CN107673356A - The method for preparing the device of high-purity nm polycrysalline silcon and preparing high-purity nm polycrysalline silcon - Google Patents
The method for preparing the device of high-purity nm polycrysalline silcon and preparing high-purity nm polycrysalline silcon Download PDFInfo
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- CN107673356A CN107673356A CN201710928955.7A CN201710928955A CN107673356A CN 107673356 A CN107673356 A CN 107673356A CN 201710928955 A CN201710928955 A CN 201710928955A CN 107673356 A CN107673356 A CN 107673356A
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- 238000000034 method Methods 0.000 title claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 185
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 185
- 239000010703 silicon Substances 0.000 claims abstract description 185
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000498 ball milling Methods 0.000 claims abstract description 32
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 20
- 238000010894 electron beam technology Methods 0.000 claims abstract description 17
- 238000005119 centrifugation Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 238000002604 ultrasonography Methods 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims description 114
- 230000008018 melting Effects 0.000 claims description 114
- 239000007788 liquid Substances 0.000 claims description 89
- 239000002210 silicon-based material Substances 0.000 claims description 39
- 238000001816 cooling Methods 0.000 claims description 38
- 239000010410 layer Substances 0.000 claims description 32
- 238000002955 isolation Methods 0.000 claims description 25
- 239000011805 ball Substances 0.000 claims description 23
- 239000011229 interlayer Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002826 coolant Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 claims description 20
- 239000000498 cooling water Substances 0.000 claims description 13
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- 230000003028 elevating effect Effects 0.000 claims description 8
- 230000002045 lasting effect Effects 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 229910021487 silica fume Inorganic materials 0.000 claims description 5
- 238000007914 intraventricular administration Methods 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 238000005253 cladding Methods 0.000 claims description 3
- -1 division board Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 8
- 238000001556 precipitation Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
- 229910052571 earthenware Inorganic materials 0.000 description 4
- 229920005591 polysilicon Polymers 0.000 description 3
- 239000004484 Briquette Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
Abstract
The present invention relates to a kind of device for preparing high-purity nm polycrysalline silcon and the method for preparing high-purity nm polycrysalline silcon, and crystal grain is prepared as Nano grade, loose porous high-purity vapor deposited silicon first with electron-beam process；Then planetary ball mill ball milling vapor deposited silicon, nano-multicrystal silicon grain is obtained；Nano-multicrystal silicon grain is mixed with water, stirring, ultrasound precipitation remove larger particles；Cast out the silicon mud for being deposited in bottom larger particles, take upper strata suspension to pour into centrifuge tube, be placed in supercentrifuge separation；The silicon grain for being deposited in centrifugation bottom of the tube is placed in vacuum drying chamber to dry, particle diameter is obtained and is less than 500nm, and D50≤ 100nm polycrysalline silcon, the problem of current silicon nanoparticle crystallinity is poor, purity is low is this method solve, improve production efficiency, the silicon grain purity height of preparation, crystallinity is good, particle diameter distribution is narrow.
Description
Technical field
The present invention relates to silicon preparing technical field, more particularly to a kind of device and system for preparing high-purity nm polycrysalline silcon
The method of standby high-purity nm polycrysalline silcon.
Background technology
Nano-multicrystal silicon has wide prospect of the application, and there are electronic luminescent material, catalyst in the field applied at present
Carrier, pharmaceutical carrier and lithium ion battery negative material etc..Especially, silicon has as lithium ion battery negative material
4200mA.h/g theoretical discharge capacity, about 10 times of carbon negative pole material theoretical capacity in the market.So silicon conduct
Cell negative electrode material is expected to solve the problems, such as that current electric automobile and electronic product portable power source needs frequent charge, shows very
Considerable potentiality.But there is charge and discharge process volumetric expansion shrinkage phenomenon, maximum volume expansion in silicon as cell negative electrode material
Rate reaches 300% or so, causes negative pole to be destroyed, serious to reduce circulating battery capacity, cycle life and cyclical stability.
The key for solving the problem is single silicon grain size reduction to below 200nm, slows down silicon grain in battery charging and discharging with this
Process volume dilation degree, so as to stable cell performance.
The apparatus and method of production polysilicon nanometer particle include aqua-solution method and high temperature reduction method etc. at present, but are making
The problem of different degrees of be present in terms of standby cost or product quality, such as preparation efficiency is low, energy consumption is big, polysilicon nanometer particle
The problems such as purity is not high, crystallinity is poor, particle diameter distribution is wide.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of device for preparing high-purity nm polycrysalline silcon and prepared high
The method of pure nano-multicrystal silicon grain, using physical vapour deposition (PVD) principle, obtain high-purity vapor deposited silicon of nanometer-size die, silicon
Nano particle purity is high, crystallinity is good, particle diameter distribution is narrow.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of device for preparing high-purity nm polycrysalline silcon, including electronic torch melting system and cooling collection system, electricity
Beamlet smelting system includes working chamber, closing hatch door, and cooling collection system includes collecting chamber, drive device, coldplate, scraper plate dress
Put, working chamber is a sealing space structure, and collecting chamber is a sealing space structure, and closing hatch door is arranged on working chamber's side wall
On, collecting chamber connects working chamber behind the side of closing hatch door, closing hatch door opening with collecting chamber, the drive being fixed in collecting chamber
Dynamic device matches with coldplate, and when closing hatch door open mode, drive device driving coldplate is transferred to working chamber or receipts
Collecting room, the screeding device and coldplate for being arranged on collecting chamber match, when coldplate is moved to collecting chamber, screeding device and cooling
Plate contacts, and strikes off the silicon deposited on coldplate.
Optimal, the coldplate includes hollow plate body, cooling medium entrance, cooling medium outlet, through hole, hollow sheeting
The through hole run through up and down is provided among body, one end of hollow plate body is provided with cooling medium entrance and cooling medium outlet；
Hollow plate body is made of resistant to elevated temperatures function-graded material, i.e., hollow plate body is at least two layers from the inside to the outside, and inner layer material
Thermal expansion coefficient is less than the thermal expansion coefficient of cladding material.
Optimal, the screeding device includes support bar, upper folder, motion bar, lower folder, and one end of support bar is arranged on collection
In chamber interior walls, the other end of support bar is provided with telescopic movable rod, and the both ends of motion bar are respectively arranged with folder and lower folder, upper folder
During with lower folder folder positioned at the both sides up and down of hollow plate body, i.e. upper folder clamping with hollow plate body upper surface, during lower folder clamping with
Hollow plate body lower surface contact, the cooling collection system also include collecting crucible, collect the upper shed of crucible and hollow plate body
Shape matches, and collects crucible and is located at screeding device bottom, the silicon that access screeding device is collected on the cooling plate；The driving dress
Put including drive rod, chute, grasping plate structure, chute is arranged on collection chamber interior walls, and one end of drive rod is provided with grasping plate structure, grabbed
Harden structure engages with chute, and grasping plate structure one end matches with coldplate, i.e., grasping plate structure catches one end of coldplate, driving
Bar driving grasping plate structure is moved in chute.
