CN109023521A - The preparation method of solar cell module polysilicon chip - Google Patents
The preparation method of solar cell module polysilicon chip Download PDFInfo
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- CN109023521A CN109023521A CN201810991724.5A CN201810991724A CN109023521A CN 109023521 A CN109023521 A CN 109023521A CN 201810991724 A CN201810991724 A CN 201810991724A CN 109023521 A CN109023521 A CN 109023521A
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- 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
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- 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
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- 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
- C30B28/10—Production of homogeneous polycrystalline material with defined structure from liquids by pulling from a melt
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- 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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/10—Etching in solutions or melts
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Abstract
The invention discloses a kind of preparation methods of solar cell module polysilicon chip, are related to the preparation method technical field of polysilicon chip.The method is during preparing polycrystalline silicon rod, the carbon in silicon melt is removed by the multiple eutectic directional solidification and plasma melting of the silicon of titanium-silicon base alloys melt and titanium disilicide first, boron, the elements such as phosphorus, then titanium is further removed by the multiple eutectic directional solidification and vacuum electron beam melting of the aluminium of aluminium-silicon alloys melt and silicon, the elements such as iron, then it is purified again by the lifting realization to polysilicon, the purification of solar-grade polysilicon is realized by above-mentioned three step, the plurality of impurities in polysilicon can be removed, the purity of the polycrystalline silicon rod of preparation is higher, therefore, the purity of the polysilicon chip of preparation is higher, to improve the photoelectric conversion efficiency of solar cell module.
Description
Technical field
The present invention relates to the preparation method technical field of silicon wafer more particularly to a kind of solar cell module polysilicon chips
Preparation method.
Background technique
Solar battery is one of the main flow direction of future source of energy development.It is partly led since silicon is that content is the most abundant in the earth's crust
Body material, therefore silica-based solar becomes the developing direction of the following clear energy sources, wherein solar-grade polysilicon is to utilize silicon substrate
The basic material of solar energy.Major impurity in industrial silicon has phosphorus, boron, carbon, bismuth, arsenic, titanium, gallium, nickel, iron, copper, aluminium etc..Polycrystalline
There are mainly two types of methods for silicon: one is chemical methods, and one is metallurgy methods.Wherein Siemens Method is chemical method representative, is mainly passed through
SiHCl3Hydrogen reduction method prepares the purity highest of high purity polycrystalline silicon, can achieve electron level.Although this method can prepare high-purity
Silicon, but this method energy consumption is high, low yield.Another method is metallurgy method, if metallurgy method include: hydrometallurgy, purifying method,
The methods of high-temperature vacuum melting, directional solidification, high energy beam melting.Directional solidification is the most common method of metallurgy method, due to most
The equilibrium segregation coefficient of number element is far smaller than 1, therefore can be solidified and be purified by multiple bearing, passes through aluminium silicon melt
Directional solidification can greatly reduce the segregation coefficient of impurity.But the segregation coefficient of phosphorus, boron and arsenic is difficult to pass through orientation close to 1
Solidification is purified.A kind of above-mentioned method is effective to single or several elements, therefore, although cost is relatively low for metallurgy method,
But method of purification is unsatisfactory.
Summary of the invention
The technical problem to be solved by the present invention is to how provide a kind of plurality of impurities that can be removed in polysilicon, improve
The preparation method of the solar cell module of preparation polysilicon chip purity.
In order to solve the above technical problems, the technical solution used in the present invention is: a kind of solar cell module polycrystalline
The preparation method of silicon wafer, it is characterised in that include the following steps:
By polycrystalline silicon rod preparation facilities growing silicon polycrystal crystal rod, the polycrystalline silicon rod is taken out and is sent to by second conveyer
Polycrystalline silicon rod cutter device is handled；
Polycrystalline silicon rod cutter device cuts the polycrystalline silicon rod, is cut into thickness and meets the polysilicon chip needed, then
The polysilicon chip is sent to silicon wafer cutting means by second conveyer to handle；
Silicon wafer cutting means carry out the polysilicon chip to cut processing, make the shape meet demand of the polysilicon chip after cutting,
Then the polysilicon chip after cutting is sent to polysilicon fluff making device by third transmission device and carries out making herbs into wool processing, made described
The surface of polysilicon chip forms flannelette；
It is obtained after carrying out cleaning and drying and processing respectively using cleaning equipment and drying equipment to the polysilicon chip after formation flannelette
To solar cell module polysilicon chip.
