WO2013125133A1 - Procédé de traitement thermique d'une matière première en phase solide et dispositif associé, procédé de production de lingot, article et cellule solaire - Google Patents

Procédé de traitement thermique d'une matière première en phase solide et dispositif associé, procédé de production de lingot, article et cellule solaire Download PDF

Info

Publication number
WO2013125133A1
WO2013125133A1 PCT/JP2012/082218 JP2012082218W WO2013125133A1 WO 2013125133 A1 WO2013125133 A1 WO 2013125133A1 JP 2012082218 W JP2012082218 W JP 2012082218W WO 2013125133 A1 WO2013125133 A1 WO 2013125133A1
Authority
WO
WIPO (PCT)
Prior art keywords
temperature
raw material
solid phase
phase raw
heat treatment
Prior art date
Application number
PCT/JP2012/082218
Other languages
English (en)
Japanese (ja)
Inventor
大石　隆一
Original Assignee
シャープ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by シャープ株式会社 filed Critical シャープ株式会社
Priority to CN201280070494.XA priority Critical patent/CN104136664B/zh
Publication of WO2013125133A1 publication Critical patent/WO2013125133A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/003—Heating or cooling of the melt or the crystallised material
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/006—Controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • H01L31/182—Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/546—Polycrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a heat treatment method and apparatus for solid phase raw materials, and a method for manufacturing ingots, processed products, and solar cells. More specifically, the present invention relates to a method for heat treatment of a solid phase raw material, a heat treatment apparatus for the solid phase raw material used therefor, an ingot (cast) such as a silicon ingot, a processed product, and a method for manufacturing a solar cell.
  • III-V compounds such as germanium and gallium arsenide
  • II-VI compounds such as zinc selenide
  • other II-IV-V2 compounds I-III-VI2 compounds
  • III-V compounds such as germanium and gallium arsenide
  • II-VI compounds such as zinc selenide
  • other II-IV-V2 compounds I-III-VI2 compounds
  • the material is easily brittle with a brittle material, and when it is used as a solar cell material, the deterioration in quality due to dislocation is remarkable. Therefore, when manufacturing these materials by casting such as crystal growth, it is important to control temperature conditions. Also, in the case of a metal material or an insulating material manufactured by casting, when adjusting to a desired crystal grain size, it is important to control the temperature conditions as in the case of a semiconductor material.
  • a container in which a solid phase raw material is loaded is generally set in the apparatus, and the solid phase raw material is heated and melted with a heater.
  • a polycrystalline silicon ingot for a solar cell is manufactured by unidirectionally solidifying the molten solid phase material from the bottom to the top of the container by lowering the temperature.
  • Patent Document 1 for the purpose of improving the characteristics of a polycrystalline silicon solar cell, a small amount of germanium is added to the raw material, and the temperature at the bottom of the container is set to 1410 at the initial stage of crystal growth.
  • a technique for growing (expressing) a dendrite crystal extending in the ⁇ 112> direction at the bottom of the silicon ingot by holding at 40 ° C. for 40 minutes is disclosed.
  • Patent Document 1 the absolute value of 1410 ° C., which is the melting point of silicon, has a great meaning, and the temperature detection means such as a thermocouple and a radiation thermometer is deteriorated with time, its installation position and temperature calibration method. It is very difficult to produce polycrystalline silicon with good reproducibility due to various variation factors such as variations in size. Further, Patent Document 1 does not present a specific measure for the variation factor.
  • the temperature of the material itself with an accuracy exceeding the measurement accuracy of the absolute value of the detection temperature in the temperature detection means. It is often necessary to control the absolute value of. In particular, when the casting is a brittle material, high accuracy is required for temperature control during heat treatment.
  • the present invention eliminates the problems of variation due to the installation state, deterioration state, calibration method, etc. of the temperature detection means in the heat treatment to solidify after heating and melting the solid phase raw material, and the heat treatment state with accuracy exceeding the measurement accuracy It is an object of the present invention to provide a method that can ensure reproducibility.
  • the inventor has introduced the concept of the reference temperature according to the deterioration state, installation state, and calibration method of the temperature detection means from time to time. The inventors have found that this can be solved, and have reached the present invention.
  • the solid phase raw material stored in the container is heated and melted by a heating means, the solid phase raw material is solidified to obtain the ingot.
  • a temperature detecting means detects the temperature of the solid phase raw material, a temperature at which the solid phase raw material becomes constant immediately before the completion of melting is set as a reference temperature Tm ° C., and a temperature control is performed based on the reference temperature Tm ° C.
  • a heat treatment method is provided.
  • a method for producing a workpiece derived from a silicon material and a method for producing a solar cell using a workpiece produced by the production method are provided.
