CN102616787A - Method for removing boron-phosphorus impurities from silicon metal - Google Patents
Method for removing boron-phosphorus impurities from silicon metal Download PDFInfo
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Abstract
A method for removing boron-phosphorus impurities from silicon metal relates to a silicon metal purifying method. The method includes: firstly, premelting slag charges 2 which are Cao-CaSi2; secondly, pressing slag charges 1 into slag balls, placing part of the slag charges 1 and silicon metal into a crucible, and vacuumizing, starting a medium-frequency induction power source to heat and smelt the materials, wherein the slag charges 1 are SiO2-Na2CO3-CaF2; thirdly, increasing the power of the medium-frequency induction power source to 80kW to 100kW, when the temperature ranges from 1300 DEG C to 1500 DEG C, adding part of slag charges 2 into the crucible, aerating while stirring, continuing to increase the power of the medium-frequency induction power source to 100kW to 120kW, and when the temperature ranges from 1600 DEG C to 1800 DEG C, adding part of slag charges 1 into the crucible, aerating while stirring, lowering the power to 80kW and waiting the temperature to drop; fourthly, repeating the step three; and fifthly, slagging, pouring liquid silicon into a receiving crucible for standing and cooling, taking out silicon ingots, and physically crushing the silicon ingots to obtain purified polycrystalline silicon ingots.
Description
Technical field
The present invention relates to a kind of method of purification of industrial silicon, especially relate to a kind of method that adopts the hydridization slag practice to remove boron and phosphorus matter in the industrial silicon.
Background technology
After 2000, photovoltaic industry presents the trend of an outburst, has totally continued more than 10 year, the about 1787MW of global photovoltaic generation total amount in 2005.Expect the year two thousand fifty, global generating capacity can arrive 18GW.In recent years, the research and development of solar cell are as an important channel of development clean energy, and the raw material that solar cell adopted above 90% is a crystalline silicon, is the waste material from HIGH-PURITY SILICON and electronic-grade silicon, and is with high costs.In order to satisfy growing polysilicon demand, develop a kind of method ten minutes necessity of producing solar energy polycrystalline silicon cheaply.
At present, produce polysilicon and mainly be divided into two kinds of methods: chemical method and physical metallurgy method.Chemical method is promptly improved Siemens Method, silane thermal decomposition process and fluidized bed process, but these method investments are big, and energy consumption is high, and process is complicated and wayward, deals with improperly environment being caused very big pollution like intermediate product.The essence of physical metallurgy method is that the silicon material remains unchanged in purification process, and process such as the metallurgical reaction through impurity, evaporation, fractional condensation is separated and directly obtained solar-grade polysilicon.Process aspect mainly comprises hydrometallurgy (pickling), slag making, directional freeze, high vacuum melting, plasma oxidation refining, alloy directional purification, fused salt electrolysis etc.
Polycrystalline silicon used for solar battery has the comparison strict restriction to the content of non-metallic element B and P, and the content that requires B is below 0.5ppm, and the content of P is below 1ppm.In the directional freeze of routine, B and P other metallic elements relatively have bigger segregation coefficient, still can rest in the solid phase, can't realize refining effect.Consider that P has higher vp, so the present high vacuum melting that adopts has suitable obvious effects for removing P, Xiamen University's metallurgical laboratory is through 1600 ℃ of pilot experiments (15kg level); 0.012 melting silicon 1h under the vacuum tightness of～0.035Pa can be reduced to 0.08ppmw (Zheng Songsheng, old court from 15ppmw with the content of impurity P; Luo Xuetao, the progress of polysilicon metallurgy method dephosphorization, material Leader; 2009,23 (10): 11-14).Mention two an amount of calcium silicides of interpolation in the process of refining solar energy polycrystalline silicon among the U.S. Pat 20110217225Al, melting under argon atmospher can make P be reduced to the solar level standard, and other impurity are also had tangible removal effect.
So far, removing B through slag making is a kind of fairly simple feasible method, the slag making refining mainly be utilize the thermodynamic stability of B oxide compound in slag high (G is low) and make that impurity can more cross be enriched in slag mutually in, thereby realize B from the silicon phase transition to the slag phase.People such as Lynch mention in International Publication No.WO 2007/127126 with slag making and follow-up technologies and remove B and P in the metalluragical silicon, and used slag system is Al
2O
3-SiO
2-CaO-MgO, slag system play the part of a rinse bath that can dissolve B and P, and whole process is led to N
2, generally, silicon needs deoxidation to make that the purifying reaction of B and P is able to carry out, and oxidation refining is carried out subsequently, removes some other impurity through directional freeze at last, is applicable to polycrystalline silicon used for solar battery thereby produce.People such as TEIXEIRA (leandro Augusto Viana TEIXEIRA and Kazuki MORITA, Removal of Boron from Molten Silicon Using CaO-SiO
2Based slags, ISIJ International, 2009,49 (6): 783-787) inquiring into the removal mechanism of B with the Calucium Silicate powder slag system, thereby obtain some more accurate thermodynamic datas, mainly is to L
B(the separation ratio of B) and the activity quotient of boron-oxygen are analyzed, and used slag system is CaO-SiO
2-CaF
2And Na
2O-CaO-SiO
2, the result shows BO
1.5Activity quotient in 0.3～7.0 scope, Na
2The interpolation of O can increase the separation ratio of boron.The people such as M.Barati of Toronto university adopt quaternary slag system Al
2O
3-CaO-MgO-SiO
2With ternary slag system Al
2O
3-BaO-SiO
2Come deeply to inquire into the partition ratio of impurity element B and P, analyze and draw the basicity of slag system and the partition ratio that the oxygen gesture influences them jointly, and these all form relevant with the component of slag system.