A further technical solution lies in, the polycrystalline silicon rod the preparation method is as follows:
Industrial silicon is placed into the crucible of furnace body, furnace body is evacuated to 10-5Pa is then charged with inert gas to 0.5Pa；
The industrial silicon fusing adjusted in the power assurance crucible of primary heater and auxiliary heater will be high after industrial silicon fusing completely
Pure titanium silk is inserted into industrial silicon melt by the titanium silk protection pipe above crucible, until the content of titanium reaches molar fraction in melt
5%, start plasma electrode；
Then the growth that polysilicon in silicon alloy melt is realized by adjusting the power of primary heater and auxiliary heater, grew
Cheng Zhong drains into impurity titanium and boron, carbon in melt, as polysilicon solidification is close to after eutectic composition, stops main heating
The power regulation of device and auxiliary heater；Silicon seed will be down in silicon alloy melt by the seed rod outside operation furnace body, together
Shi Kaiqi gas tube makes the silicon alloy melt in crucible cold enough, until the generation of silicon seed end eutectic growth, realizes Eutectic Silicon in Al-Si Cast Alloys
With the eutectic growth of eutectic titanium disilicide two-phase, which lifts out the melt containing impurity in a manner of eutectic crystallization
Crucible realizes boron, carbon, oxygen removal of impurities in purification melt；
After remaining silicon alloy melt is close by lifting, the power for adjusting primary heater and auxiliary heater realizes crucible
The remelting of middle polysilicon；Then high purity titanium silk is added into melt again, after being added to required ingredient, stops addition, then leads to
The power for overregulating primary heater and auxiliary heater realizes the growth of polysilicon in silicon alloy melt, will be miscellaneous in growth course
Matter titanium and boron, carbon drain into melt, as polysilicon solidification is close to after eutectic composition, stop heater and auxiliary heating
The power regulation of device；Silicon seed is down in silicon alloy melt, while opening gas tube and making silicon alloy melt cold enough, until silicon
The generation of seed crystal end eutectic growth realizes that the eutectic growth of Eutectic Silicon in Al-Si Cast Alloys and eutectic titanium disilicide two-phase, the eutectic growth will contain
The melt of impurity mentions draw-out crucible in a manner of eutectic crystallization, realizes the removal of impurities of the boron, carbon, oxygen element in purification melt again；
Boron, carbon, oxygen impurities are reduced until required content until reaching repeatedly；
The power for adjusting primary heater and auxiliary heater, realizes the fusing of polysilicon, then by high-purity aluminium wire by crucible
In the aluminium wire protection pipe insertion industrial silicon melt of side, until stopping adding after the content of aluminium reaches molar fraction 5%-20% in melt
Add, the growth of polysilicon in silicon alloy melt is then realized by adjusting the power of primary heater and auxiliary heater, was grown
Cheng Zhong drains into impurity titanium, bismuth, arsenic, titanium, gallium, nickel, iron and copper in melt, as polysilicon is solidified close to eutectic composition
After, stop the power regulation of primary heater and auxiliary heater；Silicon seed is down in silicon alloy melt, while opening inflation
Pipe is so that silicon alloy melt is cooled to the generation in silicon seed end eutectic growth, the eutectic of realization Eutectic Silicon in Al-Si Cast Alloys and eutectic aluminum two-phase enough
Melt containing impurity is mentioned draw-out crucible by growth, the eutectic growth in a manner of eutectic crystallization, realize titanium in purification melt,
The removal of impurities of bismuth, arsenic, titanium, gallium, nickel, iron and copper；
After remaining silicon alloy melt is close by lifting, the power for adjusting primary heater and auxiliary heater realizes crucible
The remelting of middle polysilicon；Then polysilicon in silicon alloy melt is realized by adjusting the power of primary heater and auxiliary heater
It grows, in growth course, impurity titanium, bismuth, arsenic, titanium, gallium, nickel, iron and copper is drained into melt, as polysilicon solidification connects
After nearly eutectic composition, stop the power regulation of heater and auxiliary heater；Silicon seed is down in silicon alloy melt, simultaneously
Opening gas tube makes silicon alloy melt be cooled to the generation in silicon seed end eutectic growth enough, realizes Eutectic Silicon in Al-Si Cast Alloys and eutectic aluminum two
The eutectic growth of phase, which will mention draw-out crucible containing the melt containing impurity in a manner of eutectic crystallization, real again
Now purify the removal of impurities of the titanium, bismuth, arsenic, titanium, gallium, nickel, iron and copper in melt；
When above-mentioned impurity is divided to set content, stop plasma electrode, high-purity aluminium wire is proposed into silicon alloy melt；It is logical
The power for overregulating primary heater and auxiliary heater realizes the fusing of polysilicon in silicon alloy melt, using above-mentioned eutectic aluminum with
Silicon continues pulling growth, and silicon melt lifting is finished, realizes the removal of impurities of aluminium element；
High-purity silicon area cutting separation in the polysilicon casting rod of lifting is contained to the polysilicon casting rod of various eutectic phases, HIGH-PURITY SILICON
Region can reach solar-grade polysilicon rank by directional solidification again；
The polycrystalline silicon rod containing various eutectic phases will be cut down, by remelting again after crushing and pickling, then passes through 1 to 2
Secondary directional solidification or lifting solidification obtain solar-grade polysilicon stick.