  • a heat treatment apparatus for use in the above-described heat treatment method for a solid phase raw material, a container for storing the solid phase raw material, a temperature detecting means for detecting the temperature of the solid phase raw material, a heating means, and the heating means.
  • a solid phase raw material heat treatment apparatus comprising temperature detecting means for detecting the temperature of the solid phase raw material.
  • the present invention in the heat treatment in which the solid phase raw material is heated and melted and then solidified, the problem of variation due to the installation state, deterioration state, calibration method, etc. of the temperature detection means is solved, and the accuracy exceeding the measurement accuracy is achieved.
  • a method capable of ensuring the reproducibility of the heat treatment state can be provided. That is, according to the present invention, it is possible to control the solid phase raw material with high accuracy and reproducibility even under conditions where temperature control is difficult. Therefore, by paying attention to various characteristics, it becomes possible to cast a casting under desired conditions with good reproducibility.
  • the solid-phase raw material heat treatment method of the present invention is installed at a position where the temperature detection means can detect a temperature which is in thermal communication with the container or the container and has a correlation with the temperature of the solid-phase raw material. In this case, the above effect is further exhibited. Further, in the heat treatment method of the solid phase raw material of the present invention, the temperature control is performed at a temperature detection means of T ° C., the difference from the reference temperature Tm ° C. (Tm ⁇ T) ° C. is ⁇ T ° C., and the desired set temperature difference in the heat treatment The above effect is further exhibited when the set temperature for control Th is corrected by ( ⁇ Ts ⁇ T) ° C. where is set to ⁇ Ts ° C.
  • the heat treatment method of the solid phase raw material of the present invention further exhibits the above effect when the solid phase raw material is a brittle material for an ingot, particularly when the brittle material is a silicon material for a polycrystalline silicon ingot. Is done.
  • a workpiece derived from a silicon material means a silicon block, a silicon wafer, and the like.
  • silicon solar cells manufactured using workpieces derived from silicon materials include “silicon solar cells” that constitute the smallest unit and “silicon solar cell modules” in which a plurality of them are electrically connected. means.
  • ingots and processed products of brittle materials having desired characteristics, particularly silicon ingots, blocks and wafers can be manufactured with good reproducibility, and thus have desired characteristics.
  • Silicon solar cells can be stably supplied to the market.
  • the solid phase raw material heat treatment method of the present invention is a solid phase raw material heat treatment method in which the solid phase raw material housed in a container is heated and melted by a heating means, and then the solid phase raw material is solidified to obtain the ingot. Yes, the temperature of the solid phase raw material is detected by temperature detection means, and the temperature at which the solid phase raw material becomes constant immediately before the completion of melting is set as a reference temperature Tm ° C., and temperature control is performed based on the reference temperature Tm ° C.
  • FIG. 1 is a conceptual diagram showing a change in the detected temperature of the container in the melting process of the solid phase raw material, that is, a change in temperature when heated by a heater to melt the solid phase raw material in the container.
  • the temperature gradually rises when heating is started (region I), but when the inside of the container is in a mixed state of a solid phase and a liquid phase, the temperature of the melt is almost solid until the solid phase material is completely melted. It becomes constant at the melting point of (region II).
  • the average value of the detected temperatures of the temperature detecting means in this state is determined as “Tm”.
  • the reference temperature Tm is a detection temperature of the temperature detection means when the melt in the container is the melting point of the solid phase raw material. After that, if the heating is continued, the temperature starts to rise again after the whole amount is melted, and when the heating is stopped, the temperature is lowered (region III).
  • the reference temperature Tm is a value reflecting all the influences of the variation factors of the absolute value of the detected temperature, that is, a value including all errors.
  • the temperature detecting means is a thermocouple
  • factors such as variations in temperature calibration method, deterioration with time after continuous use after calibration, variation in installation position, variation in contact degree with peripheral components, and the like are included.
  • thermocouples there is a method of setting a reference temperature junction (for example, 0 ° C. in ice water as a cold junction) as a method to increase the measurement accuracy, and this can surely suppress temperature variations in the cold junction, It has no effect on other variations (errors).
  • the temperature detecting means is a radiation thermometer
  • factors such as variations in temperature calibration method, deterioration of detection elements with time, variations in observation points, and variations due to fogging of the temperature measurement window are included.