Optimal, the side wall of the working chamber and collecting chamber is that centre is provided with water-cooling sandwich；It is described collection crucible be
Bilayer zone water-cooling structure made of steel or copper product, and recirculated cooling water is provided between bilayer, collect inner surface of crucible
Thin layer silicon nanoparticle is scribbled, the bore for collecting crucible is 400~600mm；The coldplate also includes dividing plate, cooling water, every
Space hollow in hollow sheeting body is divided into the zigzag a turned back path by plate, and the both ends of zigzag path are to cool down to be situated between
Matter entrance and cooling medium outlet, cooling water circulates in the path that hollow plate body dividing plate is formed, coldplate for diameter 300~
500mm circular slab, the aperture of coldplate centre through hole is 50~200mm.
Optimal, the collecting chamber includes internal protecting wall, outer furnace wall, middle interlayer, path dividing plate, cold water inlet, goes out cold water outlet,
Internal protecting wall and outer furnace wall are made of steel materials, and are provided with one layer of nano silica fume coating on the inside of internal protecting wall, are arranged on internal layer
Internal protecting wall and be arranged on outer layer outer furnace wall between have a middle interlayer, the top of middle interlayer is provided with cold water inlet and goes out cold water
Mouthful, path dividing plate is in turn back helical spiral in middle interlayer, the path for downward spiral of being turned back after one spiral of formation is upward, spiral shell
The both ends of rotation path are cold water inlet respectively and go out cold water outlet；The cooling collection system also includes being arranged on leading in working chamber
Rail, guide rail are fixedly connected with melting chamber interior walls, and guide rail matches with coldplate, and guide rail includes left recessed groove, right groove and disk roller,
Left recessed groove and right recessed groove are relative, and the bottom in left recessed groove and right recessed groove is provided with disk roller, the both sides difference of coldplate
It is placed in left recessed groove and right recessed groove on disk roller, and is slided in left recessed groove and right recessed groove.
Optimal, the electronic torch melting system also includes silicon material entrance, melting kettle, solid-liquid baffle plate, overfall, electronics
Rifle, crucible, aqueous cold plate, mobile melting kettle device, transfer undertaking crucible device, adsorption plate, observation window are accepted, working chamber includes
Inwall, outer wall, interlayer, division board, water inlet, delivery port, inner and outer wall is made of steel material, and inner wall is set
Have one layer of nano silica fume coating, be arranged on the inwall of internal layer and be arranged on outer layer outer wall between have interlayer, the top of interlayer is set
Water inlet and delivery port are equipped with, division board spirals in interlayer in double-layer spiral shape, spiral of being turned back after one spiral of formation is upward
Downward path, the both ends of path are water inlet and delivery port respectively；Observation window, observation window connection melting are provided with working chamber
Chamber interior and the external world；Upper wall in working chamber is provided with adsorption plate, and adsorption plate is the heat-resistance stainless steel net of high density mesh；It is molten
The top of refining room is provided with silicon material entrance, and the melting kettle being arranged in working chamber matches with silicon material entrance, and electron gun is fixed
On working chamber top, electron gun corresponds with melting kettle and undertaking crucible, and electron gun is located at melting kettle and accepts earthenware
The top of crucible, is provided with solid-liquid baffle plate in melting kettle, and the inwall of top half is close in the both ends of solid-liquid baffle plate and melting kettle
Sealing is determined, and has silicon liquid path between the bottom of solid-liquid baffle plate and melting kettle, and melting kettle is isolated into dress by solid-liquid baffle plate
Silicon material part and dress silicon liquid part, the side of melting kettle dress silicon liquid part are provided with overfall, accept crucible and be arranged on overflow
The side of mouth, overfall match with accepting crucible, i.e., the silicon liquid in melting kettle is flowed into by overfall and accepted in crucible,
Accept crucible inner bottom part and be provided with aqueous cold plate, the cooling medium for having circulation in aqueous cold plate；Melting kettle and undertaking crucible are all double
Copper crucible of the layer with water-cooling structure, and recirculated cooling water is provided between bilayer；Mobile melting kettle device includes melting kettle
Base, pulley, mobile bar, melting kettle are placed on melting kettle base, and melting kettle base bottom is provided with pulley, are moved
Lever is fixedly connected with melting kettle base；Transferring undertaking crucible device includes elevating lever and tray, and elevating lever, which is fixed on, to be held
Tray bottom is connect, undertaking crucible is put on tray, elevating lever drives the undertaking crucible on tray to rise or fall；The cooling
Collection system also includes the dodge gate for being arranged on collecting chamber side wall.
A kind of method for preparing high-purity nm polycrysalline silcon, comprises the following steps：
Electronic torch melting prepares vapor deposited silicon：Solid-state silicon is fused into silicon liquid using the electron beam that electron gun is sent, after
It is continuous to allow high-power electron beam to beat in surface of the silicon liquid so that silicon liquid is gasificated into gas-phase silicon, and gas-phase silicon is deposited on cooling after running into coldplate
On plate, the silicon deposited on the cooling plate is scraped, obtains vapor deposited silicon.
Optimal,
The electronic torch melting prepares vapor deposited silicon step：Added into working chamber in melting kettle and account for melting
The solid-state silicon of crucible capacity 1/3rd, it is 10 by force in melting intraventricular pressure-4~10-3Pa, melting indoor temperature is more than 2273K's
Under the conditions of, the electron gun directly over melting kettle preheats first, to after obtaining high pressure and stablize electron beam, scans in melting kettle
Solid-state silicon, and increase the power of electron gun, lasting scanning, solid-state silicon be fused into silicon liquid；Then from silicon material entrance to melting
Solid-state silicon is added in crucible, electron beam continues to scan on solid-state silicon, solid-state silicon is melted into silicon liquid；Silicon liquid in melting kettle is by overflowing
Head piece, which flows out to, to be accepted in crucible, is accepted the electron gun directly over crucible and is preheated first, to after obtaining high pressure and stablize electron beam,
The silicon liquid in crucible is accepted in scanning, and increases the power of electron gun, lasting scanning, silicon liquid is gasificated into gas-phase silicon, gas-phase silicon is waved
Hair, and deposited on the cooling plate after running into coldplate, the collection intraventricular pressure of working chamber's isolation hatch door opposite side is 10 by force-4~10- 3Pa, after coldplate is collected into setting time, isolation hatch door is opened, coldplate is transferred to receipts by working chamber using drive device
Collect room, close isolation hatch door, will deposit silicon on the cooling plate using screeding device scrapes to collecting in crucible, then open every
From hatch door, coldplate is transferred to working chamber by collecting chamber using drive device, closes isolation hatch door, gas-phase silicon continues volatilization and met
Deposit on the cooling plate, so volatilized completely to the silicon liquid accepted in crucible repeatedly, electron gun is stopped, and treats after to coldplate
Pressure in working chamber and collecting chamber takes out close to normal pressure, and in working chamber and collecting chamber during temperature near room temperature from dodge gate
Crucible is collected, obtains vapor deposited silicon.
