CN103911654B - The method preparing the monocrystal silicon of a diameter of more than 400mm - Google Patents
The method preparing the monocrystal silicon of a diameter of more than 400mm Download PDFInfo
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Abstract
A kind of method of monocrystal silicon preparing a diameter of more than 400mm, the method uses and manufactures monocrystal silicon by vertical pulling method, and the method comprises the steps: charging and fusing；Seeding；Necking down；Shouldering；Isodiametric growth: silica crucible and the mutual opposite direction of crystal rotate, according to melt and the situation of single crystal growing furnace, controls crystal isometrical production Len req, and wherein at the isometrical initial stage, import argon flow velocity is 0.9m/s～1.5m/s, furnace pressure 22Torr, and liquid mouth is away from for 20mm；Ending；Cooling.Said method can reduce the fluctuating margin of " W-shape " solid liquid interface, improve silicon chip radially oxygen content uniformity, make " W-shape " solid liquid interface maximum point move to crystal edge, increase the content of germ nucleus homogeneity range, and then ensure the quality of large-diameter monocrystalline silicon.
Description
Technical field
The present invention relates to solar electrical energy generation monocrystal silicon manufacturing technology field, particularly to a kind of method of monocrystal silicon preparing a diameter of more than 400mm.
Background technology
Crystal silicon class solaode accounts for the share of whole photovoltaic market and reaches more than 90%.Vertical pulling method is one of main production process preparing crystal silicon series products, wherein, use vertical pulling method prepare the process of monocrystal silicon be broadly divided into material, seeding, shouldering, isometrical, finish up and cool down several stage.
So far, the conversion efficiency of the monocrystalline silicon battery prepared by vertical pulling method can reach more than 23%, but its cost of electricity-generating still can be in any more, and this significantly limit the penetration and promotion of this product.Ever-larger diameters is one of inexorable trend of monocrystal silicon used for solar batteries development, is greatly improved the production efficiency of product in the unit interval, significantly reduces the production cost of monocrystal silicon.
But, increase along with grain size, furnace binding increases therewith, compared with traditional minor diameter monocrystalline silicon production process, thermal field and gas flowfield in stove change therewith, this will largely effect on crystal silicon solid-liquid interface shape in growth course and the mass transfer in microcell, heat transfer, the isometrical initial stage in crystal silicon growth, typical " W-shape " solid liquid interface is defined in large-diameter monocrystalline silicon, on the one hand, the type interface exacerbates the interface fluctuation in growth course, thus reduce the stability of crystal pulling process, crystalline substance is interrupted in growth course, the occurrence probability of the defects such as dislocation increases；On the other hand, have impact on the impurity transmission of near interface, the distribution fluctuation of impurity is more obvious diametrically, reduces the performance (including that oxygen content fluctuates) of crystal.
Summary of the invention
In view of this, it is necessary to a kind of method providing monocrystal silicon preparing a diameter of more than 400mm, the method can improve the uniformity in isometrical initial stage large-diameter monocrystalline silicon radial performance, and then ensures the quality of large-diameter monocrystalline silicon.
A kind of method of monocrystal silicon preparing a diameter of more than 400mm, the method uses and manufactures monocrystal silicon by vertical pulling method, and the method for this monocrystal silicon preparing a diameter of more than 400mm comprises the steps:
Charging and fusing: high purity polycrystalline silicon material is pulverized, and in the mixed solution of nitric acid and Fluohydric acid., clean outer surface, remove possible metal impurities；High purity polycrystalline silicon material after pulverizing puts into high-purity silica crucible, silica crucible size >=800mm；Silica crucible is put in the graphite crucible in single crystal growing furnace；By single crystal growing furnace evacuation, being re-filled with argon, finally heated intensification is with melting polycrystalline silicon material；
Seeding: single crystal seed is fixed on seed shaft, and rotate together with seed shaft；After seed crystal is slowly declined with seed crystal is immersed gently molten silicon, make head dissolve the most on a small quantity, then with molten silicon formed a solid liquid interface；Seed crystal is gradually risen, be connected with seed crystal and leave solid liquid interface silicon temperature reduce, formed monocrystal silicon；
Necking down: quickly upwards lift seed crystal, to form crystal；
Shouldering: crystal is controlled to required aimed dia；
Isodiametric growth: silica crucible and the mutual opposite direction of crystal rotate, according to melt and the situation of single crystal growing furnace, controls crystal isometrical production Len req, and wherein at the isometrical initial stage, import argon flow velocity is 0.9m/s～1.5m/s, furnace pressure 22Torr, and liquid mouth is away from for 20mm；
Ending: crystal diameter is gradually reduced, and leaves melt；
Cooling: reduce temperature, gradually chilling temperature.