  • the temperature detecting means is preferably installed at a position where the container or the container is in thermal conduction and capable of detecting a temperature having a correlation with the temperature of the solid phase raw material.
  • the vicinity of the center of the lower surface is particularly preferable because a value that best reflects the temperature of the molten solid phase raw material in the container can be obtained.
  • the temperature control is such that the detected temperature of the temperature detecting means is T ° C., the difference from the reference temperature Tm ° C. (Tm ⁇ T) ° C. is ⁇ T ° C., and the desired set temperature in the heat treatment
  • the control set temperature Th is preferably corrected by ( ⁇ Ts ⁇ T) ° C. Specifically, it will be described in detail in Examples.
  • Solid phase raw material examples include semiconductor materials such as silicon and germanium; III-V group compounds such as gallium arsenide; II-VI group compounds such as zinc selenide; Compound semiconductor materials such as IV-V2 group compounds and I-III-VI2 group compounds; metal materials such as aluminum, copper, titanium, chromium and their alloys; insulating materials such as oxides, nitrides and sulfides .
  • semiconductor materials such as silicon and germanium
  • III-V group compounds such as gallium arsenide
  • II-VI group compounds such as zinc selenide
  • Compound semiconductor materials such as IV-V2 group compounds and I-III-VI2 group compounds
  • metal materials such as aluminum, copper, titanium, chromium and their alloys
  • insulating materials such as oxides, nitrides and sulfides .
  • a brittle material is preferable and a silicon material is particularly preferable in that the effects of the present invention are sufficiently exhibited.
  • the heat treatment apparatus for a solid phase raw material of the present invention includes a container for storing the solid phase raw material, a temperature detection means for detecting the temperature of the solid phase raw material, a heating means, and a temperature detection means for detecting the temperature of the heating means.
  • the heat treatment apparatus that can be used in the solid phase raw material heat treatment method of the present invention is not particularly limited, and any known apparatus can be used as long as it includes the above-described means.
  • the molten raw material in the container is And an apparatus of a method of gradually solidifying from the above.
  • a cooling mechanism such as a refrigerant circulation provided on the pedestal side of the container and moving the container away from the heating mechanism by an elevating drive mechanism
  • the molten raw material in the container is And an apparatus of a method of gradually solidifying from the above.
  • the vicinity of the center of the bottom of the container is particularly preferable because it is not easily affected by a heater or the like.
  • the temperature detecting means of the container cannot be installed at the above position.
  • the temperature detection means of the container can be installed at a position where the container is thermally conductive.
  • the reference temperature Tm is determined by the temperature detection means, and the detected temperature T of the container at a certain time is measured. Then, (T ⁇ Tm) is set as the corrected container detection temperature, and the value of (T ⁇ Tm) at a specific time point among the heat treatment conditions is the same as the previous condition (desired condition). What is necessary is just to change the setting temperature Th for control of a heater.
  • temperature control may be performed using the relationship between the detected temperature of the heater and Tm that has been examined during the heat treatment up to the previous time.
  • variations occurring at that time are included, which is not preferable.
  • FIG. 2 is a schematic cross-sectional view showing an example of a heat treatment apparatus to which the heat treatment method of the present invention can be applied.
  • This apparatus is generally used for casting a polycrystalline silicon ingot, and has a chamber (sealed container) 7 constituting a resistance heating furnace.
  • a container 1 made of graphite, quartz (SiO 2 ) or the like is disposed inside the chamber 7 so that the atmosphere inside the chamber 7 can be maintained in a sealed state.
  • a graphite container table 3 that supports the container 1 is disposed in the chamber 7 in which the container 1 is accommodated.
  • the container table 3 can be moved up and down by the lift drive mechanism 12, and the refrigerant (cooling water) in the cooling tank 11 is circulated therein.
  • An outer container 2 made of graphite or the like is disposed on the upper part of the container base 3, and the container 1 is disposed therein.
  • a cover made of graphite or the like surrounding the container 1 may be disposed.
  • a heater 10 such as a graphite heater is disposed so as to surround the outer container 2, and a heat insulating material 8 is disposed so as to cover these from above.
  • the heater 10 can be heated from the periphery of the container 1 to melt the silicon of the solid phase raw material 4 in the container 1. If the temperature control of the present invention is possible by heating from the heater 10, cooling from the lower side of the container 1 by the cooling tank 11 and raising and lowering the container 1 by the elevating drive mechanism 12, a heating mechanism such as a heating element,
  • the form and arrangement are not particularly limited.
