CN209276166U - A kind of high purity polycrystalline silicon purifying plant for solar battery - Google Patents
A kind of high purity polycrystalline silicon purifying plant for solar battery Download PDFInfo
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- CN209276166U CN209276166U CN201821901378.9U CN201821901378U CN209276166U CN 209276166 U CN209276166 U CN 209276166U CN 201821901378 U CN201821901378 U CN 201821901378U CN 209276166 U CN209276166 U CN 209276166U
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- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 215
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 215
- 239000010703 silicon Substances 0.000 claims abstract description 215
- 239000007788 liquid Substances 0.000 claims abstract description 182
- 230000003647 oxidation Effects 0.000 claims abstract description 72
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 72
- 238000007670 refining Methods 0.000 claims abstract description 37
- 239000002893 slag Substances 0.000 claims abstract description 37
- 239000012535 impurity Substances 0.000 claims abstract description 34
- 230000008018 melting Effects 0.000 claims abstract description 34
- 238000002844 melting Methods 0.000 claims abstract description 34
- 238000007711 solidification Methods 0.000 claims abstract description 27
- 230000008023 solidification Effects 0.000 claims abstract description 27
- 230000015271 coagulation Effects 0.000 claims abstract description 19
- 238000005345 coagulation Methods 0.000 claims abstract description 19
- 238000010894 electron beam technology Methods 0.000 claims abstract description 12
- 229920005591 polysilicon Polymers 0.000 claims abstract description 10
- 238000007872 degassing Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 99
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 48
- 238000003860 storage Methods 0.000 claims description 31
- 229910052786 argon Inorganic materials 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 230000005674 electromagnetic induction Effects 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 5
- 239000011819 refractory material Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 3
- 229910052571 earthenware Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052796 boron Inorganic materials 0.000 abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 8
- 239000011574 phosphorus Substances 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 230000001429 stepping effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- -1 calcirm-fluoride Inorganic materials 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000017105 transposition Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
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- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 238000005070 sampling Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Abstract
The utility model belongs to semiconductor material preparation field, and in particular to a kind of high purity polycrystalline silicon purifying plant for solar battery, comprising: melting slag making device, ladder dephosphorization apparatus, step-by-step oxidation device and refining coagulation system.Silicon liquid after slag making cleans, into ladder dephosphorization apparatus, when silicon liquid is flowed out from silicon liquid chute mouth, is bombarded the silicon liquid flowed out from notch with the high-power electron beam of electron gun, to quickly remove the phosphorus impurities in silicon liquid by the utility model.With different concise gas stepping actions in step-by-step oxidation device, remove boron impurities, the carbon, metal impurities in silicon liquid, again by degassing after concise, directional solidification, cut off the high impurity part of silicon ingot, the solar-grade polysilicon product of high-purity is obtained, realizes the continuous industrial production of high purity polycrystalline silicon.
Description
Technical field
The utility model belongs to semiconductor material preparation field, and in particular to a kind of High Purity Polycrystalline for solar battery
Silicon purifying plant.
Background technique
High purity polycrystalline silicon is the important intermediate products in silicon product industrial chain, is to manufacture silicon polished, solar battery
Primary raw material.For integrated circuit industry, high purity polycrystalline silicon is the direct material for producing monocrystalline silicon, is the present age artificial intelligence
The electronics and information infrastructure material of the semiconductor devices such as energy, automatic control, information processing, photoelectric conversion.
Although polycrystalline silicon industry starting in China's is not late, since production technology mostly uses traditional Siemens Method, production scale
Small, technical level is low, and technique is outmoded, and equipment is poor, and labor productivity is low, leads to low output, material consumption, energy consumption are high, raw material
Comprehensive utilization degree is poor, and product cost is high, and quality, which is difficult to ensure, has compared larger gap with world level.
Polysilicon mainly uses chemical purification to produce at present.Chemical purification methods mainly have Siemens Method (gaseous phase deposition
Reaction method), monosilane thermal decomposition method, fluidization bed process, capital fund threshold and technical requirements are relatively high.In chemical purification
Method produces in polysilicon process, can generate a large amount of chloride and silane, and to the seriously polluted of environment, and energy consumption is also very big,
High production cost.Therefore, in recent years, solar level is directly prepared from metallurgical grade industrial silicon using the metallurgical preparation method of low cost
The method of high purity polycrystalline silicon has obtained extensive research.
Utility model content
The purpose of this utility model is the presence of the above problem in view of the prior art, proposes that a kind of speed of melting is fast, removes
It is miscellaneous it is convenient and efficient, can be realized that continuous production, directly to prepare solar level high-purity suitable for the slave metallurgical grade industrial silicon of industrialization
The purifying plant of polysilicon.