Optimal,
It is further comprising the steps of：
Ball mill prepares nano particle：The spheroidal graphite of ball mill is poured into after obtained vapor deposited silicon is mixed with ball-milling medium
In tank, the mixture of nano silicon particles and ball-milling medium is obtained；
Separate silicon grain：The mixture of obtained nano silicon particles and ball-milling medium and water are thoroughly mixed, then
It is placed in ultrasound environments and is ultrasonically treated, removes the silicon grain for being deposited in bottom, take the silicon water mixed liquid on top, that is, obtain silicon
Water mixed liquid；
Obtain silicon grain：Obtained silicon water mixed liquid is centrifuged, sediment is collected, puts the precipitate in vacuum drying chamber
Dry, obtain high-purity nm silicon grain.
Optimal,
Ball mill prepares nano particle：The vapor deposited silicon of one mass parts is mixed with the ball-milling medium of three mass parts, after
Pour into the spheroidal graphite tank of planetary ball mill, ball milling 16~24 hours, obtain the mixture of nano silicon particles and ball-milling medium.
Separate silicon grain：By the water of the mixture and 50~200 mass parts of the nano silicon particles of 1 mass parts and ball-milling medium
Mix and be sufficiently stirred, be subsequently placed in ultrasonic power as 70%, temperature be carried out in 25 DEG C of ultrasound environments supersound process 10~
30 minutes, persistently stirred during supersound process, stop stirring after supersound process, staticly settle at least 15 minutes, take the silicon on top
Water mixed liquid, give up the bulky grain silicon grain for being deposited in bottom, that is, obtain silicon water mixed liquid；
Obtain silicon grain：Obtained silicon water mixed liquid is centrifuged, centrifugal rotational speed 9000-11000r/min, centrifugation time
For 10~20min, sediment is collected, puts the precipitate in 130~150 DEG C of vacuum drying chambers and dries at least 2 hours, obtain grain
Footpath is less than 500nm, and D50≤ 100nm high-purity nm silicon grain.
As shown from the above technical solution, the device provided by the invention for preparing high-purity nm polycrysalline silcon and prepare high-purity
The method of nano-multicrystal silicon grain, the device for preparing high-purity nm polycrysalline silcon are mainly received by electronic torch melting system and water cooling
Collecting system two parts form, and electronic torch melting system melts silicon, and high temperature high vacuum causes liquid-state silicon to become saturated vapor silicon, it
Afterwards by water cooling collection device, driving gas-phase silicon fast deposition and forming core, while sufficient supercooling suppresses crystal grain and grown up, so as to
To nanocrystal, high-purity vapor deposited silicon of nanometer-size die is obtained；Then planetary ball mill ball milling vapor deposited silicon, is obtained
Polysilicon nanometer particle；Nano-multicrystal silicon grain is mixed with water, stirred, ultrasound precipitation classification；Cast out and be deposited in the big of bottom
Particle, upper strata suspension is taken to be placed in supercentrifuge separation；Nano silicon particles of the precipitation and separation in centrifugation bottom of the tube are placed at
Vacuum drying chamber is dried, and is obtained particle diameter and is less than 500nm, and D50≤ 100nm High Purity Polycrystalline nano silicon particles.The device can connect
Continuous production, can high efficiency obtain the good loose porous high-purity vapor deposited silicon of crystallinity, and nano silicon particles purity
Height, crystallinity is good, particle diameter distribution is narrow.
Brief description of the drawings
Accompanying drawing 1 is the front view for the device for efficiently preparing high-purity vapor deposited silicon.
Accompanying drawing 2 is the side view for the device for efficiently preparing high-purity vapor deposited silicon.
Accompanying drawing 3 is the microscopic appearance of vapor deposited silicon.
Accompanying drawing 4 is the XRD spectrums of vapor deposited silicon.
Accompanying drawing 5 is the particle diameter distribution for the silicon nanoparticle that embodiment 2 obtains.
Accompanying drawing 6 is the microscopic appearance for the silicon nanoparticle that embodiment 2 obtains.
Accompanying drawing 7 is the particle diameter distribution for the silicon nanoparticle that embodiment 3 obtains.
Accompanying drawing 8 is the microscopic appearance for the silicon nanoparticle that embodiment 3 obtains.
In figure：Electronic torch melting system 100, working chamber 101, closing hatch door 102, silicon material entrance 103, melting kettle 104,
Solid-liquid baffle plate 105, overfall 106, electron gun 107, undertaking crucible 108, mobile melting kettle device 109, aqueous cold plate 110, suction
Attached plate 111, observation window 112, cooling collection system 20, collecting chamber 21, drive device 22, coldplate 23, screeding device 24, collection
Crucible 25, dodge gate 26.
Embodiment
With reference to the accompanying drawing of the present invention, the technical scheme of inventive embodiments is further elaborated.
Referring to the drawings 1 and accompanying drawing 2 shown in, a kind of device for preparing high-purity nm polycrysalline silcon, including electronic torch melting
System 100 and cooling collection system 20.Electronic torch melting system 100 includes working chamber 101, closing hatch door 102, silicon material entrance
103rd, melting kettle 104, solid-liquid baffle plate 105, overfall 106, electron gun 107, undertaking crucible 108, aqueous cold plate 110, movement are molten
Crucible device 109 is refined, transfers and accepts crucible device, adsorption plate 111, observation window 112.Cooling collection system 20 includes collecting chamber
21st, drive device 22, coldplate 23, screeding device 24, collection crucible 25, guide rail, dodge gate 26.
Working chamber 101 is a sealing space structure, and collecting chamber 21 is a sealing space structure, working chamber 101 and receipts
The side wall of collection room 21 is that centre is provided with water-cooling sandwich, and closing hatch door 102 is arranged in the side wall of working chamber 101, collecting chamber 21
In the side of closing hatch door 102, working chamber 101 is connected with collecting chamber 21 after closing hatch door 102 is opened, and the side wall of collecting chamber 21 is set
There is dodge gate 26, the side wall of working chamber 101 is provided with observation window 112.
Collecting chamber 21 includes internal protecting wall, outer furnace wall, middle interlayer, path dividing plate, cold water inlet, goes out cold water outlet, internal protecting wall and
Outer furnace wall is made of steel material, and is provided with one layer of nano silica fume coating on the inside of internal protecting wall, is arranged on the internal protecting wall of internal layer
And be arranged between the outer furnace wall of outer layer and have middle interlayer, the top of middle interlayer is provided with cold water inlet and goes out cold water outlet, path every
Plate is in turn back helical spiral in middle interlayer, the path for downward spiral of being turned back after one spiral of formation is upward, spiral channel
Both ends are cold water inlet respectively and go out cold water outlet.