  • a container lower thermocouple 5 is disposed near the center of the lower surface of the container 1, and an outer container lower thermocouple 6 is disposed near the center of the lower surface of the outer container 2. Record the temperature data. Further, the heater temperature is detected by the heater detection means (output control thermocouple 13), and the heating state by the heater 10 is controlled. In addition to the thermocouple described above, a thermocouple or a radiation thermometer for detecting temperature may be arranged. In the present invention, the temperature at which the solid phase raw material becomes constant immediately before the completion of melting is detected by the above-mentioned thermocouple 5 under the container and the thermocouple 6 under the outer container, and is set as the reference temperature Tm.
  • the inside of the chamber 7 can be kept in a sealed state so that external oxygen gas, nitrogen gas, etc. do not flow in.
  • an inert gas such as argon gas is introduced to maintain an inert atmosphere.
  • the solid phase raw material 4 in the container 1 is filled with silicon, degassed (evacuated), replaced with gas in the chamber 7 by introducing an inert gas, and solid phase raw material by heating.
  • the polycrystalline silicon ingot is heat-treated by the steps of 4 melting, melting confirmation and holding, temperature control and solidification start by operation of the lift drive mechanism 12, solidification completion confirmation and annealing, and ingot removal.
  • the heat treatment method of the solid phase raw material of the present invention includes a casting method having a different method, a CZ method used for pulling a single crystal, and a wafer shape directly from a melt.
  • the present invention can also be applied to a heat treatment method and a heat treatment apparatus such as a ribbon method for growing a crystal of the crystal, a spherical silicon method for crystallizing a droplet of melt in an inert gas such as argon.
  • the ingot (cast) of the present invention is produced by the solid-phase raw material heat treatment method of the present invention.
  • the solid phase raw material is a silicon material
  • a silicon ingot is manufactured.
  • the processed product of the present invention is obtained by processing an ingot.
  • the solid phase raw material is a silicon material
  • a workpiece derived from the silicon material is obtained.
  • a workpiece derived from a silicon material means a silicon block, a silicon wafer, and the like.
  • the silicon block can be obtained, for example, by cutting the silicon ingot of the present invention into a prismatic shape using a known device such as a band saw. Moreover, you may grind
  • a silicon wafer can be obtained by, for example, slicing the above silicon block to a desired thickness using a known apparatus such as a multi-wire saw. At present, a thickness of about 170 to 200 ⁇ m is generally used, but the trend is to reduce the thickness for cost reduction.
  • the silicon solar cell of the present invention is manufactured using a workpiece (silicon wafer) derived from the silicon material of the present invention.
  • a silicon solar battery cell can be manufactured by a well-known solar battery cell process, for example, using the silicon wafer of the present invention. That is, in the case of a silicon wafer doped with a p-type impurity by a known method using a known material, an n-type impurity is doped to form an n-type layer to form a pn junction, and the surface electrode And a back surface electrode is formed and a silicon photovoltaic cell is obtained.
  • a p-type impurity is doped to form a p-type layer to form a pn junction, and a surface electrode and a back electrode are formed to form a silicon solar battery cell.
  • a MIS type solar cell in which a metal is deposited with a thin insulating layer interposed therebetween, for example, a silicon thin film such as a conductive amorphous material opposite to a wafer is formed.
  • p-type and n-type silicon heterojunctions having different structures.
  • the plurality are electrically connected to obtain a silicon solar cell module.
  • silicon solar battery As described above, in this specification, the concept including “solar battery cell” and “solar battery module” is simply referred to as “solar battery”. Therefore, for example, what is described as “silicon solar battery” means “silicon solar battery cell” and “silicon solar battery module”.
  • Test Example 1 Examination of variation in crystal grain size of polycrystalline silicon ingot Using the heat treatment apparatus shown in FIG. 2, using the heat treatment method for the solid phase raw material of the present invention and the conventional method, respectively, polycrystalline silicon The ingot was heat-treated, and the variation in crystal grain size (crystal nucleus generation density) sensitive to temperature conditions was evaluated.
  • the graphite outer container 2 (inner dimensions: 900 mm ⁇ 900 mm ⁇ height 460 mm, bottom plate thickness and side surface) on the graphite container table 3 (880 mm ⁇ 880 mm ⁇ thickness 200 mm) in the heat treatment apparatus shown in FIG.
  • a quartz container 1 (inner dimensions: 830 mm ⁇ 830 mm ⁇ 420 mm, bottom plate thickness and side wall thickness 22 mm) was installed therein. Further, as a container temperature detection means, a container lower thermocouple (thermocouple A) 5 is disposed near the center of the lower surface of the container 1, and an outer container lower thermocouple (thermocouple B) 6 is disposed near the center of the lower surface of the outer container 2 (20 mm below the container). Installed in two places. Further, as a temperature detection means of the heater, a thermocouple (thermocouple H) 13 for controlling the output of the heater was installed at a position 40 mm away from the heater (graphite heater) 10.