The purpose of this utility model can be realized by the following technical scheme: a kind of High Purity Polycrystalline for solar battery
Silicon purifying plant, including,
Melting slag making device, the middle part is provided with electromagnetic induction heater, equipped with molten inside the electromagnetic induction heater
Crucible is refined, is provided with silicon feeder and slag former feeder above the melting kettle, the crucible bottom is provided with the first silicon
The melting slag making bottom of device of liquid switch, the first silicon liquid switch lower section is provided with the first valve；
Ladder dephosphorization apparatus is set to below melting slag making device, is provided with the first storage immediately below first valve
Slot, first sump bottom are provided with the second silicon liquid switch, and the second silicon liquid switch lower section is provided with successively arranges obliquely
Several silicon liquid chutes of column, the silicon liquid chute are obliquely installed and are respectively arranged with electronics in each silicon liquid outflow direction side
Rifle, is provided with the second storage tank for receiving temporary silicon liquid below the ladder dephosphorization apparatus, and second sump bottom is provided with the
The ladder dephosphorization apparatus bottom of three silicon liquids switch, third silicon liquid switch lower section is provided with the second valve；
Step-by-step oxidation device is set to below ladder dephosphorization apparatus, and it is different that band is provided in the distribution oxidation unit
The firstth area, the secondth area, third area and the 4th area of refinery gas are provided with several in the step-by-step oxidation device for loading
Silicon liquid carries out oxidation oxidation crucible, and the oxidation crucible passes through the firstth area, the secondth area and third area in order and aoxidized, described
Second valve is set to above the firstth area, and the step-by-step oxidation bottom of device below the 4th area is provided with third valve；
Coagulation system is refined, is set to below step-by-step oxidation device, the refining coagulation system side is connected to third valve
Door, the third valve lower section is provided with moveable refining copple and the bottom of other side refining coagulation system is provided with orientation
Bed die is solidified, the refining copple bottom is provided with refinery gas nozzle, and the refining copple refines after silicon liquid reaches quantitative
Crucible is moved into above directional solidification bed die, and the directional solidification bed die lower section, which is provided with to drive, solidifies what bed die moved down
Pull ring system；
Metallurgical grade silicon cleans via slag making removal of impurities, ladder dephosphorization, step-by-step oxidation and degassing refining, directional solidification, by silicon ingot
High impurity part cut off to obtain solar-grade polysilicon.
In a kind of above-mentioned high purity polycrystalline silicon purifying plant for solar battery, the melting slag making device, rank
Terraced dephosphorization apparatus, step-by-step oxidation device and being respectively set for coagulation system of refining are communicated with vacuum system.
In a kind of above-mentioned high purity polycrystalline silicon purifying plant for solar battery, setting at the top of the melting kettle
There is sampler.
In a kind of above-mentioned high purity polycrystalline silicon purifying plant for solar battery, the melting kettle and electromagnetism sense
It answers and is provided with refractory material between heater, the refractory material bottom is provided with consent to be opened/closed, and the consent can be with
One silicon liquid switch is connected.
In a kind of above-mentioned high purity polycrystalline silicon purifying plant for solar battery, setting on the outside of first storage tank
There is the first heating and heat-insulating device, is provided with the second heating and heat-insulating device below the silicon liquid chute.
In a kind of above-mentioned high purity polycrystalline silicon purifying plant for solar battery, the silicon liquid chute be set as to
Lower 10-30 ° of inclination.
In a kind of above-mentioned high purity polycrystalline silicon purifying plant for solar battery, the electron beam light of the electron gun
Spot diameter is greater than silicon liquid flow diameter.
In a kind of above-mentioned high purity polycrystalline silicon purifying plant for solar battery, it is provided with above firstth area
First plasma gun is the mixed gas of argon gas and oxygen in first plasma gun, and the is provided with above secondth area
Two plasma guns, the interior mixed gas for argon gas and chlorine of second plasma gun, the third area top are provided with third
Plasma gun, the interior mixed gas for argon gas and vapor of the third plasma gun, the 4th area top are provided with the 4th
Plasma gun, the interior mixed gas for argon gas, vapor and hydrogen of the 4th plasma gun.
In a kind of above-mentioned high purity polycrystalline silicon purifying plant for solar battery, firstth area, the secondth area,
3rd area and the distribution of the 4th Qu Chengtian word, the step-by-step oxidation device are provided centrally with rotational structure, set on the rotational structure
Set connection there are four oxidation crucible and each oxidation crucible can by rotate successively pass through the firstth area, the secondth area, third area and
4th area.
In a kind of above-mentioned high purity polycrystalline silicon purifying plant for solar battery, the 4th area is arranged in side
There is the manipulator for crucible overturning will to be aoxidized.