The method of the above-mentioned monocrystal silicon preparing a diameter of more than 400mm, at the isometrical initial stage, ensure import argon flow velocity be 0.9m/s～1.5m/s, furnace pressure 22Torr, liquid mouth be away from for 20mm, reduce the fluctuating margin of " W-shape " solid liquid interface, improve silicon chip radially oxygen content uniformity, and make " W-shape " solid liquid interface maximum point move to crystal edge, increase the content of germ nucleus homogeneity range, and then ensure the quality of large-diameter monocrystalline silicon.
Accompanying drawing explanation
Accompanying drawing 1 is the flow chart of steps of the method for the monocrystal silicon preparing a diameter of more than 400mm of a better embodiment.
Fig. 2 is the oxygen content scattergram radially of the crystal bar in embodiment 1.
Fig. 3 is the oxygen content scattergram radially of the crystal bar in embodiment 2.
In figure: prepare method step S300～S306 of the monocrystal silicon of a diameter of more than 400mm.
Detailed description of the invention
The present invention is by changing the gas flowfield in single crystal growing furnace at isometrical initial adjustment import argon flow velocity, reduce the fluctuating margin of " W-shape " solid liquid interface, improve silicon chip radially oxygen content uniformity, and make " W-shape " solid liquid interface maximum point move to crystal edge, increase the content of germ nucleus homogeneity range, and then ensure the quality of large-diameter monocrystalline silicon.
Refer to Fig. 1, it is the method flow diagram of the monocrystal silicon preparing a diameter of more than 400mm of a better embodiment, and the method uses and manufactures monocrystal silicon by vertical pulling method, and the method for this monocrystal silicon preparing a diameter of more than 400mm comprises the steps:
Step S300, feeds and melts: pulverized by high purity polycrystalline silicon material, and cleans outer surface in the mixed solution of nitric acid and Fluohydric acid., removes possible metal impurities；High purity polycrystalline silicon material after pulverizing puts into high-purity silica crucible, silica crucible size >=800mm；Silica crucible is put in the graphite crucible in single crystal growing furnace；By single crystal growing furnace evacuation, being re-filled with argon, finally heated intensification is with melting polycrystalline silicon material.
Step S301, seeding: single crystal seed is fixed on seed shaft, and rotate together with seed shaft；After seed crystal is slowly declined with seed crystal is immersed gently molten silicon, make head dissolve the most on a small quantity, then with molten silicon formed a solid liquid interface；Seed crystal is gradually risen, be connected with seed crystal and leave solid liquid interface silicon temperature reduce, formed monocrystal silicon.
Step S302, necking down: quickly upwards lift seed crystal, to form crystal.Wherein step S302 is particularly as follows: quickly upwards lift seed crystal, makes the diameter of the monocrystal silicon newly crystallized reach 3mm, and length is about 6～10 times of now crystal diameter, and the rotary speed of crystal is 2～10rpm；Silica crucible rotates along crystal rightabout, the rotary speed of crystal fast 1～3 times than silica crucible.
Step S303, shouldering: crystal is controlled to required aimed dia.