  • the subscripts are added to the detected temperatures of the respective thermocouples to obtain Ta, Tb and Th.
  • the temperature was controlled by the control device 9 by a method in which the detected temperature Th was set and the output of the heater 10 was adjusted, and the detected temperatures Ta, Tb and Th were recorded at intervals of 10 seconds.
  • Drawing numbers 7 and 8 in Drawing 2 show a chamber and a heat insulating material, respectively.
  • Table 1 shows the optimum value (° C.) as the optimum temperature condition.
  • ⁇ Ta is (detection temperature ⁇ detection temperature at the time of melting stability of solid phase raw material) Ta-Tma of thermocouple A
  • ⁇ Tb is (detection temperature ⁇ melting of solid phase raw material of thermocouple B). Detected temperature at the time of stability) Tb-Tmb.
  • ⁇ Ta and ⁇ Tb match within the error range regardless of which data of thermocouple A and thermocouple B is used, and can be appropriately selected for correction of the heating control temperature. Also, from this result, it can be inferred that the same control can be performed by installing a temperature detecting means in a portion that is thermally connected to the container 1.
  • the control set temperature Th is corrected from ( ⁇ Ts ⁇ T) so that ⁇ Ta and ⁇ Tb become ⁇ 20 ° C. in the first to fifth embodiments.
  • the value was calculated, and the subsequent heat treatment conditions were corrected by the correction value. That is, if ⁇ Ta and ⁇ Tb are each ⁇ 23 ° C., the set temperature is increased by 3 ° C. because it is 3 ° C. lower than the ideal temperature difference ⁇ Ts ( ⁇ 20 ° C.).
  • Th was changed from 1450 ° C. to 1453 ° C., and all temperature programs were corrected by the correction value in the same manner.
  • the heat treatment was performed without the above temperature correction.
  • Each of the obtained silicon ingots was processed into 25 silicon blocks (each 156 mm ⁇ 156 mm ⁇ 200 mm) using a band saw, further sliced using a wire saw, and a silicon wafer (156 mm ⁇ 156 mm ⁇ thickness of 0.1 mm). 18 mm) About 12,000 sheets were obtained.
  • the evaluation of the crystal grain size was performed on the wafer closest to the bottom of the 25 blocks cut out from each ingot, and the average value of the crystal grain sizes of the 25 wafers was taken as the average crystal grain size of the ingot.
  • the ⁇ 3 grain boundary often found on the surface of the polycrystalline silicon wafer was not counted as a grain boundary here.
  • the ⁇ 3 grain boundary is a grain boundary in which the sigma value defined by the reciprocal of the volume ratio of the unit cell of the corresponding lattice to the unit cell of the crystal is 3 in the corresponding lattice theory.
  • the ⁇ 3 grain boundary originates from stacking faults that enter the crystal grain grown from a single crystal nucleus due to the influence of stress, etc., and should be counted as a grain boundary when evaluating the number of crystal nucleus occurrences It was not counted here as a grain boundary.
  • the crystal grain size was measured using a digital microscope (manufactured by Keyence Corporation, model: VHX-1000).
  • Table 2 shows the results of setting the average value of 5 times of the example to 100, and the example has a smaller standard deviation of 5 times than the conventional example, the average crystal grain size is uniform, and the reproducibility is good. It can be seen that the temperature control is working well.
  • the obtained silicon wafer is put into a normal solar cell process to produce 12,000 solar cells (outer dimensions 156 mm ⁇ 156 mm ⁇ thickness 0.18 mm) per ingot, and the output (W ) was measured.
  • Table 2 shows the results of taking the average value of the output in each ingot unit and setting the average value of five times in the example to 100. From this result, it can be seen that the example has a small standard deviation of 5 times as compared with the conventional example, and has less variation in terms of solar cell characteristics.
  • the conventional example is higher than the average value of the example, but when compared with the average value of 5 times, the conventional example is 0.32% lower than the example. It can be considered that the output decreased overall due to the variation.
  • the solar cell module of the solar cell of the example was obtained in the same manner as the solar cell. There was a tendency that the average output was higher and the variation was smaller than that of the conventional example.
  • the polycrystalline silicon ingot is illustrated as an example of the embodiment of the present invention, but solidification can be controlled with good reproducibility for other materials by using the same concept of temperature control.
  • ductile materials such as metals exhibit various characteristics depending on the difference in crystal structure
  • the heat treatment method of the present invention can be applied.
  • cracks may occur due to the thermal stress inside the casting, and in the case of semiconductor materials, crystal defects (dislocations, etc.) are introduced by the stress, and the characteristics as electronic devices are improved.
  • the crystal grain size may greatly affect the characteristics as in the case of silicon, and the heat treatment method of the present invention is more effective.
  • thermocouple (Thermocouple A) 6 Outer container lower thermocouple (20mm below container thermocouple B) 7 Chamber 8 Heat insulating material 9 Control device 10 Heating heater (graphite heater) DESCRIPTION OF SYMBOLS 11 Cooling tank 12 Elevating drive mechanism 13 Heater output thermocouple