The utility model by silicon liquid after slag making cleans, into ladder dephosphorization apparatus, when silicon liquid is flowed out from silicon liquid chute mouth
When, the silicon liquid flowed out from notch is bombarded with the high-power electron beam of electron gun, to quickly remove the phosphorus impurities in silicon liquid.Dividing
It walks in oxidation unit with different concise gas stepping actions, removes boron impurities, carbon, metal impurities in silicon liquid, then pass through
After the concise, directional solidification that deaerates, the high impurity part of silicon ingot is cut off, obtains the solar-grade polysilicon product of high-purity, is realized
The continuous industrial production of high purity polycrystalline silicon.
Detailed description of the invention
Fig. 1 is the apparatus structure total figure schematic diagram of the utility model；
Fig. 2 is the melting slag making apparatus structure schematic diagram of the utility model；
Fig. 3 is the ladder dephosphorization apparatus structural schematic diagram of the utility model；
Fig. 4 is the step-by-step oxidation apparatus structure schematic diagram of the utility model；
Fig. 5 is the concise coagulation system structural schematic diagram of the utility model.
Such as figure, melting slag making device 100, electromagnetic induction heater 110, melting kettle 120, silicon feeder 130, slag former
Feeder 140, sampler 150, the first silicon liquid switch 160, the first valve 170, refractory material 180, consent 190, ladder dephosphorization
Device 200, the first storage tank 210, the second silicon liquid switch 211, the first heating and heat-insulating device 212, silicon liquid chute 220, the second heating
Attemperator 221, electron gun 230, the second storage tank 240, third silicon liquid switch 241, the second valve 250, step-by-step oxidation device
300,310 first plasma gun 311 of the firstth area, the second area 320, the second plasma gun 321,330 third plasma gun of third area
331, the 4th area 340, the 4th plasma gun 341 aoxidizes 350 rotational structure 360 of crucible, manipulator 370, third valve 380, essence
Refine coagulation system 400, refining copple 410, refinery gas nozzle 411, directional solidification bed die 420, pull ring system 421, vacuum system
System 500.
Specific embodiment
It is specific embodiment of the utility model and in conjunction with attached drawing below, the technical solution of the utility model is made further
Description, but the utility model is not limited to these examples.
As Figure 1-Figure 5, a kind of high purity polycrystalline silicon purifying plant for solar battery, comprising: melting slag making dress
100, ladder dephosphorization apparatus 200, step-by-step oxidation device 300 and refining coagulation system 400 are set, four part-structures constitute a set of complete
Whole high purity polycrystalline silicon purification system, can be realized metallurgical grade silicon to solar-grade high-purity polycrystalline silicon continuous industrial production.
It is provided with electromagnetic induction heater 110 in the middle part of melting slag making device 100, is equipped with inside electromagnetic induction heater 110
Melting kettle 120 is provided with silicon feeder 130 and slag former feeder 140 above melting kettle 120, and crucible bottom is provided with
100 bottom of melting slag making device of first silicon liquid switch 160,160 lower section of the first silicon liquid switch is provided with the first valve 170.
Technical grade silicon blocks of solid or powder are added in melting kettle 120 by silicon feeder 130, pass through electromagnetism sense
Answer heater 110 to heat silicon material, the frequency of electromagnetic induction heater 110 is 500-100000Hz, melting silicon materials at
Liquid-state silicon.Silicon liquid temperature is gradually warming up to 1600-2000 DEG C, keeps the temperature 10-120 minutes, during which according to the sampling point of sampler 150
As a result, adjusting the dosage and ingredient of slag former, slag former is added in the silicon liquid of melting by slag former feeder 140 for analysis.Slag making
The ingredient of agent is calcium oxide, calcirm-fluoride, strontium oxide strontia and silica, weight ratio 2-4:1-2:0-1:2-4, the total amount of slag former
For the 5-50% of silicon liquid.
The temperature of holding system is 1600-2000 DEG C, adjusts the frequency of electromagnetic induction coil, sufficiently agitation silicon liquid, makes silicon
Phosphorus, boron and metal impurities in liquid are dissolved in slag former, after the reaction was completed, open consent 190 and the first silicon liquid switch 160,
Silicon liquid is flowed out from melting kettle 120, is transferred in the first storage tank 210 in ladder dephosphorization apparatus 200.
Ladder dephosphorization apparatus 200 is set to the lower section of melting slag making device 100, and the is provided with immediately below the first valve 170
One storage tank 210,210 bottom of the first storage tank are provided with the second silicon liquid switch 211, and 211 lower section of the second silicon liquid switch is provided with successively
Several silicon liquid chutes 220 arranged obliquely, silicon liquid chute 220 are obliquely installed and distinguish in each silicon liquid outflow direction side
It is provided with electron gun 230, the second storage tank 240 for receiving temporary silicon liquid, the second storage tank are provided with below ladder dephosphorization apparatus 200
240 bottoms are provided with third silicon liquid switch 241, and 200 bottom of ladder dephosphorization apparatus of 241 lower section of third silicon liquid switch is provided with the
Two valves 250.