Step S304, isodiametric growth: silica crucible and the mutual opposite direction of crystal rotate, according to melt and the situation of single crystal growing furnace, control crystal isometrical production Len req, wherein at the isometrical initial stage, import argon flow velocity is 0.9m/s～1.5m/s, furnace pressure 22Torr, liquid mouth is away from for 20mm, wherein, the described isometrical initial stage is the stage that isometrical beginning to crystal diameter reaches 300mm, and liquid mouth is away from the distance for edge under guide shell to melt liquid level.Further, isometrical pulling rate 0.75～1mm/min, the rotary speed of crystal is 8～9rpm, and the rotary speed of silica crucible is 5～6rpm, so can ensure that the quality of large-diameter monocrystalline silicon is higher.
Step S305, ending: crystal diameter is gradually reduced, and leaves melt.
Step S306, cooling: reduce temperature, gradually chilling temperature.
Method below in conjunction with the concrete the drawings and the specific embodiments monocrystal silicon to preparing a diameter of more than 400mm is described further:
Embodiment
1
Charging and fusing: high purity polycrystalline silicon material is pulverized, and in the mixed solution of nitric acid and Fluohydric acid., clean outer surface, remove possible metal impurities；High-purity silica crucible put into by high purity polycrystalline silicon material after pulverizing, silica crucible a size of 800mm；Silica crucible is put in the graphite crucible in single crystal growing furnace；By single crystal growing furnace evacuation, being re-filled with argon, finally heated intensification is with melting polycrystalline silicon material.
Seeding: single crystal seed is fixed on seed shaft, and rotate together with seed shaft；After seed crystal is slowly declined with seed crystal is immersed gently molten silicon, make head dissolve the most on a small quantity, then with molten silicon formed a solid liquid interface；Seed crystal is gradually risen, be connected with seed crystal and leave solid liquid interface silicon temperature reduce, formed monocrystal silicon.
Necking down: quickly upwards lift seed crystal, to form crystal.
Shouldering: crystal is controlled to required aimed dia.
Isodiametric growth: silica crucible and the mutual opposite direction of crystal rotate, according to melt and the situation of single crystal growing furnace, control crystal isometrical production Len req, wherein at the isometrical initial stage, the rotary speed of crystal is 8rpm, and the rotary speed of silica crucible is 5rpm, import argon flow velocity is 0.9m/s, furnace pressure 22Torr, isometrical pulling rate 0.75mm/min, liquid mouth is away from for 20mm.
Ending: crystal diameter is gradually reduced, and leaves melt.
Cooling: reduce temperature, gradually chilling temperature.
Silicon single crystal rod crystal after channel angular 300mm is analyzed, and the change of its radially oxygen content is as shown in table 1, and compared with not improving before technique, the average radial oxygen content of isometrical initial stage monocrystal rod is by 6.83 × 1017/atm·cm-3Drop to 5.79 × 1017/atm·cm-3, and the fluctuation percentage ratio of crystal bar center oxygen content drops to 16.9% by 17.1%, it is seen that the optimization of argon flow velocity during crystal pulling, and reduce the fluctuation of radially oxygen content, improve the silicon single crystal rod quality at the isometrical initial stage.Referring to Fig. 2, figure is tried to achieve oxygen content transition point in radial directions by tangential method, before and after contrast improves technique, it appeared that the relatively uniform district of oxygen content in radial directions of isometrical initial stage is increased to 83.7% by account for whole crystal bar cross section 70.6%.
Table 1
| Parameter Technique | Before improvement: argon flow velocity 0.6m/s | After improvement: argon flow velocity 0.9m/s |
| Isometrical initial stage monocrystal rod radially averaged Oxygen content (1017/atm·cm-3) | 6.83 | 5.79 |
| Isometrical initial stage monocrystal rod center oxygen content (1017/atm·cm-3) | 7.99 | 6.77 |
| Oxygen content radial undulation value (%) | 17.1 | 16.9 |
Embodiment
2
Charging and fusing: high purity polycrystalline silicon material is pulverized, and in the mixed solution of nitric acid and Fluohydric acid., clean outer surface, remove possible metal impurities；High purity polycrystalline silicon material after pulverizing puts into high-purity silica crucible, silica crucible size 900mm；Silica crucible is put in the graphite crucible in single crystal growing furnace；By single crystal growing furnace evacuation, being re-filled with argon, finally heated intensification is with melting polycrystalline silicon material.