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Silicon Compounds (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne un procédé de traitement thermique d'une matière première en phase solide qui, à l'aide d'un moyen de chauffage, chauffe et fait fondre une matière première en phase solide placée dans un récipient puis la solidifie de façon à en faire un lingot. La température de la matière première en phase solide est détectée par un moyen de détection de température. Si la température qui reste constante juste avant la fin d'une fusion de la matière première en phase solide est définie comme une température de référence Tm °C, la régulation thermique est réalisée sur la base de la température de référence Tm °C.
PCT/JP2012/082218 2012-02-22 2012-12-12 Procédé de traitement thermique d'une matière première en phase solide et dispositif associé, procédé de production de lingot, article et cellule solaire WO2013125133A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201280070494.XA CN104136664B (zh) 2012-02-22 2012-12-12 固相原料的热处理方法、其装置以及锭块、加工物及太阳能电池的制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-036244 2012-02-22
JP2012036244A JP2013170108A (ja) 2012-02-22 2012-02-22 固相原料の熱処理方法とその装置およびインゴットとその用途

Publications (1)

Publication Number Publication Date
WO2013125133A1 true WO2013125133A1 (fr) 2013-08-29

Family

ID=49005333

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/082218 WO2013125133A1 (fr) 2012-02-22 2012-12-12 Procédé de traitement thermique d'une matière première en phase solide et dispositif associé, procédé de production de lingot, article et cellule solaire

Country Status (4)

Country Link
JP (1) JP2013170108A (fr)
CN (1) CN104136664B (fr)
TW (1) TWI460318B (fr)
WO (1) WO2013125133A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108505112B (zh) * 2018-05-22 2021-02-02 英利能源（中国）有限公司 高效多晶硅锭的制备方法及高效多晶硅锭