A further technical solution lies in: the method for carrying out making herbs into wool processing to the polysilicon chip is as follows: by polysilicon chip
Making herbs into wool is carried out under the conditions of the Woolen-making liquid containing hydrofluoric acid and nitric acid, wherein temperature is 5 DEG C ± 0.5 DEG C, the weight of the hydrofluoric acid
Measuring concentration is 7.5% ± 0.5%, and the weight concentration of nitric acid is 38% ± 0.5%.
The beneficial effects of adopting the technical scheme are that the method is during preparing polycrystalline silicon rod,
It is removed in silicon melt by the multiple eutectic directional solidification and plasma melting of the silicon of titanium-silicon base alloys melt and titanium disilicide first
The elements such as carbon, boron, phosphorus, then further pass through the multiple eutectic directional solidification and vacuum of the aluminium of aluminium-silicon alloys melt and silicon
Electron-beam smelting removes the elements such as titanium, iron, is then purified by the lifting realization to polysilicon, is realized again by above-mentioned three step
The purification of solar-grade polysilicon can remove the plurality of impurities in polysilicon, and the purity of the polycrystalline silicon rod of preparation is higher, because
This, the purity of the polysilicon chip of preparation is higher.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the functional block diagram of system described in the embodiment of the present invention；
Fig. 2 is the structural schematic diagram of polycrystalline silicon rod preparation facilities in system described in the embodiment of the present invention；
Fig. 3 is polycrystalline silicon rod preparation facilities described in the embodiment of the present invention in the schematic diagram for carrying out silicon lifting solidification dedoping step；
Wherein: 1: seed rod；2: electrode stem；3: high purity titanium silk；4: lifting eutectic protective cover；4-1: gas tube；4-2: exhaust is logical
Road；5: plasma electrode；6: titanium silk protection pipe；7: silicon seed；8: Eutectic Silicon in Al-Si Cast Alloys；9: eutectic titanium disilicide；10: eutectic aluminum；11: etc.
Ionic arc；12: crucible: 13: primary heater；14: polysilicon；15: auxiliary heater；16: crucible pole；17: melt；18: aluminium
Silk protection pipe；19: crucible supporting；20: high-purity aluminium wire；21: furnace body；22: high-purity silicon area；23: polycrystalline silicon rod preparation facilities 24:
Silicon rod cutting device；25: silicon wafer cutting means；26: polysilicon fluff making device；27: second conveyer；28: the second transmission dresses
It sets；29: third transmission device；30: cleaning equipment；31: drying equipment；32: the four transmission devices；33: the five transmission devices.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description, it is clear that described embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, but the present invention can be with
Implemented using other than the one described here other way, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by the specific embodiments disclosed below.
As shown in Figure 1, the embodiment of the invention discloses a kind of preparation system of solar cell module polysilicon chip, packet
Include polycrystalline silicon rod preparation facilities 23, silicon rod cutting device 24, silicon wafer cutting means 25, polysilicon fluff making device 26, cleaning equipment
30 and drying equipment 31.The polycrystalline silicon rod preparation facilities 23 is used for growth for solar battery polycrystalline silicon rod, the silicon rod
Second conveyer 27 is provided between preparation facilities and the cutter device, the second conveyer 27 is used for the life
The polycrystalline silicon rod of growth device growth is transferred to the cutter device, and the cutter device is for cutting the polycrystalline silicon rod
It cuts, prepares the satisfactory polysilicon chip of thickness；The second transmission is provided between the cutter device and the cutting means
Device 28, the second conveyer 28 are used to the polysilicon chip after cutter device cutting being sent to the silicon wafer and cut
Device is cut, and the cutting means process the shape of needs for carrying out cutting processing to the silicon wafer；It is described to cut
Third transmission device 29 is provided between device and the polysilicon fluff making device, the third transmission device 29 is used for will be described
Polysilicon chip after cutting means are cut is sent to the polysilicon fluff making device, and the polysilicon fluff making device is used for cutting
Polysilicon chip afterwards carries out polycrystalline making herbs into wool processing using hydrofluoric acid and nitric acid, and the surface of the polysilicon chip is made to form flannelette；Clearly
Equipment 30 is washed, the polysilicon chip after making herbs into wool is started the cleaning processing, removes the impurity and acid solution on polysilicon chip surface；It dries
Dry equipment 31 removes the water of its surface residual for starting the cleaning processing to the polysilicon chip after cleaning.