There is the first heating and heat-insulating device 212 outside first storage tank 210, the first heating and heat-insulating device 212 can be intermediate frequency or height
Frequency induction heating, is also possible to resistance heating, and silicon liquid temperature is made to be maintained at 1600-2000 DEG C.Height is obtained by vacuum system 500
Vacuum keeps vacuum degree in 10-1 to 10-5Pa, opens the second silicon liquid switch 211, silicon liquid is made to flow into silicon liquid from the first storage tank 210
In chute 220, there is the second heating and heat-insulating device 221 around silicon liquid chute 220, keep silicon liquid temperature between 1500-2000 DEG C,
Silicon liquid chute 220 keeps down 10-30 ° of inclination angle, guarantees that silicon liquid smooth can flow through silicon liquid chute 220.The second silicon liquid is adjusted to open
211 opening and closing degree is closed, can control the flow of silicon liquid, silicon liquid flows to following silicon liquid chute 220 from silicon liquid chute 220 above
In, it finally flows into the second storage tank 240.
Electron gun 230 is equipped between two silicon liquid chutes 220.When silicon liquid is from the 220 mouthfuls of outflows of silicon liquid chute, height is started
Energy electron gun 230 adjusts electron beam spot diameter and is slightly larger than silicon liquid flow diameter, and high-power electron beam bombards the silicon flowed out from notch
Liquid, to quickly remove the phosphorus impurities in silicon liquid, the phosphorus impurities gas evaporated is discharged by vacuum system 500.
In order to reinforce phosphor-removing effect, settable multiple silicon liquid chutes 220 and high energy electron rifle 230, make silicon liquid with shallow bid
It is repeatedly bombarded and thorough dephosphorization by high-power electron beam during line flowing.Silicon liquid after dephosphorization finally flows into the second storage tank 240
In, the furnace space where the second storage tank 240 is as small as possible, and it is relatively independent, it is around provided with heat insulation system, passes through vacuum
System 500 adjusts internal vacuum degree.
The method that traditional metallurgy method removes phosphorus impurities in silicon liquid is to be provided with a certain number of silicon liquids in a crucible, from silicon
Exhausted big portion in silicon liquid and crucible above liquid using high-power electron beam bombardment silicon liquid and after dephosphorization, with the direct contact dephosphorization of electron beam
The advantages of point not the silicon liquid of dephosphorization does not mix rapidly in crucible, leads to the poor effect of whole system dephosphorization, the present apparatus is silicon
After one or many high-power electron beams bombard dephosphorization, silicon liquid can never mix liquid with the silicon liquid of non-dephosphorization in former crucible,
Therefore dephosphorization speed is fast, and high-efficient, effect is good.The phosphorus impurities concentration in Industrial Metal silicon can be reduced to by this technique
0.02ppm or less.
Step-by-step oxidation device 300 is set to 200 lower section of ladder dephosphorization apparatus, is distributed in oxidation unit and is provided with band not
With the first area 310 of refinery gas, the second area 320, third area 330 and the 4th area 340, it is provided in step-by-step oxidation device 300
Several carry out oxidation oxidation crucible 350 for loading silicon liquid, and oxidation crucible 350 passes through the first area 310, the secondth area in order
320 and third area 330 aoxidized, the second valve 250 is set to the top of the firstth area 310, the step-by-step oxidation of 340 lower section of the 4th area
300 bottom of device is provided with third valve 380.
There is an oxidation crucible 350 in each area, they can be by the effect of rotational structure 360 along clockwise or inverse
Clockwise rotation.Each crucible can fill 0.5-5 kilograms of silicon liquid, have thermal insulation material outside crucible, provide heat by high-temperature plasma
Source, can also be used electromagnetic induction heating or resistance heating heat preservation, silicon liquid temperature are maintained at 1450-2000 degree.
From the oxidation crucible 350 that the silicon liquid being transferred out of in the second storage tank 240 flows into the first area 310, when the first area 310
Silicon liquid amount in small crucible reaches in advance when requiring, and starts rotational structure 360, so that four oxidation crucibles 350 is made 90 degree and rotate, this
When the first area 310 oxidation crucible 350 rotate to the second area 320, the oxidation crucible 350 in the second area 320 rotates to third area
330, the oxidation crucible 350 in third area 330 rotates to the 4th area 340, successively transposition, and the silicon liquid in the 4th area 340 is transferred to
Concise coagulation system, empty oxidation crucible 350 enter the first area 310, receive ladder dephosphorization apparatus 200 again and are transferred into the silicon come
Liquid, so circulation are operated.