Drive device 22, coldplate 23, screeding device 24, collection crucible 25 are provided with collecting chamber 21, is fixed on collection
Drive device 22 in room 21 matches with coldplate 23, and coldplate 23 includes hollow plate body, dividing plate, cooling water, cooling medium
Entrance, cooling medium export, through hole, are provided with the through hole run through up and down among hollow plate body, are provided with hollow plate body
Space hollow in hollow sheeting body is divided into the zigzag turned back to lead to by cooling medium entrance and cooling medium outlet, dividing plate
Road, the both ends of zigzag path are cooling medium entrance and cooling medium outlet, and cooling water is formed in hollow plate body dividing plate
Circulate in path, coldplate is 300~500mm of diameter circular slab, the aperture of 23 middle through hole of coldplate for 50~
200mm；Hollow plate body is made of resistant to elevated temperatures function-graded material, i.e., hollow plate body is at least two layers from the inside to the outside, and internal layer
The thermal expansion coefficient of material is less than the thermal expansion coefficient of cladding material.Drive device 22 includes drive rod, chute, grasping plate knot
Structure, chute are arranged on the inwall of collecting chamber 21, and one end of drive rod is provided with grasping plate structure, and grasping plate structure engages with chute, and grabs
Harden structure one end matches with coldplate 23, i.e., grasping plate structure catches one end of coldplate 23, and drive rod driving grasping plate structure exists
Moved in chute, drive device 22 drives coldplate 23 to be transferred to working chamber 101 or collecting chamber 21, and guide rail is arranged on working chamber
In 101, guide rail is fixedly connected with the inwall of working chamber 101, and guide rail matches with coldplate 23, and guide rail is recessed including left recessed groove, the right side
Groove and disk roller, left recessed groove and right recessed groove are relative, and the bottom in left recessed groove and right recessed groove is provided with disk roller, coldplate
Both sides are placed in left recessed groove and right recessed groove on disk roller respectively, and are slided in left recessed groove and right recessed groove, and guide rail is used
In putting the coldplate 23 in working chamber 101, when closing 102 open mode of hatch door, the screeding device 24 of collecting chamber 21 is arranged on
Match with coldplate 23, screeding device 24 includes support bar, upper folder, motion bar, lower folder, and one end of support bar is arranged on collection
On the inwall of room 21, the other end of support bar is provided with telescopic movable rod, and the both ends of motion bar are respectively arranged with folder and lower folder, on
When folder and lower folder folder are positioned at the both sides up and down of hollow plate body, i.e. upper folder clamping with hollow plate body upper surface, during lower folder clamping
Contacted with hollow plate body lower surface, when coldplate 23 is moved to collecting chamber 21, upper folder and lower folder contact with coldplate 23 simultaneously, scrape
Except the silicon deposited on coldplate 23.The upper shed for collecting crucible 25 matches with hollow plate shape, and collection crucible 25, which is located at, to be scraped
The bottom of panel assembly 24, the silicon that access screeding device 24 is collected on coldplate 23.It is steel or copper product system to collect crucible 25
Into bilayer zone water-cooling structure, and recirculated cooling water is provided between bilayer, collects the inner surface of crucible 25 and scribble thin layer nano-silicon
Particle, the bore for collecting crucible 25 is 400~600mm.
Working chamber 101 includes inwall, outer wall, interlayer, division board, water inlet, delivery port, and inner and outer wall is steel material
Material is made, and inner wall is provided with one layer of nano silica fume coating, the inwall for being arranged on internal layer and be arranged on outer layer outer wall it
Between have interlayer, the top of interlayer is provided with water inlet and delivery port, and division board spirals in interlayer in double-layer spiral shape, formed one
The path for downward spiral of being turned back after individual spiral is upward, the both ends of path are water inlet and delivery port respectively.It is upper in working chamber 101
Wall is provided with adsorption plate 111, and adsorption plate 111 is the heat-resistance stainless steel net of high density mesh, and the top of working chamber 101 is provided with silicon
Expect entrance 103, the melting kettle 104 being arranged in working chamber 101 matches with silicon material entrance 103, and electron gun 107 is fixed on molten
The top of room 101 is refined, electron gun 107 corresponds with melting kettle 104 and undertaking crucible 108, and electron gun 107 is located at melting earthenware
Crucible 104 and the top for accepting crucible 108, are provided with solid-liquid baffle plate 105 in melting kettle 104, the both ends of solid-liquid baffle plate 105 with it is molten
The inner wall sealing of top half is fixed in refining crucible 104, and has silicon between the bottom of solid-liquid baffle plate 105 and melting kettle 104
Melting kettle 104 is isolated into dress silicon material part and dress silicon liquid part by liquid path, solid-liquid baffle plate 105, and melting kettle 104 fills silicon liquid
Partial side is provided with overfall 106, accepts the side that crucible 108 is arranged on overfall 106, overfall 106 is with accepting earthenware
Crucible 108 matches, i.e., the silicon liquid in melting kettle 104 is flowed into by overfall 106 and accepted in crucible 108.
Melting kettle 104 is the copper crucible of bilayer zone water-cooling structure, and recirculated cooling water is provided between bilayer.It is mobile molten
Refining crucible device 109 includes the base of melting kettle 104, pulley, mobile bar, and melting kettle 104 is placed at the bottom of melting kettle 104
On seat, the base bottom of melting kettle 104 is provided with pulley, and mobile bar is fixedly connected with the base of melting kettle 104, and mobile bar drives
Melting kettle 104 on the base of melting kettle 104 moves in working chamber 101.
Accepting crucible 108 is the copper crucible of bilayer zone water-cooling structure, and recirculated cooling water is provided between bilayer, accepts earthenware
The inner bottom part of crucible 108 is provided with aqueous cold plate 110, there is the cooling medium of circulation in aqueous cold plate 110.Transfer and accept crucible device including rising
Drop bar and tray, elevating lever are fixed on undertaking tray bottom, are put on tray and accept crucible 108, and elevating lever drives tray
On undertaking crucible 108 rise or fall.
The present invention also provides a kind of method for preparing high-purity nm polycrysalline silcon.
Embodiment 1：
S1：Electronic torch melting prepares vapor deposited silicon step：Added into working chamber 101 in melting kettle 104
The solid-state silicon of the capacity 1/3rd of melting kettle 104 is accounted for, pressure is 10 in working chamber 101-4~10-3Pa, in working chamber 101
Temperature is more than under conditions of 2273K, and the electron gun 107 directly over melting kettle 104 preheats first, and to obtaining, high pressure and stabilization are electric
After beamlet, the solid-state silicon in melting kettle 104 is scanned, and increases the power of electron gun 107, lasting scanning, solid-state silicon is melted
Into silicon liquid；Then solid-state silicon is added into melting kettle 104 from silicon material entrance 103, electron beam continues to scan on solid-state silicon, by solid-state
Silicon is melted into silicon liquid；Silicon liquid in melting kettle 104 is flowed out to by overfall 106 to be accepted in crucible 108, is accepting crucible 108 just
The electron gun 107 of top is preheated first, and to after obtaining high pressure and stablize electron beam, the silicon liquid in crucible 108 is accepted in scanning, and is increased
Add the power of electron gun 107, lasting scanning, silicon liquid is gasificated into gas-phase silicon, gas-phase silicon volatilization, and deposited after running into coldplate 23
On coldplate 23, it is 10 that working chamber 101, which isolates pressure in the collecting chamber 21 of hatch door opposite side,-4~10-3Pa, coldplate 23 are received
After collecting setting time, isolation hatch door is opened, coldplate 23 is transferred to collecting chamber by working chamber 101 using drive device 22
21, isolation hatch door is closed, the silicon being deposited on coldplate 23 is scraped to collecting in crucible 25 using screeding device 24, then opened
Isolation hatch door is opened, coldplate 23 is transferred to working chamber 101 by collecting chamber 21 using drive device 22, closes isolation hatch door, gas
Phase silicon continues to be deposited on coldplate 23 after volatilization runs into coldplate 23, so repeatedly complete to the silicon liquid accepted in crucible 108
Volatilization, electron gun 107 is stopped, and treats pressure in working chamber 101 and collecting chamber 21 close to normal pressure, and working chamber 101 and receives
When collecting temperature near room temperature in room 21, taken out from dodge gate 26 and collect crucible 25, obtain vapor deposited silicon.