It should be noted that the silicon rod cutting device 24, silicon wafer cutting means 25, polysilicon fluff making device 26, cleaning
Equipment 30, drying equipment 31 and second conveyer to the 5th transmission device can use equipment in the prior art,
This will not be repeated here for specific structure.
As shown in Fig. 2-Fig. 3, the polycrystalline silicon rod preparation facilities 23 includes furnace body 21, and the upper end of crucible pole 16 is located at described
In furnace body 21, and the upper end of crucible pole 16 is provided with crucible supporting 19, and the lower end of crucible pole 16 is located at outside the furnace body 21.It is described
Crucible 12 is provided in crucible supporting 19, the periphery of the crucible supporting 19 is provided with primary heater 13, the crucible supporting 19
Downside be provided with auxiliary heater 15, the middle part right above the crucible 12 is provided with lifting eutectic protective cover 4, the lifting
Gas tube 4-1 is provided on eutectic protective cover 4, the lower end of the gas tube 4-1 is located in the protective cover, and does not insert
In the melt for entering the crucible 12.The upper end of the gas tube 4-1 sequentially pass through from top to bottom the epipleural of the protective cover with
And stretched out after furnace body 21 from the upside of furnace body 21, outlet passageway 4-2 is provided on the side wall of the protective cover；The gas tube 4-
Seed rod 1 is provided between 1, the upper end of the seed rod 1 is located at the outside of the furnace body 21, and the lower end of the seed rod 1 is prolonged
It reaches in the protective cover, and the lower end of the seed rod 1 is provided with silicon seed 7.It is provided at left and right sides of the protective cover
Plasma electrode 5, the upper end of the plasma electrode 5 are provided with electrode stem 2, and the upper end of the electrode stem 2 extends to the furnace
Outside body 21, the left side of the plasma electrode 5 in left side is provided with aluminium wire protection pipe 18, the plasma positioned at right side
The right side of electrode 5 is provided with titanium silk protection pipe 6, and the plasma electrode 5, titanium silk protection pipe 6 and aluminium wire protection pipe 18
In the surface of the crucible 12.
Further, the outside of the furnace body 21 is provided with crucible pole rotation drive device, and the driving device is for driving
Move the crucible rotation.The exhaust passage 4-2 is obliquely installed, and the lower end of exhaust passage 4-2 is higher than under the protective cover
End.It being provided with drain tap on the furnace body, when for guaranteeing that gas tube 4-1 is filled with gas, excessive gas being discharged,
Volatile gas is taken into the gas being discharged from melt out of melt together simultaneously.
The invention also discloses a kind of preparation methods of solar cell module polysilicon chip, include the following steps:
By 23 growing silicon polycrystal crystal rod of polycrystalline silicon rod preparation facilities, the polycrystalline silicon rod is taken out and is passed by second conveyer 27
Polycrystalline silicon rod cutter device 24 is given to be handled；
Polycrystalline silicon rod cutter device 24 cuts the polycrystalline silicon rod, is cut into thickness and meets the polysilicon chip needed, so
The polysilicon chip is sent to silicon wafer cutting means 25 by second conveyer 28 afterwards to handle；
Silicon wafer cutting means 25 carry out the polysilicon chip to cut processing, and the shape of the polysilicon chip after cutting is made to meet need
It asks, then the polysilicon chip after cutting is sent to polysilicon fluff making device 26 by third transmission device 29 and carried out at making herbs into wool
Reason makes the surface of the polysilicon chip form flannelette；
Cleaning and drying and processing are carried out respectively using cleaning equipment 30 and drying equipment 31 to the polysilicon chip after formation flannelette
After obtain solar cell module polysilicon chip.