There is a plasma gun above each area, four areas.It is the first plasma gun 311 above first area 310, the
Gas in one plasma gun 311 is the mixed gas of argon gas and oxygen, and wherein the volume ratio of oxygen is 0.1-3%, gaseous mixture
Body flow is 2-100L/min, and gas enters the oxidation crucible in the first area 310 after heating and ionize by the first ion gun
350, handle silicon liquid, working time 1-60min.The purpose that oxygen is added be make boron impurities, carbon and part iron in silicon liquid,
The metal impurities such as manganese, aluminium, titanium are oxidized to corresponding oxide；It is the second plasma gun 321 above the second area 320, second etc.
Gas in ion gun 321 is the mixed gas of argon gas and chlorine, and wherein the volume ratio of chlorine is 0.5-10%, mixed gas stream
Amount is 2-100L/min, and gas enters the oxidation crucible in the second area 320 after heating and ionize by the second plasma gun 321
350, handle silicon liquid, working time 1-60min.The purpose that chlorine is added is to remove the light metals impurity such as aluminium, calcium in silicon liquid；
It is third plasma gun 331 above third area 330, the gas in third plasma gun 331 is the mixing of argon gas and vapor
Gas, wherein the volume ratio of vapor is 5-20%, mixed gas flow 2-100L/min, and gas added by third ion gun
Enter the oxidation crucible 350 in third area 330 after heat and ionization, handles silicon liquid, working time 1-60min.Water is added to steam
The purpose of gas is further boron impurities, carbon and the metal impurities removed in silicon liquid；It is the 4th plasma gun above the 4th area 340
341, the gas in the 4th plasma gun 341 is the mixed gas of argon gas, vapor and hydrogen, and wherein the volume ratio of vapor is
1-10%, the volume ratio of hydrogen are 10-50%, mixed gas flow 2-100L/min, and gas passes through the heating of the 4th ion gun
And enter the oxidation crucible 350 in the 4th area 340 after ionizing, handle silicon liquid, working time 1-60min.Addition contains water
The hydrogen of steam is the impurity such as the further trace impurity boron removed in silicon liquid, carbon, while hydrogen can also protect silicon liquid
Oxidation reduces the oxygen content in silicon liquid.After the silicon liquid in the 4th area 340, which is handled, to be completed, manipulator 370 is pulled, is handled well
Silicon liquid poured into concise coagulation system via third valve 380.
Pressure control in step-by-step oxidation device 300 is adjusted by vacuum system 500 and is pressed within the scope of 1000-80000Pa
Power is also discharged by vacuum system 500 at any time by the gas that plasma gun is sent into, can be abundant using this technology and device
Remove the impurity in silicon liquid, the especially impurity such as boron, carbon.Boron impurity concentration in Industrial Metal silicon can be reduced to by the technology
0.1ppm or less.
Coagulation system 400 is refined, is set to the lower section of step-by-step oxidation device 300, refining 400 side of coagulation system connection the
Three valves 380 are provided with the bottom of moveable refining copple 410 and other side refining coagulation system 400 below third valve 380
Portion is provided with directional solidification bed die 420, and 410 bottom of refining copple is provided with refinery gas nozzle 411, and refining copple 410 works as silicon
Refining copple 410 is moved into 420 top of directional solidification bed die after liquid reaches quantitatively, and being provided with below directional solidification bed die 420 can
The pull ring system 421 for driving solidification bed die to move down.
Refining copple 410 collect step-by-step oxidation device 300 be transferred into come silicon liquid, keep the temperature of silicon liquid 1450 DEG C with
On, it is passed through gas from the concise gas nozzle of 410 bottom of refining copple, gas componant is high-purity argon gas, gas flow 20-
200L/min.The purpose for being passed through high-purity argon gas gas is to remove other remaining gaseous impurities in silicon liquid.When in refining copple 410
After the amount of silicon liquid reaches requirement, refining copple 410 is pushed into the directional solidification system of side, starts pull ring system 421, it is fixed to drive
It is moved down to solidification bed die 420, realizes directional solidification, remove the metal impurities in silicon, directional solidification speed is 0.1-5mm/
min.According to metal freezing principle, during material crystalline, solute will reallocate, and element of the equilibrium distribution coefficient less than 1 can
To be enriched in final solidified position by directional solidification, the high impurity part of silicon ingot is cut off, the solar energy of high-purity is obtained
Grade polysilicon product.