S2：Ball mill prepares nano particle：The vapor deposited silicon of one mass parts is mixed with the ball-milling medium of three mass parts,
Pour into afterwards in the spheroidal graphite tank of planetary ball mill, ball milling 16~24 hours, obtain the mixture of nano silicon particles and ball-milling medium.
S3：Separate silicon grain：By the nano silicon particles of 1 mass parts and the mixture and 50~200 mass parts of ball-milling medium
Water mix and be sufficiently stirred, be subsequently placed in ultrasonic power as 70%, temperature is to be ultrasonically treated in 25 DEG C of ultrasound environments
10~30 minutes, persistently stirred during supersound process, stop stirring after supersound process, staticly settle at least 15 minutes, take top
Silicon water mixed liquid, give up the bulky grain silicon grain for being deposited in bottom, that is, obtain silicon water mixed liquid；
S4：Obtain silicon grain：Obtained silicon water mixed liquid is centrifuged, centrifugal rotational speed 9000-11000r/min, during centrifugation
Between be 10~20min, collect sediment, put the precipitate in 130~150 DEG C of vacuum drying chambers dry at least 2 hours, obtain
Particle diameter is less than 500nm, and D50≤ 100nm high-purity nm silicon grain.
Embodiment 2：
S1：High-purity silicon raw material is loaded into melting kettle 104 through silicon material entrance 103, charge weight is about that melting kettle 104 holds
/ 3rd of amount, high purity polycrystalline silicon particle is spread accepting the bottom of crucible 108, will be molten using mobile melting kettle device 109
The mobile working position of crucible 104 is refined, i.e. overfall 106 is being accepted above crucible 108, closes isolation hatch door, dodge gate 26, He Guan
Examine window 112 so that collecting chamber 21 and working chamber 101 seal.
S2：Start vacuum system, the vacuum of working chamber 101 is extracted into less than 10-3Pa, to meet the work atmosphere of electron gun 107
Enclose.
S3：Transfer electron gun 107 so that the solid-state in the corresponding melting kettle 104 of the electron beam scanning of electron gun 107
Silicon.Electron gun 107 is gradually preheated, after reaching high pressure and stablizing electronic beam current, scans solid-state silicon material, increase electron gun 107
Power, it is lasting to scan about 10min so that the solid-state silicon in melting kettle 104 all melts.
S4：Appropriate silicon material is continuously added to melting kettle 104 from silicon material entrance 103.
S5：Electron beam continues to scan on the silicon material of melting kettle 104, until solid-state silicon all melts, the fusing of dress silicon material part
Silicon liquid flow into dress silicon liquid part from the bottom of solid-liquid baffle plate 105.The silicon material that now overfall 106 is solidified blocks repeat step
S4 and S5 so that block the melting silicon materials of overfall 106.
S6：Silicon liquid in melting kettle 104 flows into from overfall 106 and accepts crucible 108, continue from silicon material entrance 103 after
It is continuous to add appropriate silicon material to melting kettle 104, repeat step S4, S5, S6, the high-purity silicon materials of 450kg are put into altogether.
S7：Start and accept the corresponding electron gun 107 of crucible 108, electron gun 107 is gradually preheated, reach high pressure and steady
After determining electronic beam current, solid-state silicon material is scanned, increases the power of electron gun 107, silicon liquid is gasificated into gas-phase silicon, gas-phase silicon is volatilized,
And it is deposited on after running into coldplate 23 on coldplate 23.
S8：When plate 23 to be cooled have collected about 2 hours, isolation hatch door is opened, isolation hatch door is opened, utilizes driving
Coldplate 23 is transferred to collecting chamber 21 by device 22 by working chamber 101, is closed isolation hatch door, will be deposited on using screeding device 24
Silicon on coldplate 23 is scraped into collection crucible 25.
S9：Coldplate 23 is being transferred to working chamber 101 by collecting chamber 21 using drive device 22, is reusing scraper plate dress
24 are put to scrape the silicon being deposited on coldplate 23 into collection crucible 25.
S10：Then isolation hatch door is opened, coldplate 23 is transferred to working chamber by collecting chamber 21 using drive device 22
101, isolation hatch door is closed, gas-phase silicon continues to be deposited on coldplate 23 after volatilization runs into coldplate 23, so repeatedly to undertaking
Silicon liquid in crucible 108 is volatilized completely.
S11：Electron gun 107 is stopped, and treats pressure in working chamber 101 and collecting chamber 21 close to normal pressure, and working chamber
101 and collecting chamber 21 in temperature near room temperature when, from dodge gate 26 take out collect crucible 25, obtain obtain 400kg vapour deposition
Silico briquette, as shown in Figure 3, crystallinity is as shown in Figure 4 for obtained vapor deposited silicon microscopic appearance.
S12：400g vapour deposition silico briquettes are taken, is crushed through simple, two 200g is divided into, by 200g vapour deposition
Silicon mixes with 600g ball-milling medium, pours into respectively in two 1L ball grinder.
S13：Two ball grinders equipped with vapor deposited silicon and ball-milling medium mixture are symmetrically mounted on planetary type ball-milling
On machine.
S14：Start ball mill, run 20 hours.
S15：After ball mill end of run, ball grinder is taken out, the mixed of the nano silicon particles and ball-milling medium for milling to obtain
Compound takes out from ball grinder.
S16：The nano silicon particles of 1 mass parts and the mixture of ball-milling medium are mixed with the water of 50 mass parts and fully stirred
Mix, pour into beaker.
S17：Mixture equipped with nano silicon particles and ball-milling medium and the beaker of water are placed in ultrasonic device.
S18：Start ultrasonic device, ultrasonic power is arranged to 70%, and temperature setting is constant at 25 DEG C, while stirs 20min.
S19：Stop stirring, staticly settle 20min.
S20：, the silicon water mixed liquid on top is taken, gives up the bulky grain silicon grain for being deposited in bottom, that is, obtains the mixing of silicon water
Liquid.
S21：Centrifuge tube is poured into while the quality such as silicon water mixed liquid will be obtained, centrifuge tube is arranged on supercentrifuge, and centrifugation turns
Speed is 9000-11000r/min, and centrifugation time is 10~20min.