Further, the polycrystalline silicon rod the preparation method is as follows:
Industrial silicon is placed into the crucible 12 of furnace body, furnace body is evacuated to 10-5Pa is then charged with inert gas extremely
0.5Pa；The industrial silicon fusing in the power assurance crucible of primary heater 13 and auxiliary heater 15 is adjusted, has been melted to industrial silicon
High purity titanium silk 3 is inserted into industrial silicon melt, until the content of titanium reaches in melt by Quan Hou by the titanium silk protection pipe above crucible
To molar fraction 5%, start plasma electrode 5；
Then the life of polysilicon 14 in silicon alloy melt 17 is realized by adjusting the power of primary heater 13 and auxiliary heater 15
It is long, in growth course, impurity titanium and boron, carbon are drained into melt, as the solidification of polysilicon 14 is close to after eutectic composition,
Stop the power regulation of primary heater 13 and auxiliary heater 15；Silicon seed 7 will be down to by the seed rod outside operation furnace body
It in silicon alloy melt 17, while opening gas tube 4-1 and making the silicon alloy melt 17 in crucible cold enough, until 7 end of silicon seed is total
The generation of crystals growth realizes that the eutectic growth of Eutectic Silicon in Al-Si Cast Alloys 8 and 9 two-phase of eutectic titanium disilicide, the eutectic growth will contain impurity
Melt mentions draw-out crucible in a manner of eutectic crystallization, realizes boron, carbon, oxygen removal of impurities in purification melt；
After remaining silicon alloy melt 17 is close by lifting, the power for adjusting primary heater 13 and auxiliary heater 16 is real
The remelting of polysilicon 14 in existing crucible 12；Then high purity titanium silk 3 is added into melt again, after being added to required ingredient, is stopped
Then the life of polysilicon 14 in silicon alloy melt 17 is realized in addition by adjusting the power of primary heater 13 and auxiliary heater 15
It is long, in growth course, impurity titanium and boron, carbon are drained into melt, as the solidification of polysilicon 14 is close to after eutectic composition,
Stop the power regulation of heater 13 and auxiliary heater 16；Silicon seed 7 is down in silicon alloy melt 17, while opening inflation
Pipe 4-1 makes silicon alloy melt 17 cold enough, until the generation of 7 end eutectic growth of silicon seed, realizes Eutectic Silicon in Al-Si Cast Alloys 8 and two silication of eutectic
Melt containing impurity is mentioned draw-out crucible by the eutectic growth of 9 two-phase of titanium, the eutectic growth in a manner of eutectic crystallization, real again
Now purify the removal of impurities of the boron, carbon, oxygen element in melt；Contain repeatedly until reaching to reduce boron, carbon, oxygen impurities to required
Until amount；
The power of primary heater 13 and auxiliary heater 15 is adjusted, the fusing of polysilicon 14 is realized, then passes through high-purity aluminium wire 20
It crosses in the aluminium wire protection pipe insertion industrial silicon melt above crucible, until the content of aluminium reaches molar fraction 5%-20% in melt
Afterwards, stop addition, then realize polycrystalline in silicon alloy melt 17 by adjusting the power of primary heater 13 and auxiliary heater 15
The growth of silicon 14 in growth course, impurity titanium, bismuth, arsenic, titanium, gallium, nickel, iron and copper is drained into melt, with polysilicon
14 solidifications stop the power regulation of primary heater 13 and auxiliary heater 15 close to after eutectic composition；Silicon seed 7 is down to silicon
In alloy melt 17, while opening gas tube 4-1 and silicon alloy melt 17 is made to be cooled to the hair in 7 end eutectic growth of silicon seed enough
It is raw, realize the eutectic growth of Eutectic Silicon in Al-Si Cast Alloys 8 and 10 two-phase of eutectic aluminum, the eutectic growth is by the melt containing impurity with eutectic crystallization
Mode mentions draw-out crucible, realizes the removal of impurities of the titanium, bismuth, arsenic, titanium, gallium, nickel, iron and copper in purification melt；
After remaining silicon alloy melt 17 is close by lifting, the power for adjusting primary heater 13 and auxiliary heater 16 is real
The remelting of polysilicon 14 in existing crucible 12；Then silicon alloy is realized by adjusting the power of primary heater 13 and auxiliary heater 15
Impurity titanium, bismuth, arsenic, titanium, gallium, nickel, iron and copper in growth course, are drained into melt by the growth of polysilicon 14 in melt 17
In, as the solidification of polysilicon 14 is close to after eutectic composition, stop the power regulation of heater 13 and auxiliary heater 16；By silicon
Seed crystal 7 is down in silicon alloy melt 17, while opening gas tube 4-1 and silicon alloy melt 17 is cooled to enough at 7 end of silicon seed