Embodiment 1
The solid-state silicon for the use of purity being 99.5% is raw material.Solid-state silicon is put into melting kettle 120, electromagnetic induction is started and adds
Hot device 110 melts solid-state silicon, and silicon liquid temperature is warming up to 1650 DEG C, keeps the temperature 30 minutes, and slag former is passed through slag former feeder
140 are added in the silicon liquid of melting, and the ingredient of slag former is calcium oxide, calcirm-fluoride, strontium oxide strontia and silica, weight ratio 2:1:
0.3:3, the total amount of slag former are the 30% of silicon liquid, after the reaction was completed, consent 190 and the first silicon liquid switch 160 are opened, by silicon liquid
It is transferred in the first storage tank 210.
After silicon liquid enters the first storage tank 210, silicon liquid temperature is made to be maintained at 1800 DEG C, keeps vacuum degree on the left side 10-3Pa
The second silicon liquid switch 211 is opened on the right side, flows into silicon liquid in first silicon liquid chute 220 from the first storage tank 210, then from first
Silicon liquid chute 220 flows to second silicon liquid chute 220, finally flows into the second storage tank 240,2 silicon liquid chutes 220 all keep to
Lower 10 ° of inclination angles.
Electron gun is all provided between first storage tank 210 and first silicon liquid chute 220 between two silicon liquid chutes 220
230, high-power electron beam bombards the silicon liquid flowed out from notch, removes the phosphorus impurities in silicon liquid.
Silicon liquid flows into step-by-step oxidation device 300 in the oxidation crucible 350 in the first area 310 from the second storage tank 240, silicon liquid temperature
Degree is maintained at 1600 degree.When the silicon liquid amount in the oxidation crucible 350 in the first area 310 reaches 1 kilogram, rotational structure 360 is started,
The area Shi Sige makees 90 degree of rotations, and the oxidation crucible 350 in the second area 320 rotates to third area 330 at this time, in the second area 320
Oxidation crucible 350 rotates to third area 330, and the oxidation crucible 350 in third area 330 rotates to the 4th area 340, successively mutually transposition
It sets, after the silicon liquid in the 4th area 340 is transferred to concise coagulation system, empty oxidation crucible 350 enters the first area 310, receives again
The silicon liquid come is transferred into from substep dephosphorization apparatus, so circulation is operated.Gas in first plasma gun 311 be argon gas and
The mixed gas of oxygen, wherein the volume ratio of oxygen is 1%, and mixed gas flow 25L/min, gas passes through the first plasma
Rifle 311 enters the oxidation crucible 350 in the first area 310 after heating and ionizing, handle silicon liquid, working time 6min.
Gas in second plasma gun 321 is the mixed gas of argon gas and chlorine, and wherein the volume ratio of chlorine is 2%,
Mixed gas flow is 20L/min, and gas enters in the second area 320 after heating and ionize by the second plasma gun 321
Crucible 350 is aoxidized, silicon liquid, working time 6min are handled.
Gas in third plasma gun 331 is the mixed gas of argon gas and vapor, and wherein the volume ratio of vapor is
10%, mixed gas flow 30L/min, gas enter third area 330 after heating and ionize by third plasma gun 331
Interior oxidation crucible 350 handles silicon liquid, working time 6min.
Gas in 4th plasma gun 341 is the mixed gas of argon gas, vapor and hydrogen, wherein the volume of vapor
Than being 10%, the volume ratio of hydrogen is 40%, mixed gas flow 40L/min, gas heated by the 4th ion gun and from
Enter the oxidation crucible 350 in the 4th area 340 after sonization, handles silicon liquid, working time 6min.
After the silicon liquid in the 4th area 340, which is handled, to be completed, manipulator 370 is pulled, the silicon liquid handled well is poured into concise solidifying
It is fixedly mounted in the refining copple 410 in setting, keeps the temperature of silicon liquid at 1500 DEG C, sprayed from the concise gas of 410 bottom of refining copple
Mouth is passed through high-purity argon gas, gas flow 40L/min.
When the amount of silicon liquid in refining copple 410 is 480 kilograms, refining copple 410 is pushed into the directional solidification system of side
System starts pull ring system 421, drives directional solidification bed die 420 to move down, is oriented solidification, directional solidification speed is
0.5mm/min.It is taken out after silicon ingot is cooling, cuts off 30% high impurity part of silicon ingot, obtain the sun that purity is 99.99998%
It can grade polysilicon product.
Embodiment 2
The solid-state silicon for the use of purity being 98% is raw material.Solid-state silicon is put into melting kettle 120, starts electromagnetic induction heating
Device 110 melts solid-state silicon, and silicon liquid temperature is warming up to 1800 DEG C, keeps the temperature 20 minutes, and slag former is passed through slag former feeder 140
It is added in the silicon liquid of melting, the ingredient of slag former is calcium oxide, calcirm-fluoride, strontium oxide strontia and silica, weight ratio 2:2:
0.2:4, the total amount of slag former are the 50% of silicon liquid, after the reaction was completed, consent 190 and the first silicon liquid switch 160 are opened, by silicon liquid
It is transferred in the first storage tank 210.
