200 ° C. to 1400 ° C., and the holding time of the ultimate temperature is 30 minutes or more, and It has been found that cooling at a rate of less than 10 ° C./min in the cooling step is a suitable condition for suppressing cracks.

  In addition, when the ultimate temperature of the solidified body bottom temperature 21 is less than 200 ° C., the reason why the generation of cracks cannot be prevented even if the subsequent cooling is performed is that the solidified body bottom temperature is not sufficiently heated. It is conceivable that the tensile stress relaxation effect is not achieved. Further, it was found that when the ultimate temperature holding time was less than 30 min, cracks occurred and the effect of relaxing the tensile stress was not exhibited. Further, as shown in FIG. 6 (c), when cooling is performed under the condition of cooling rate = 15 ° C./min, even if the cracks disappear in FIGS. 6 (a) and (b), Under these conditions, cracks occurred after cutting the solidified body. This is considered to be because cracking occurred because the bottom of the solidified body was heated, but the effect of relaxing the tensile stress was obtained, but it was rapidly cooled again.

  Next, the following experimental results were obtained for the processing time for manufacturing a semiconductor (silicon) ingot. A solidified body having a size of 70 cm × 70 cm × 280 cm was used.

  First, as a conventional example, when cooling is performed at a cooling rate of 1.5 ° C./min after unidirectional solidification so that cracks do not occur due to residual stress, it takes from the start of melting of the silicon raw material to removal of the solidified body from the casting furnace. The total casting time was about 30 hours (melting: about 5 hours, unidirectional solidification: about 9 hours, cooling: about 16 hours). The cooling here is simply cooling to room temperature and is different from the cooling step in the annealing step.

  On the other hand, as a present Example, when it cools preliminarily at a cooling rate of 15 ° C./min, the bottom of the silicon solidified body is held at an ultimate temperature of 1000 ° C. for 60 min, and cooled at 1.5 ° C./min, the total casting time Can be shortened to about 20 hours (melting: about 5 hours, unidirectional solidification: about 9 hours, pre-cooling: about 2 hours, heating / cooling: about 4 hours), and the cycle time of the casting process in the casting furnace It was found that a significant reduction can be achieved.

  As in the second embodiment and the third embodiment described above, even when the annealing process is carried out from the casting furnace, it is solidified even if cut to a desired dimension, as in the results of the above examples. There were no cracks in the body. In this case, since the annealing process is performed outside the casting furnace, the total casting time can be shortened to about 14 hours (melting: about 5 hours, unidirectional solidification: about 9 hours). It was found that the cycle time can be greatly shortened.

It is a schematic sectional drawing showing the casting apparatus used for the manufacturing method of the semiconductor ingot concerning this invention, (a) is a crucible, (b) is a figure which shows a casting_mold | template. BRIEF DESCRIPTION OF THE DRAWINGS The schematic sectional drawing for demonstrating the manufacturing method of the semiconductor ingot which concerns on this invention, Especially the annealing process in a casting apparatus is demonstrated. It is a schematic sectional drawing for demonstrating the manufacturing method of the semiconductor ingot concerning this invention, especially the annealing process outside a casting apparatus, (a) is the annealing process in a heating container, (b) is explaining the annealing process outside a casting_mold | template. To do. (A) is a schematic sectional drawing which shows typically the residual stress distribution of the solidified body which concerns on this invention, (b) is a figure which shows the result of having measured the residual stress distribution of the solidified body which concerns on this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows the solar cell element formed using this invention, (a) is a schematic sectional drawing, (b) is the top view seen from upper direction, (c) is the bottom view seen from the downward direction. . It is a figure which shows the presence or absence of the crack generation | occurrence | production of the solidified body at the time of changing the cooling rate in a cooling process, (a) is a cooling rate of 1.5 degreeC / min, (b) is a cooling rate of 10 degreeC / min. (C) has a cooling rate of 15 ° C./min.

Explanation of symbols

1a: Melting crucible 1b: Holding crucible 2: Pouring spout 3: Heating means 4: Silicon melt 5: Mold 5a: Bottom member 5b: Side member 6: Mold release material 7: Mold heat insulating material 8: Cooling plate 9: Mold upper heating Means 10: Lower mold heating means 11: Silicon coagulated body 12: Silicon coagulated body 21: Thermocouple 1 for temperature measurement at the bottom of the coagulated body
22: Thermocouple 2 for temperature measurement at the bottom of the solidified body
23: Thermocouple 3 for controlling the residual stress removal process at the bottom of the solidified body
30: Hot plate 31: Heating element 32: Heating container 41: Semiconductor substrate 42: Reverse conductivity type diffusion region 43: Antireflection film 44: Front electrode 44a: Front side bus bar electrode 44b: Front side finger electrode 45: Back electrode 45a: Extraction electrode 45b on the back side: current collecting electrode 46 on the back side: electric field area on the back side

Claims (8)

A method for producing a semiconductor ingot for unidirectionally solidifying a semiconductor melt inside a mold,
Have a annealing step of Yakinamasu only solidification starting end portion of the obtained solidified body by the unidirectional solidification,
In the annealing step, the solidification start end is heated at 1400 ° C. as an upper limit temperature and the temperature is maintained for 30 minutes or more, and the solidification start end after the heating step is less than 10 ° C./min. A cooling process for cooling under the conditions of
The method of manufacturing a semiconductor ingot, wherein the heating step is performed after a precooling step of cooling the solidified body obtained by the unidirectional solidification under a condition of 10 ° C./min or more .   The method for producing a semiconductor ingot according to claim 1, wherein the solidification start end portion is a region of 1/3 or less of the entire solidified body. The annealing step is a 660Pa to 0.1 MPa, and method of manufacturing a semiconductor ingot according to claim 1 or 2, characterized in that is carried out in an atmosphere of an inert gas stream or atmosphere. The annealing step is a method of manufacturing a semiconductor ingot according to any one of claims 1 to 3, characterized in that the solidified body is performed in a state in said mold. The heating step is a method of manufacturing a semiconductor ingot according to any one of claims 1 to 4, characterized in that is carried out using a heating means disposed below the mold. The annealing step is a method of manufacturing a semiconductor ingot according to any one of claims 1 to 5, characterized in that performed the solidified body in a state of taking out the outside of the mold. The method of manufacturing a semiconductor ingot according to claim 6 , wherein the heating step is performed by placing the solidified body on a heating member. The manufacturing method of a solar cell element which has the process of cut | disconnecting the semiconductor ingot obtained by the manufacturing method of the semiconductor ingot in any one of Claim 1 thru | or 7, and obtaining the semiconductor substrate for solar cell elements.

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