The generation of eutectic growth realizes that the eutectic growth of Eutectic Silicon in Al-Si Cast Alloys 8 and 10 two-phase of eutectic aluminum, the eutectic growth will contain and contain impurity
Melt mentions draw-out crucible in a manner of eutectic crystallization, realizes titanium, bismuth, arsenic, titanium, gallium, nickel, iron and copper coin in purification melt again
The removal of impurities of element；
When above-mentioned impurity is divided to set content, stop plasma electrode 11, the proposition silicon alloy of high-purity aluminium wire 20 is melted
Body 17；Power by adjusting primary heater 13 and auxiliary heater 15 realizes the fusing of polysilicon 14 in silicon alloy melt 17,
Continue pulling growth using above-mentioned eutectic aluminum and silicon, silicon melt lifting is finished, realizes the removal of impurities of aluminium element；
The cutting separation of high-purity silicon area 22 in the polysilicon casting rod of lifting is contained to the polysilicon casting rod of various eutectic phases, it is high-purity
Silicon area 22 can reach solar-grade polysilicon rank by directional solidification again；
The polycrystalline silicon rod containing various eutectic phases will be cut down, by remelting again after crushing and pickling, then passes through 1 to 2
Secondary directional solidification or lifting solidification obtain solar-grade polysilicon stick.
During using more than 3 purifications of high purity titanium silk, the content of titanium elements in every secondary control alloy melt are as follows: 5%,
Every time when it is 14% that 17 solidification and crystallization of silicon alloy melt, which is completed to remainder melt to reach Ti content to be molar fraction, begin through
The eutectic growth of lifting eutectic Eutectic Silicon in Al-Si Cast Alloys 8 and 9 two-phase of eutectic titanium disilicide will mention draw-out crucible containing the more melt of impurity.?
During high-purity aluminium wire more than 20 times purifications, the content of titanium elements in every secondary control alloy melt are as follows: 5-20% works as every time
17 solidification and crystallization of silicon alloy melt is completed to remainder melt to reach aluminium content to be molar fraction when being 11.7%, begins through lifting
The eutectic growth of Eutectic Silicon in Al-Si Cast Alloys 8 and 10 two-phase of eutectic aluminum will mention draw-out crucible containing the more melt of impurity.
There are 2 plasma electrodes 5 on the outside of crucible 12, it will be in silicon alloy melt 17 by the high temperature that plasma melting generates
P elements evaporate into atmosphere, plasma electrode 5 work when, crucible rotation, guarantee melt in uniformity of temperature profile, be convenient for
Lift the progress of eutectic ingot.It is equipped with gas tube 4-1 and exhaust passage 4-2 on lifting eutectic protective cover 4, gas tube 4-1 is used for
Importing gas reduces lifting eutectic ingot and lifts the temperature of silicon alloy melt 17 in eutectic protective cover 4, guarantees lifting eutectic ingot
It carries out.Exhaust passage 4-2 guarantees that lifting eutectic protective cover 4 is not pressed for the gas tube 4-1 gas imported to be discharged into melt
Power is destroyed, while the gas being discharged can take the phosphorus in melt out of melt, advanced optimize refining effect.
Exhaust passage 4-2 has a certain degree on lifting 4 wall of eutectic protective cover with it, guarantees that outboard exhaust is logical
The outlet road 4-2 is higher than lifting 4 wall lower end of eutectic protective cover, guarantees that discharge gas is stablized to be put into from exhaust passage 4-2 in this way and exports
Steadily eject.It being provided with drain tap on furnace body 21, when for guaranteeing that gas tube 4-1 is filled with gas, excessive gas being discharged,
The foreign gas being discharged from melt is discharged simultaneously, not only can guarantee the stabilization of atmosphere pressures in furnace body 21, but also can be reduced discharge
The partial pressure of foreign gas guarantees that foreign gas is endlessly discharged.
High purity titanium silk 3 enters melt by titanium silk protection pipe 6, and high-purity aluminium wire 20 enters melt by aluminium wire protection pipe 18
In.Titanium silk protection pipe 6 and aluminium wire protection pipe 18 can prevent high purity titanium silk 3 and high-purity aluminium wire 20 from being melted by plasma-arc 11,
And other positions are blown to by plasma-arc 11 and atmosphere convection current.During plasma-arc 11 works, high purity titanium silk 3 or high-purity
Aluminium wire 20 will be contacted with silicon alloy melt 17, and high purity titanium silk 3 or high-purity aluminium wire 20 also act as other than providing titanium source and silicon source
Conductive effect.