After silicon liquid enters the first storage tank 210, silicon liquid temperature is made to be maintained at 1700 DEG C, keeps vacuum degree on the left side 10-3Pa
The second silicon liquid switch 211 is opened on the right side, flows into silicon liquid in first silicon liquid chute 220 from the first storage tank 210, then from first
Silicon liquid chute 220 flows to second silicon liquid chute 220, finally flows into the second storage tank 240.2 silicon liquid chutes 220 all keep to
Lower 15 degree of inclination angle.
Electron gun is all provided between first storage tank 210 and first silicon liquid chute 220 between two silicon liquid chutes 220
230, high-power electron beam bombards the silicon liquid flowed out from notch, removes the phosphorus impurities in silicon liquid.
Silicon liquid flows into step-by-step oxidation device 300 in the oxidation crucible 350 in the first area 310 from the first storage tank 210, silicon liquid temperature
Degree is maintained at 1650 degree.When the silicon liquid amount in the oxidation crucible 350 in the first area 310 reaches 1.5 kilograms, rotational structure is started
360th, Shi Sige area make 90 degree of rotations, and the oxidation crucible 350 in the first area 310 rotates to the second area 320 at this time, in the secondth area
320 oxidation crucible 350 rotates to third area 330, and the oxidation crucible 350 in third area 330 rotates to the 4th area 340, successively
Transposition, after the silicon liquid in the 4th area 340 is transferred to concise coagulation system, empty oxidation crucible 350 enters the first area 310, weight
Newly receive substep dephosphorization apparatus and be transferred into the silicon liquid come, so circulation is operated.Gas in first plasma gun 311 is argon
The mixed gas of gas and oxygen, wherein the volume ratio of oxygen is 1.5%, and mixed gas flow 40L/min, gas passes through first
Plasma gun 311 enters the small crucible in the area a after heating and ionizing, handle silicon liquid, working time 12min.
Gas in second plasma gun 321 is the mixed gas of argon gas and chlorine, and wherein the volume ratio of chlorine is
1.5%, mixed gas flow 25L/min, gas enter in the second area 320 after heating and ionize by the second ion gun
Crucible 350 is aoxidized, silicon liquid, working time 12min are handled.
Gas in third plasma gun 331 is the mixed gas of argon gas and vapor, and wherein the volume ratio of vapor is
12%, mixed gas flow 20L/min, gas enter small in the area c after heating and ionize by third plasma gun 331
Crucible handles silicon liquid, working time 12min.
Gas in 4th plasma gun 341 is the mixed gas of argon gas, vapor and hydrogen, wherein the volume of vapor
Than being 8%, the volume ratio of hydrogen is 35%, and mixed gas flow 30L/min, gas is heated by the 4th plasma gun 341
And enter the oxidation crucible 350 in the 4th area 340 after ionizing, handle silicon liquid, working time 12min.
After the silicon liquid in the 4th area 340, which is handled, to be completed, manipulator 370 is pulled, the silicon liquid handled well is poured into concise solidifying
It is fixedly mounted in the refining copple 410 in setting, keeps the temperature of silicon liquid at 1520 DEG C, sprayed from the concise gas of 410 bottom of refining copple
Mouth is passed through high-purity argon gas, gas flow 30L/min.
When the amount of silicon liquid in refining copple 410 is 480 kilograms, the orientation of 410 pushing in device side of refining copple is coagulated
Gu system starts pull ring system 421, drives directional solidification bed die 420 to move down, be oriented solidification, directional solidification speed
For 1mm/min.It is taken out after silicon ingot is cooling, cuts off 30% high impurity part of silicon ingot, obtain the sun that purity is 99.99995%
It can grade polysilicon product.
The utility model is compact-sized, cleans quick and convenient, and product purity is high, and quality is stablized, and it is continuous to be suitable for industrialization
Production is able to achieve the industrial metaplasia of low cost, large-scale solar-grade high-purity polycrystalline silicon using the production technology and device
It produces.
The specific embodiments described herein are merely examples of the spirit of the present invention.The utility model institute
Belonging to those skilled in the art can make various modifications or additions to the described embodiments or using similar
Mode substitute, but without departing from the spirit of the present application or beyond the scope of the appended claims.