Seeding: single crystal seed is fixed on seed shaft, and rotate together with seed shaft；After seed crystal is slowly declined with seed crystal is immersed gently molten silicon, make head dissolve the most on a small quantity, then with molten silicon formed a solid liquid interface；Seed crystal is gradually risen, be connected with seed crystal and leave solid liquid interface silicon temperature reduce, formed monocrystal silicon.
Necking down: quickly upwards lift seed crystal, to form crystal.
Shouldering: crystal is controlled to required aimed dia.
Isodiametric growth: silica crucible and the mutual opposite direction of crystal rotate, according to melt and the situation of single crystal growing furnace, control crystal isometrical production Len req, wherein at the isometrical initial stage, the rotary speed of crystal is 9rpm, and the rotary speed of silica crucible is 6rpm, import argon flow velocity is 1.5m/s, furnace pressure 22Torr, isometrical pulling rate 1mm/min, liquid mouth is away from for 20mm.
Ending: crystal diameter is gradually reduced, and leaves melt.
Cooling: reduce temperature, gradually chilling temperature.
Silicon single crystal rod crystal after channel angular 300mm is analyzed, and the change of its radially oxygen content is as shown in table 2, and compared with not improving before technique, the average radial oxygen content of isometrical initial stage monocrystal rod is by 6.83 × 1017/atm·cm-3Drop to 5.61 × 1017/atm·cm-3, and the fluctuation percentage ratio of crystal bar center oxygen content drops to 15.9% by 17.1%, it is seen that the optimization of argon flow velocity during crystal pulling, and reduce the fluctuation of radially oxygen content, improve the silicon single crystal rod quality at the isometrical initial stage.Referring to Fig. 3, figure is tried to achieve oxygen content transition point in radial directions by tangential method.Before and after contrast improves technique, it appeared that the relatively uniform district of oxygen content in radial directions of isometrical initial stage is increased to 85.6% by account for whole crystal bar cross section 70.6%.
Table 2
| Parameter Technique | Before improvement: argon flow velocity 0.6m/s | After improvement: argon flow velocity 0.9m/s |
| Isometrical initial stage monocrystal rod radially averaged Oxygen content (1017/atm·cm-3) | 6.83 | 5.61 |
| Isometrical initial stage monocrystal rod center oxygen content (1017/atm·cm-3) | 7.99 | 6.5 |
| Oxygen content radial undulation value (%) | 17.1 | 15.9 |
Claims (3)
1. the method preparing the monocrystal silicon of a diameter of more than 400mm, the method uses and manufactures monocrystal silicon by vertical pulling method, and the method for this monocrystal silicon preparing a diameter of more than 400mm comprises the steps:
Charging and fusing: high purity polycrystalline silicon material is pulverized, and in the mixed solution of nitric acid and Fluohydric acid., clean outer surface, remove possible metal impurities；Will pulverize after high purity polycrystalline silicon material put into high-purity silica crucible, silica crucible a size of >=800mm；Silica crucible is put in the graphite crucible in single crystal growing furnace；By single crystal growing furnace evacuation, being re-filled with argon, finally heated intensification is with melting polycrystalline silicon material；
Seeding: single crystal seed is fixed on seed shaft, and rotate together with seed shaft；After slowly being declined by seed crystal, seed crystal is immersed gently molten silicon, makes head dissolve the most on a small quantity, then form a solid liquid interface with molten silicon；Seed crystal is gradually risen, be connected with seed crystal and leave solid liquid interface silicon temperature reduce, formed monocrystal silicon；
Necking down: quickly upwards lift seed crystal, to form crystal；
Shouldering: crystal is controlled to required aimed dia；
Isodiametric growth: silica crucible and the mutual opposite direction of crystal rotate, according to melt and the situation of single crystal growing furnace, controls crystal isometrical production Len req, and wherein at the isometrical initial stage, import argon flow velocity is 0.9m/s～1.5m/s, furnace pressure 22Torr, and liquid mouth is away from for 20mm；The described isometrical initial stage is the stage that isometrical beginning to crystal diameter reaches 300mm；
Ending: crystal diameter is gradually reduced, and leaves melt；
Cooling: reduce temperature, gradually chilling temperature.