S22：Centrifuge tube supernatant liquid is poured out, and the upper liquid is repeatedly applied to S16 and substitutes water, retains centrifugation bottom of the tube
Sediment.
S23：Put the precipitate in 130 DEG C of vacuum drying chambers and dry 3 hours, obtain particle diameter and be less than 500nm, and D50≤
100nm high-purity nm silicon grain.Obtained high-purity nm silicon grain particle diameter distribution as shown in Figure 5, microscopic appearance such as accompanying drawing 6
It is shown.
Embodiment 3：
S1：High-purity silicon raw material is loaded into melting kettle 104 through silicon material entrance 103, charge weight is about that melting kettle 104 holds
/ 3rd of amount, high purity polycrystalline silicon particle is spread accepting the bottom of crucible 108, will be molten using mobile melting kettle device 109
The mobile working position of crucible 104 is refined, i.e. overfall 106 is being accepted above crucible 108, closes isolation hatch door, dodge gate 26, He Guan
Examine window 112 so that collecting chamber 21 and working chamber 101 seal.
S2：Start vacuum system, the vacuum of working chamber 101 is extracted into less than 10-3Pa, to meet the work atmosphere of electron gun 107
Enclose.
S3：Transfer electron gun 107 so that the solid-state in the corresponding melting kettle 104 of the electron beam scanning of electron gun 107
Silicon.Electron gun 107 is gradually preheated, after reaching high pressure and stablizing electronic beam current, scans solid-state silicon material, increase electron gun 107
Power, it is lasting to scan about 10min so that the solid-state silicon in melting kettle 104 all melts.
S4：Appropriate silicon material is continuously added to melting kettle 104 from silicon material entrance 103.
S5：Electron beam continues to scan on the silicon material of melting kettle 104, until solid-state silicon all melts, the fusing of dress silicon material part
Silicon liquid flow into dress silicon liquid part from the bottom of solid-liquid baffle plate 105.The silicon material that now overfall 106 is solidified blocks repeat step
S4 and S5 so that block the melting silicon materials of overfall 106.
S6：Silicon liquid in melting kettle 104 flows into from overfall 106 and accepts crucible 108, continue from silicon material entrance 103 after
It is continuous to add appropriate silicon material to melting kettle 104, repeat step S4, S5, S6, the high-purity silicon materials of 450kg are put into altogether.
S7：Start and accept the corresponding electron gun 107 of crucible 108, electron gun 107 is gradually preheated, reach high pressure and steady
After determining electronic beam current, solid-state silicon material is scanned, increases the power of electron gun 107, silicon liquid is gasificated into gas-phase silicon, gas-phase silicon is volatilized,
And it is deposited on after running into coldplate 23 on coldplate 23.
S8：When plate 23 to be cooled have collected about 2 hours, isolation hatch door is opened, isolation hatch door is opened, utilizes driving
Coldplate 23 is transferred to collecting chamber 21 by device 22 by working chamber 101, is closed isolation hatch door, will be deposited on using screeding device 24
Silicon on coldplate 23 is scraped into collection crucible 25.
S9：Coldplate 23 is being transferred to working chamber 101 by collecting chamber 21 using drive device 22, is reusing scraper plate dress
24 are put to scrape the silicon being deposited on coldplate 23 into collection crucible 25.
S10：Then isolation hatch door is opened, coldplate 23 is transferred to working chamber by collecting chamber 21 using drive device 22
101, isolation hatch door is closed, gas-phase silicon continues to be deposited on coldplate 23 after volatilization runs into coldplate 23, so repeatedly to undertaking
Silicon liquid in crucible 108 is volatilized completely.
S11：Electron gun 107 is stopped, and treats pressure in working chamber 101 and collecting chamber 21 close to normal pressure, and working chamber
101 and collecting chamber 21 in temperature near room temperature when, from dodge gate 26 take out collect crucible 25, obtain obtain 400kg vapour deposition
Silico briquette.
S12：400g vapour deposition silico briquettes are taken, is crushed through simple, two 200g is divided into, by 200g vapour deposition
Silicon mixes with 1000g ball-milling medium, pours into respectively in two 1L ball grinder.
S13：Two ball grinders equipped with vapor deposited silicon and ball-milling medium mixture are symmetrically mounted on planetary type ball-milling
On machine.
S14：Start ball mill, run 18 hours.
S15：After ball mill end of run, ball grinder is taken out, the mixed of the nano silicon particles and ball-milling medium for milling to obtain
Compound takes out from ball grinder.
S16：The nano silicon particles of 1 mass parts and the mixture of ball-milling medium are mixed with the water of 50 mass parts and fully stirred
Mix, pour into beaker.
S17：Mixture equipped with nano silicon particles and ball-milling medium and the beaker of water are placed in ultrasonic device.
S18：Start ultrasonic device, ultrasonic power is arranged to 70%, and temperature setting is constant at 25 DEG C, while stirs 20min.
S19：Stop stirring, staticly settle 20min.
S20：, the silicon water mixed liquid on top is taken, gives up the bulky grain silicon grain for being deposited in bottom, that is, obtains the mixing of silicon water
Liquid.
S21：Centrifuge tube is poured into while the quality such as silicon water mixed liquid will be obtained, centrifuge tube is arranged on supercentrifuge, and centrifugation turns
Speed is 9000-11000r/min, and centrifugation time is 10~20min.
S22：Centrifuge tube supernatant liquid is poured out, and the upper liquid is repeatedly applied to S16 and substitutes water, retains centrifugation bottom of the tube
Sediment.
S23：Put the precipitate in 130 DEG C of vacuum drying chambers and dry 3 hours, obtain particle diameter and be less than 500nm, and D50≤
100nm high-purity nm silicon grain.Obtained high-purity nm silicon grain particle diameter distribution as shown in Figure 7, microscopic appearance such as accompanying drawing 8
It is shown.
Claims (10)
- A kind of 1. device for preparing high-purity nm polycrysalline silcon, it is characterised in that：Received including electronic torch melting system and cooling Collecting system, electronic torch melting system include working chamber, closing hatch door, and cooling collection system includes collecting chamber, drive device, cooling Plate, screeding device, working chamber are a sealing space structures, and collecting chamber is a sealing space structure, and closing hatch door is arranged on In working chamber's side wall, collecting chamber connects working chamber behind the side of closing hatch door, closing hatch door opening with collecting chamber, is fixed on receipts The indoor drive device of collection matches with coldplate, and when closing hatch door open mode, drive device driving coldplate is transferred to molten Room or collecting chamber are refined, the screeding device and coldplate for being arranged on collecting chamber match, when coldplate is moved to collecting chamber, scraper plate Device contacts with coldplate, strikes off the silicon deposited on coldplate.