Claims (10)
1. a kind of high purity polycrystalline silicon purifying plant for solar battery characterized by comprising
Melting slag making device is equipped with melting earthenware the middle part is provided with electromagnetic induction heater inside the electromagnetic induction heater
Crucible, the melting kettle top are provided with silicon feeder and slag former feeder, and the crucible bottom is provided with the first silicon liquid and opens
It closes, the melting slag making bottom of device of the first silicon liquid switch lower section is provided with the first valve；
Ladder dephosphorization apparatus is set to below melting slag making device, is provided with the first storage tank, institute immediately below first valve
It states the first sump bottom and is provided with the second silicon liquid switch, successively arranged obliquely if second silicon liquid switch lower section is provided with
Dry silicon liquid chute, the silicon liquid chute are obliquely installed and are respectively arranged with electron gun in each silicon liquid outflow direction side, institute
The second storage tank for being provided with below ladder dephosphorization apparatus and receiving temporary silicon liquid is stated, second sump bottom is provided with third silicon liquid
The ladder dephosphorization apparatus bottom of switch, third silicon liquid switch lower section is provided with the second valve；
Step-by-step oxidation device is set to below ladder dephosphorization apparatus, is provided in the distribution oxidation unit with different refinings
The firstth area, the secondth area, third area and the 4th area of gas are provided with several in the step-by-step oxidation device for loading silicon liquid
Oxidation oxidation crucible is carried out, the oxidation crucible passes through the firstth area, the secondth area and third area in order and is aoxidized, and described second
Valve is set to above the firstth area, and the step-by-step oxidation bottom of device below the 4th area is provided with third valve；
Coagulation system is refined, is set to below step-by-step oxidation device, the refining coagulation system side is connected to third valve, institute
It states and is provided with the bottom of moveable refining copple and other side refining coagulation system below third valve and is provided with directional solidification
Bed die, the refining copple bottom are provided with refinery gas nozzle, refining copple refining copple after silicon liquid reaches quantitatively
It is moved into above directional solidification bed die, the pull ring that solidification bed die can be driven to move down is provided with below the directional solidification bed die
System；
Metallurgical grade silicon cleans via slag making removal of impurities, ladder dephosphorization, step-by-step oxidation and degassing refining, directional solidification, by the height of silicon ingot
Impurity part cuts off to obtain solar-grade polysilicon.
2. a kind of high purity polycrystalline silicon purifying plant for solar battery according to claim 1, which is characterized in that institute
It states melting slag making device, ladder dephosphorization apparatus, step-by-step oxidation device and being respectively set for coagulation system of refining and is communicated with vacuum system
System.
3. a kind of high purity polycrystalline silicon purifying plant for solar battery according to claim 1, which is characterized in that institute
It states and is provided with sampler at the top of melting kettle.
4. a kind of high purity polycrystalline silicon purifying plant for solar battery according to claim 1, which is characterized in that institute
It states and is provided with refractory material between melting kettle and electromagnetic induction heater, the refractory material bottom is provided with plug to be opened/closed
Hole, the consent can be switched with the first silicon liquid to be connected.
5. a kind of high purity polycrystalline silicon purifying plant for solar battery according to claim 1, which is characterized in that institute
It states and is provided with the first heating and heat-insulating device on the outside of the first storage tank, be provided with the second heating and heat-insulating device below the silicon liquid chute.
6. a kind of high purity polycrystalline silicon purifying plant for solar battery according to claim 1, which is characterized in that institute
Silicon liquid chute is stated to be set as tilting down 10-30 °.
7. a kind of high purity polycrystalline silicon purifying plant for solar battery according to claim 1, which is characterized in that institute
The electron beam spot diameter for stating electron gun is greater than silicon liquid flow diameter.
8. a kind of high purity polycrystalline silicon purifying plant for solar battery according to claim 1, which is characterized in that institute
It states and is provided with the first plasma gun above the firstth area, be the mixed gas of argon gas and oxygen in first plasma gun, it is described
It is provided with the second plasma gun above secondth area, is the mixed gas of argon gas and chlorine in second plasma gun, described the
It is provided with third plasma gun above 3rd area, is the mixed gas of argon gas and vapor in the third plasma gun, described the
It is provided with the 4th plasma gun above 4th area, is the mixed gas of argon gas, vapor and hydrogen in the 4th plasma gun.
9. a kind of high purity polycrystalline silicon purifying plant for solar battery according to claim 1, which is characterized in that institute
The firstth area, the secondth area, third area and the distribution of the 4th Qu Chengtian word are stated, the step-by-step oxidation device is provided centrally with rotation knot
Structure, setting connection is there are four oxidation crucible on the rotational structure and each oxidation crucible can be by rotating successively by first
Area, the secondth area, third area and the 4th area.
10. a kind of high purity polycrystalline silicon purifying plant for solar battery according to claim 1, which is characterized in that
4th area is provided with the manipulator for that will aoxidize crucible overturning in side.
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| CN201821901378.9U CN209276166U (en) | 2018-11-19 | 2018-11-19 | A kind of high purity polycrystalline silicon purifying plant for solar battery |
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