The method of the monocrystal silicon preparing a diameter of more than 400mm the most according to claim 1, it is characterised in that: wherein at the isometrical initial stage, the rotary speed of crystal is 8～9rpm, and the rotary speed of silica crucible is 5～6rpm.
The method of the monocrystal silicon preparing a diameter of more than 400mm the most according to claim 2, it is characterised in that: wherein at the isometrical initial stage, isometrical pulling rate is 0.75～1mm/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105063744A (en) * | 2015-07-15 | 2015-11-18 | 包头市山晟新能源有限责任公司 | Silicon single crystal drawing method |
| CN105803519B (en) * | 2016-05-31 | 2018-02-13 | 邢台晶龙电子材料有限公司 | A kind of M2 types monocrystalline silicon quickly finishes up method |
| CN105803520B (en) * | 2016-05-31 | 2018-02-13 | 邢台晶龙电子材料有限公司 | The single crystal growing furnaces of CZ 80 finish up method automatically |
| CN108977878A (en) * | 2017-06-01 | 2018-12-11 | 江苏拓正茂源新能源有限公司 | Method based on monocrystalline growth with czochralski silicon |
| CN107268071A (en) * | 2017-06-06 | 2017-10-20 | 界首市七曜新能源有限公司 | A kind of solar panel monocrystal silicon preparation technology |
| CN111850674A (en) * | 2019-04-25 | 2020-10-30 | 新特能源股份有限公司 | Method for producing monocrystalline silicon by using abnormal raw materials |
| CN110257901B (en) * | 2019-07-15 | 2021-05-28 | 乐山新天源太阳能科技有限公司 | Preparation process of large-diameter efficient N-type monocrystalline silicon |
| CN114108073B (en) * | 2021-12-01 | 2023-06-30 | 新美光(苏州)半导体科技有限公司 | Growth method of large-diameter monocrystalline silicon |
| CN114855263A (en) * | 2022-04-01 | 2022-08-05 | 上海新昇半导体科技有限公司 | Crystal growth method and growth device |
| CN116024650B (en) * | 2022-12-06 | 2024-01-26 | 晶科能源股份有限公司 | Crystal pulling process and monocrystalline silicon |
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| WO2002103091A1 (en) * | 2001-06-15 | 2002-12-27 | Shin-Etsu Handotai Co., Ltd. | SILICON SINGLE CRYSTAL WAFER HAVING VOID DENUDED ZONE ON THE SUFRACE AND DIAMETER OF AVOBE 300 mm AND ITS PRODUCTION METHOD |
| CN1422990A (en) * | 2002-12-02 | 2003-06-11 | 浙江大学 | Method for growing silicon single crystal |
| WO2005019506A1 (en) * | 2003-08-20 | 2005-03-03 | Shin-Etsu Handotai Co., Ltd. | Process for producing single crystal and silicon single crystal wafer |
| CN103014840A (en) * | 2012-12-24 | 2013-04-03 | 上海申和热磁电子有限公司 | Method for reducing oxidation stacking fault of head of N-type single crystal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002103091A1 (en) * | 2001-06-15 | 2002-12-27 | Shin-Etsu Handotai Co., Ltd. | SILICON SINGLE CRYSTAL WAFER HAVING VOID DENUDED ZONE ON THE SUFRACE AND DIAMETER OF AVOBE 300 mm AND ITS PRODUCTION METHOD |
| CN1422990A (en) * | 2002-12-02 | 2003-06-11 | 浙江大学 | Method for growing silicon single crystal |
| WO2005019506A1 (en) * | 2003-08-20 | 2005-03-03 | Shin-Etsu Handotai Co., Ltd. | Process for producing single crystal and silicon single crystal wafer |
| CN103014840A (en) * | 2012-12-24 | 2013-04-03 | 上海申和热磁电子有限公司 | Method for reducing oxidation stacking fault of head of N-type single crystal |
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