Further, as follows to the method for polysilicon chip progress making herbs into wool processing: polysilicon chip is being contained into hydrofluoric acid
With making herbs into wool is carried out under the conditions of the Woolen-making liquid of nitric acid, wherein temperature is 5 DEG C ± 0.5 DEG C, and the weight concentration of the hydrofluoric acid is 7.5%
± 0.5%, the weight concentration of nitric acid is 38% ± 0.5%.
The system and method pass through the silicon and two silicon of titanium-silicon base alloys melt during preparing polycrystalline silicon rod first
Change the elements such as carbon, boron, the phosphorus in the multiple eutectic directional solidification and plasma melting removal silicon melt of titanium, then further passes through
The elements such as the aluminium of aluminium-silicon alloys melt and the multiple eutectic directional solidification of silicon and vacuum electron beam melting removal titanium, iron, then lead to
It crosses the lifting realization to polysilicon to purify again, the purification of solar-grade polysilicon is realized by above-mentioned three step, can be removed more
The purity of plurality of impurities in crystal silicon, the polycrystalline silicon rod of preparation is higher, and therefore, the purity of the polysilicon chip of preparation is higher.
Claims (3)
1. a kind of preparation method of solar cell module polysilicon chip, it is characterised in that include the following steps:
By polycrystalline silicon rod preparation facilities (23) growing silicon polycrystal crystal rod, polycrystalline silicon rod taking-up is passed through into second conveyer
(27) polycrystalline silicon rod cutter device (24) is sent to be handled；
Polycrystalline silicon rod cutter device (24) cuts the polycrystalline silicon rod, is cut into thickness and meets the polysilicon chip needed,
Then the polysilicon chip is sent to silicon wafer cutting means (25) by second conveyer (28) to handle；
Silicon wafer cutting means (25) carry out the polysilicon chip to cut processing, and the shape of the polysilicon chip after cutting is made to meet need
It asks, then sends the polysilicon chip after cutting to polysilicon fluff making device (26) by third transmission device (29) and carry out making herbs into wool
Processing makes the surface of the polysilicon chip form flannelette；
Polysilicon chip after formation flannelette is cleaned and dried respectively using cleaning equipment (30) and drying equipment (31)
Solar cell module polysilicon chip is obtained after processing.
2. the preparation method of solar cell module polysilicon chip as described in claim 1, it is characterised in that: described is more
Crystalline silicon rod the preparation method is as follows:
Industrial silicon is placed into the crucible (12) of furnace body, furnace body is evacuated to 10-5Pa is then charged with inert gas extremely
0.5Pa；The industrial silicon fusing in the power assurance crucible of primary heater (14) and auxiliary heater (15) is adjusted, it is molten to industrial silicon
After changing completely, high purity titanium silk (3) are inserted into industrial silicon melt by the titanium silk protection pipe above crucible, until titanium in melt
Content reaches molar fraction 5%, starts plasma electrode (5)；
Then polysilicon in silicon alloy melt (17) is realized by adjusting the power of primary heater (13) and auxiliary heater (15)
(14) in growth course, impurity titanium and boron, carbon are drained into melt for growth, as polysilicon (14) solidification is close to altogether
After brilliant ingredient, stop the power regulation of primary heater (13) and auxiliary heater (15)；The seed crystal outside operation furnace body will be passed through
Silicon seed (7) is down in silicon alloy melt (17) by bar, while being opened gas tube (4-1) and being made silicon alloy melt in crucible
(17) cold enough, until the generation of silicon seed (7) end eutectic growth, realization Eutectic Silicon in Al-Si Cast Alloys (8) are total to eutectic titanium disilicide (9) two-phase
Melt containing impurity is mentioned draw-out crucible by crystals growth, the eutectic growth in a manner of eutectic crystallization, is realized in purification melt
Boron, carbon, oxygen removal of impurities；
When remaining silicon alloy melt (17) by lifting after, adjust primary heater (13) and auxiliary heater (16)
Power realizes the remelting of polysilicon (14) in crucible (12)；Then high purity titanium silk (3) are added into melt again, needed for being added to
After ingredient, stop addition, then realizes silicon alloy melt by adjusting the power of primary heater (13) and auxiliary heater (15)
(17) growth of polysilicon (14) in growth course, impurity titanium and boron, carbon is drained into melt, with polysilicon