- 2. the device according to claim 1 for preparing high-purity nm polycrysalline silcon, it is characterised in that：The coldplate bag Hollow plate body, cooling medium entrance, cooling medium outlet, through hole are included, running through of running through up and down is provided among hollow plate body Hole, one end of hollow plate body are provided with cooling medium entrance and cooling medium outlet；Hollow plate body is resistant to elevated temperatures gradient function Material is made, i.e., hollow plate body is at least two layers from the inside to the outside, and the thermal expansion coefficient of inner layer material is less than cladding material Thermal expansion coefficient.
- 3. the device according to claim 2 for preparing high-purity nm polycrysalline silcon, it is characterised in that：The screeding device Including support bar, upper folder, motion bar, lower folder, one end of support bar, which is arranged on, is collected in chamber interior walls, and the other end of support bar is set Have a telescopic movable rod, the both ends of motion bar are respectively arranged with folder and lower folder, upper folder and lower folder folder positioned at hollow plate body up and down With hollow plate body upper surface during both sides, i.e. upper folder clamping, contacted with hollow plate body lower surface during lower folder clamping, the cooling Collection system also includes collecting crucible, and the upper shed and hollow plate shape for collecting crucible match, and collects crucible and is located at scraper plate Device bottom, the silicon that access screeding device is collected on the cooling plate；The drive device includes drive rod, chute, grasping plate structure, Chute is arranged on collection chamber interior walls, and one end of drive rod is provided with grasping plate structure, and grasping plate structure engages with chute, and grasping plate structure One end matches with coldplate, i.e., grasping plate structure catches one end of coldplate, and drive rod driving grasping plate structure is moved in chute.
- 4. the device according to claim 3 for preparing high-purity nm polycrysalline silcon, it is characterised in that：The working chamber and The side wall of collecting chamber is that centre is provided with water-cooling sandwich；The collection crucible is bilayer zone water made of steel or copper product Air-cooled structure, and recirculated cooling water is provided between bilayer, collect inner surface of crucible and scribble thin layer silicon nanoparticle, collect crucible Bore is 400~600mm；The coldplate also includes dividing plate, cooling water, and space hollow in hollow sheeting body is divided into by dividing plate One zigzag path turned back, the both ends of zigzag path are cooling medium entrance and cooling medium outlet, and cooling water exists Circulated in the path that hollow plate body dividing plate is formed, coldplate is 300~500mm of diameter circular slab, through hole among coldplate Aperture be 50~200mm.
- 5. the device according to claim 4 for preparing high-purity nm polycrysalline silcon, it is characterised in that：The collecting chamber bag Include internal protecting wall, outer furnace wall, middle interlayer, path dividing plate, cold water inlet, go out cold water outlet, internal protecting wall and outer furnace wall are steel materials It is made, and one layer of nano silica fume coating is provided with the inside of internal protecting wall, is arranged on the internal protecting wall of internal layer and is arranged on the outer stove of outer layer There is middle interlayer between wall, the top of middle interlayer is provided with cold water inlet and goes out cold water outlet, and path dividing plate is in helical spiral of turning back In middle interlayer, the path for downward spiral of being turned back after one spiral of formation is upward, the both ends of spiral channel are cold water inlet respectively With go out cold water outlet；The cooling collection system also includes the guide rail being arranged in working chamber, and guide rail is fixed with melting chamber interior walls to be connected Connect, guide rail matches with coldplate, and guide rail includes left recessed groove, right groove and disk roller, and left recessed groove and right recessed groove are relative, left Bottom in recessed groove and right recessed groove is provided with disk roller, and the both sides of coldplate are placed in left recessed groove and right recessed groove respectively On disk roller, and slided in left recessed groove and right recessed groove.
- 6. the device for preparing high-purity nm polycrysalline silcon according to any one in Claims 1 to 5, its feature exist In：The electronic torch melting system also include silicon material entrance, melting kettle, solid-liquid baffle plate, overfall, electron gun, accept crucible, Aqueous cold plate, mobile melting kettle device, transfer and accept crucible device, adsorption plate, observation window, working chamber includes inwall, outer wall, folder Layer, division board, water inlet, delivery port, inner and outer wall is made of steel material, and inner wall is provided with one layer of nano-silicon Powder coating, be arranged on the inwall of internal layer and be arranged on outer layer outer wall between have an interlayer, the top of interlayer be provided with water inlet and Delivery port, division board spiral in interlayer in double-layer spiral shape, the path for downward spiral of being turned back after one spiral of formation is upward, lead to The both ends on road are water inlet and delivery port respectively；Observation window, observation window connection working chamber inside and the external world are provided with working chamber； Upper wall in working chamber is provided with adsorption plate, and adsorption plate is the heat-resistance stainless steel net of high density mesh；The top of working chamber is set Silicon material entrance is equipped with, the melting kettle being arranged in working chamber matches with silicon material entrance, and electron gun is fixed on working chamber top, Electron gun corresponds with melting kettle and undertaking crucible, and electron gun is located at melting kettle and accepts the top of crucible, melting It is provided with solid-liquid baffle plate in crucible, the inner wall sealing of top half is fixed in the both ends of solid-liquid baffle plate and melting kettle, and solid-liquid There is silicon liquid path between the bottom of baffle plate and melting kettle, melting kettle is isolated into dress silicon material part and dress silicon by solid-liquid baffle plate Liquid part, the side of melting kettle dress silicon liquid part are provided with overfall, accept the side that crucible is arranged on overfall, overfall Match with accepting crucible, i.e., the silicon liquid in melting kettle is flowed into by overfall and accepted in crucible, accepts crucible inner bottom part Aqueous cold plate is provided with, the cooling medium for having circulation in aqueous cold plate；Melting kettle and undertaking crucible are all bilayer zone water-cooling structures Copper crucible, and recirculated cooling water is provided between bilayer；Mobile melting kettle device includes melting kettle base, pulley, movement Bar, melting kettle are placed on melting kettle base, and melting kettle base bottom is provided with pulley, mobile bar and melting kettle Base is fixedly connected；Transferring undertaking crucible device includes elevating lever and tray, and elevating lever is fixed on undertaking tray bottom, tray On put undertaking crucible, elevating lever drives the undertaking crucible on tray to rise or fall；The cooling collection system also includes It is arranged on the dodge gate of collecting chamber side wall.
- A kind of 7. method for preparing high-purity nm polycrysalline silcon, it is characterised in that comprise the following steps：Electronic torch melting prepares vapor deposited silicon：Solid-state silicon is fused into silicon liquid using the electron beam that electron gun is sent, continues to allow High-power electron beam is beaten in surface of the silicon liquid so that and silicon liquid is gasificated into gas-phase silicon, and gas-phase silicon deposits on the cooling plate after running into coldplate, The silicon deposited on the cooling plate is scraped, obtains vapor deposited silicon.