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0477654A (ja) * 1990-07-20 1992-03-11 Seiko Instr Inc 熱機械的分析の温度補正方法
JPH09315887A (ja) * 1996-05-31 1997-12-09 Japan Energy Corp 単結晶の製造方法及びそれに用いられる単結晶製造装置
JP2002080215A (ja) * 2000-09-04 2002-03-19 Sharp Corp 多結晶半導体インゴットの製造方法
JP2005147935A (ja) * 2003-11-18 2005-06-09 Terametsukusu Kk 温度校正法及びそれを用いた装置

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008280215A (ja) * 2007-05-11 2008-11-20 Sony Corp ガラス基板、表示パネルおよびその製造方法
US20110259262A1 (en) * 2008-06-16 2011-10-27 Gt Solar, Inc. Systems and methods for growing monocrystalline silicon ingots by directional solidification
CN102242390B (zh) * 2011-06-15 2013-09-25 安阳市凤凰光伏科技有限公司 铸造法生产类似单晶硅锭化料加热方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0477654A (ja) * 1990-07-20 1992-03-11 Seiko Instr Inc 熱機械的分析の温度補正方法
JPH09315887A (ja) * 1996-05-31 1997-12-09 Japan Energy Corp 単結晶の製造方法及びそれに用いられる単結晶製造装置
JP2002080215A (ja) * 2000-09-04 2002-03-19 Sharp Corp 多結晶半導体インゴットの製造方法
JP2005147935A (ja) * 2003-11-18 2005-06-09 Terametsukusu Kk 温度校正法及びそれを用いた装置

Also Published As

Publication number Publication date
TW201335449A (zh) 2013-09-01
CN104136664B (zh) 2016-09-07
CN104136664A (zh) 2014-11-05
TWI460318B (zh) 2014-11-11
JP2013170108A (ja) 2013-09-02

Similar Documents

Publication Publication Date Title
EP2089319B1 (fr) Procede de purification de silicium metallurgique par solidification dirigee
US20110168081A1 (en) Apparatus and Method for Continuous Casting of Monocrystalline Silicon Ribbon
US20070006916A1 (en) Solar-cell polycrystalline silicon and method for producing the same
JP2006335582A (ja) 結晶シリコン製造装置とその製造方法
JP5135467B1 (ja) 多結晶シリコンインゴットの製造方法
Ganesh et al. Growth and characterization of multicrystalline silicon ingots by directional solidification for solar cell applications
JP2016033102A (ja) サファイア単結晶およびその製造方法
JP2013112581A (ja) 坩堝、多結晶シリコンインゴットの製造方法、多結晶シリコンインゴット、多結晶シリコンウエハ、多結晶シリコン太陽電池、多結晶太陽電池モジュール
WO2013125133A1 (fr) Procédé de traitement thermique d'une matière première en phase solide et dispositif associé, procédé de production de lingot, article et cellule solaire
JP2004196577A (ja) 多結晶シリコンの製造方法
JP5140778B1 (ja) 多結晶シリコンインゴットの製造方法
JP6487675B2 (ja) 多結晶シリコンインゴット製造方法、多結晶シリコンインゴットの用途の製造方法及び多結晶シリコンインゴット
JP6014336B2 (ja) シリコン鋳造用鋳型、シリコン鋳造方法、シリコン材料の製造方法および太陽電池の製造方法
JP2016132599A (ja) サファイア単結晶製造装置、及びサファイア単結晶の製造方法
JP2006273669A (ja) 半導体インゴットの製造方法
JP6095060B2 (ja) Ｓｉ多結晶インゴットの製造方法
JP2013220951A (ja) 多結晶シリコンインゴットとその製造方法およびその用途
WO2011104796A1 (fr) Silicium polycristallin pour cellule solaire
JP2016169112A (ja) サファイア単結晶の製造方法
JP2004277239A (ja) 板状シリコンの製造方法、板状シリコン及び太陽電池
JP2013133268A (ja) 多結晶シリコンインゴットの製造方法及びその製造物
JP2004161565A (ja) 粒状シリコン結晶の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12869272

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12869272

Country of ref document: EP

Kind code of ref document: A1