(14) solidification stops the power regulation of heater (13) and auxiliary heater (16) close to after eutectic composition；By silicon seed (7)
It is down in silicon alloy melt (17), while opening gas tube (4-1) and making silicon alloy melt (17) cold enough, until silicon seed (7)
The generation of eutectic growth is held, realizes that the eutectic growth of Eutectic Silicon in Al-Si Cast Alloys (8) and eutectic titanium disilicide (9) two-phase, the eutectic growth will contain
There is the melt of impurity to mention draw-out crucible in a manner of eutectic crystallization, realizes that the boron in purification melt, carbon, oxygen element remove again
It is miscellaneous；Boron, carbon, oxygen impurities are reduced until required content until reaching repeatedly；
The power of primary heater (13) and auxiliary heater (15) is adjusted, the fusing of polysilicon (14) is realized, then by rafifinal
Silk (20) is inserted into industrial silicon melt by the aluminium wire protection pipe above crucible, until the content of aluminium reaches molar fraction in melt
After 5%-20%, stop addition, then realizes that silicon alloy is molten by adjusting the power of primary heater (13) and auxiliary heater (15)
The growth of polysilicon (14) in body (17) in growth course, impurity titanium, bismuth, arsenic, titanium, gallium, nickel, iron and copper is drained into molten
In body, as polysilicon (14) solidification is close to after eutectic composition, stop the function of primary heater (13) and auxiliary heater (15)
Rate is adjusted；Silicon seed (7) is down in silicon alloy melt (17), while opening gas tube (4-1) and making silicon alloy melt (17)
It is cooled to the generation in silicon seed (7) end eutectic growth enough, realizes the eutectic growth of Eutectic Silicon in Al-Si Cast Alloys (8) and eutectic aluminum (10) two-phase,
Melt containing impurity is mentioned draw-out crucible by the eutectic growth in a manner of eutectic crystallization, realize titanium in purification melt, bismuth,
The removal of impurities of arsenic, titanium, gallium, nickel, iron and copper；
When remaining silicon alloy melt (17) by lifting after, adjust primary heater (13) and auxiliary heater (16)
Power realizes the remelting of polysilicon (14) in crucible (12)；Then by adjusting primary heater (13) and auxiliary heater (15)
Power realizes the growth of polysilicon (14) in silicon alloy melt (17), in growth course, by impurity titanium, bismuth, arsenic, titanium, gallium, nickel,
Iron and copper drain into melt, as polysilicon (14) solidification is close to after eutectic composition, stops heater (13) and assist
The power regulation of heater (16)；Silicon seed (7) is down in silicon alloy melt (17), while opening gas tube (4-1) and making
Silicon alloy melt (17) is cooled to the generation in silicon seed (7) end eutectic growth enough, realizes Eutectic Silicon in Al-Si Cast Alloys (8) and eutectic aluminum (10) two
The eutectic growth of phase, which will mention draw-out crucible containing the melt containing impurity in a manner of eutectic crystallization, real again
Now purify the removal of impurities of the titanium, bismuth, arsenic, titanium, gallium, nickel, iron and copper in melt；
When above-mentioned impurity is divided to set content, stop plasma electrode (11), high-purity aluminium wire (20) are proposed that silicon closes
Golden melt (17)；Power by adjusting primary heater (13) and auxiliary heater (15) realizes polycrystalline in silicon alloy melt (17)
The fusing of silicon (14) continues pulling growth using above-mentioned eutectic aluminum and silicon, and silicon melt lifting is finished, realizes removing for aluminium element
It is miscellaneous；
High-purity silicon area (22) cutting separation in the polysilicon casting rod of lifting is contained to the polysilicon casting rod of various eutectic phases, it is high
Pure silica region (22) can reach solar-grade polysilicon rank by directional solidification again；
The polycrystalline silicon rod containing various eutectic phases will be cut down, by remelting again after crushing and pickling, then passes through 1 to 2
Secondary directional solidification or lifting solidification obtain solar-grade polysilicon stick.
3. the preparation method of solar cell module polysilicon chip as claimed in claim 2, which is characterized in that described more
The method that crystal silicon chip carries out making herbs into wool processing is as follows: by polysilicon chip in the Woolen-making liquid under the conditions of system containing hydrofluoric acid and nitric acid
Suede, wherein temperature is 5 DEG C ± 0.5 DEG C, and the weight concentration of the hydrofluoric acid is 7.5% ± 0.5%, and the weight concentration of nitric acid is
38% ± 0.5%.
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