- 8. the method according to claim 7 for preparing high-purity nm polycrysalline silcon, it is characterised in that：The electron beam melts Refining standby vapor deposited silicon step is specially：Added into working chamber in melting kettle and account for consolidating for melting kettle capacity 1/3rd State silicon, it is 10 by force in melting intraventricular pressure-4~10-3Pa, melting indoor temperature are more than under conditions of 2273K, directly over melting kettle Electron gun preheat first, to obtaining high pressure and after stablizing electron beam, scan the solid-state silicon in melting kettle, and increase electron gun Power, lasting scanning, solid-state silicon is fused into silicon liquid；Then solid-state silicon, electronics are added into melting kettle from silicon material entrance Beam continues to scan on solid-state silicon, and solid-state silicon is melted into silicon liquid；Silicon liquid in melting kettle is flowed out to by overfall to be accepted in crucible, The electron gun directly over crucible is accepted to preheat first, to after obtaining high pressure and stablize electron beam, the silicon liquid in crucible is accepted in scanning, And increase the power of electron gun, lasting scanning, silicon liquid is gasificated into gas-phase silicon, gas-phase silicon volatilization, and deposited after running into coldplate On the cooling plate, the collection intraventricular pressure of working chamber's isolation hatch door opposite side is 10 by force-4~10-3Pa, when coldplate is collected into setting Between after, open isolation hatch door, coldplate be transferred to collecting chamber by working chamber using drive device, isolation hatch door is closed, uses Screeding device scrapes the silicon deposited on the cooling plate to collecting in crucible, then opens isolation hatch door, will using drive device Coldplate is transferred to working chamber by collecting chamber, closes isolation hatch door, and gas-phase silicon continues to be deposited on cooling after volatilization runs into coldplate On plate, so volatilized completely to the silicon liquid accepted in crucible repeatedly, electron gun is stopped, and treats the pressure in working chamber and collecting chamber By force close to normal pressure, and in working chamber and collecting chamber during temperature near room temperature, taken out from dodge gate and collect crucible, be vapor-deposited Silicon.
- 9. the method for preparing high-purity nm polycrysalline silcon according to any one in claim 7~8, its feature exist In further comprising the steps of：Ball mill prepares nano particle：The spheroidal graphite tank of ball mill is poured into after obtained vapor deposited silicon is mixed with ball-milling medium In, obtain the mixture of nano silicon particles and ball-milling medium；Separate silicon grain：The mixture of obtained nano silicon particles and ball-milling medium and water are thoroughly mixed, are subsequently placed in It is ultrasonically treated in ultrasound environments, removes the silicon grain for being deposited in bottom, take the silicon water mixed liquid on top, that is, obtain silicon water and mix Close liquid；Obtain silicon grain：Obtained silicon water mixed liquid is centrifuged, collects sediment, puts the precipitate in vacuum drying chamber and does It is dry, obtain high-purity nm silicon grain.
- 10. the method according to claim 9 for preparing high-purity nm polycrysalline silcon, it is characterised in that：Ball mill prepares nano particle：The vapor deposited silicon of one mass parts is mixed with the ball-milling medium of three mass parts, after pour into In the spheroidal graphite tank of planetary ball mill, ball milling 16~24 hours, the mixture of nano silicon particles and ball-milling medium is obtained.Separate silicon grain：The mixture of the nano silicon particles of 1 mass parts and ball-milling medium is mixed with the water of 50~200 mass parts And be sufficiently stirred, it is 70% to be subsequently placed in ultrasonic power, and temperature is to carry out 10~30 points of supersound process in 25 DEG C of ultrasound environments Clock, persistently stir during supersound process, stop stirring after supersound process, staticly settle at least 15 minutes, take the silicon water on top to mix Liquid is closed, gives up the bulky grain silicon grain for being deposited in bottom, that is, obtains silicon water mixed liquid；Obtain silicon grain：Obtained silicon water mixed liquid is centrifuged, centrifugal rotational speed 9000-11000r/min, centrifugation time 10 ~20min, sediment is collected, put the precipitate in 130~150 DEG C of vacuum drying chambers and dry at least 2 hours, it is small to obtain particle diameter In 500nm, and D50≤ 100nm high-purity nm silicon grain.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07309614A (en) * | 1994-03-24 | 1995-11-28 | Kawasaki Steel Corp | Method for purifying silicon |
| CN101708850A (en) * | 2009-11-19 | 2010-05-19 | 大连理工大学 | Method and device for removing phosphorus and boron in polysilicon by continuous smelting |
| CN102120579A (en) * | 2011-01-29 | 2011-07-13 | 大连隆田科技有限公司 | Method and device for efficiently and continuously smelting and purifying polysilicon with electron beams |
| CN102126726A (en) * | 2011-01-29 | 2011-07-20 | 大连隆田科技有限公司 | Method and equipment for efficiently purifying polysilicon powder by utilizing electron beams |
| CN102259866A (en) * | 2011-06-09 | 2011-11-30 | 宁夏银星多晶硅有限责任公司 | Polysilicon purification electron beam smelting high efficiency apparatus |
| WO2012100485A1 (en) * | 2011-01-29 | 2012-08-02 | 大连隆田科技有限公司 | Method and apparatus for smelting and purifying polycrstalline silicon by means of electron beam and shallow melt pool |
| US20130291595A1 (en) * | 2012-05-04 | 2013-11-07 | Korea Institute Of Energy Research | Apparatus for manufacturing high purity polysilicon using electron-beam melting and method of manufacturing high purity polysilicon using the same |
| CN207313146U (en) * | 2017-10-09 | 2018-05-04 | 宁夏东梦能源股份有限公司 | Efficiently prepare the device of high-purity vapor deposited silicon |
-
2017
- 2017-10-09 CN CN201710928955.7A patent/CN107673356A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07309614A (en) * | 1994-03-24 | 1995-11-28 | Kawasaki Steel Corp | Method for purifying silicon |
| CN101708850A (en) * | 2009-11-19 | 2010-05-19 | 大连理工大学 | Method and device for removing phosphorus and boron in polysilicon by continuous smelting |
| WO2011060717A1 (en) * | 2009-11-19 | 2011-05-26 | 大连理工大学 | Method and apparatus for removing phosphorus and boron from polysilicon by continuously smelting |
| CN102120579A (en) * | 2011-01-29 | 2011-07-13 | 大连隆田科技有限公司 | Method and device for efficiently and continuously smelting and purifying polysilicon with electron beams |
| CN102126726A (en) * | 2011-01-29 | 2011-07-20 | 大连隆田科技有限公司 | Method and equipment for efficiently purifying polysilicon powder by utilizing electron beams |
| WO2012100485A1 (en) * | 2011-01-29 | 2012-08-02 | 大连隆田科技有限公司 | Method and apparatus for smelting and purifying polycrstalline silicon by means of electron beam and shallow melt pool |
| CN102259866A (en) * | 2011-06-09 | 2011-11-30 | 宁夏银星多晶硅有限责任公司 | Polysilicon purification electron beam smelting high efficiency apparatus |
| US20130291595A1 (en) * | 2012-05-04 | 2013-11-07 | Korea Institute Of Energy Research | Apparatus for manufacturing high purity polysilicon using electron-beam melting and method of manufacturing high purity polysilicon using the same |
| CN207313146U (en) * | 2017-10-09 | 2018-05-04 | 宁夏东梦能源股份有限公司 | Efficiently prepare the device of high-purity vapor deposited silicon |
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