Chinese patent CN 1016710239 adopts two kinds and helps slag agent slag making; Heating is worked as the silicon liquid temp and is reached about 1550 ℃; First kind that adds fritting is helped the slag agent; Continue to be warming up to about 1650 ℃, second kind that adds fritting is helped the slag agent, slag making accomplish in the back polysilicon of purifying the content of B impurity below 1ppm.The slag agent of being selected for use usually will meet the following conditions usually: more impurity is avoided in (1); (2) good mobility is provided; (3) lower melt temperature is provided, makes slag keep molten state; (4) help the density of slag agent density and Pure Silicon Metal that certain difference will be arranged; (5) provide enough oxygenant and the B in the silicon liquid fully to react.
Usually the slag system of being studied mainly concentrates on CaO-SiO
2, Na
2O-SiO
2, an amount of interpolation CaF
2Help to reduce the melt temperature of slag system, expand its basicity scope, Al in addition
2O
3As the also frequent component of a kind of neutral oxide as the slag agent.Theoretically, reduce production costs, improve and remove boron efficient, must improve its partition ratio, partition ratio is then closely related with the component of slag agent, so the selection of slag agent is extremely important.
Summary of the invention
The object of the present invention is to provide a kind of method of removing boron and phosphorus matter in the industrial silicon.
The present invention includes following steps:
1) with slag charge 2 fritting, said slag charge 2 is CaO-CaSi
2, by mass percentage, CaO is 40%～70%, CaSi
2Be 30～50%;
2) slag charge 1 is pressed into the slag ball, puts part slag charge 1 and industrial silicon into crucible, vacuumize, open the medium frequency induction power supply heating, make material melting, said slag charge 1 is SiO
2-Na
2CO
3-CaF
2, by mass percentage, SiO
2Be 40%～80%, Na
2CO
3Be 20%～50%, CaF
2Be 5%～20%;
3) power to 80 of rising medium frequency induction power supply～100kW when temperature during at 1300～1500 ℃, joins part slag charge 2 in the crucible; Aeration-agitation continues power to the 100～120kW of rising medium frequency induction power supply, when temperature during at 1600～1800 ℃; Part slag charge 1 is joined in the crucible, and aeration-agitation again reduces power to 80kW; Keep for some time, treat that temperature lowers;
4) repeating step 3);
5) after the slag making silicon liquid poured into and accept crucible, leave standstill the cooling back and take out silicon ingot, the polycrystal silicon ingot that the physics fragmentation obtains purifying.
In step 1), said temperature of dissolving in advance can be 1650～1850 ℃; By mass percentage, CaO can be 50%～60%, CaSi
2Be 40～50%;
In step 2) in, the said slag ball that is pressed into can adopt spherical grinding tool, and the diameter of said slag ball can be 5～20cm; By mass percentage, SiO
2Can be 50%～70%; Na
2CO
3Can be 30%～45%; CaF
2Can be 8%～15%; Said part slag charge 1 can be 1 with the mass ratio of industrial silicon: (10～0.5), and preferred 1: (5～0.5) are preferably 1: (2.5～0.5); Said part slag charge 1 can account for 1/3～1/2 of whole slag charges 1 by mass ratio; The said vacuum tightness that vacuumizes can be below the 450Pa.
In step 3), the gas of said aeration-agitation can be Ar gas, and the time of said aeration-agitation can be kept 1～10min, preferably keeps 2～5min; The gas of said aeration-agitation again can be Cl
2Gas, the time of said aeration-agitation again can be 2～15min, is preferably 3～10min.
In step 4), said multiple number of times can be 3～10 times, is preferably 4～6 times.
In step 5), the time of said slag making can be 20～80min, is preferably 30～60min; The said time of leaving standstill can be 40～60min.
Prepared polycrystal silicon ingot, ICP-MS is adopted in the sampling back, i.e. and plasma inductance coupling spectrometer analysis is measured the content that remains B and P in the silicon.
The slag former partition ratio that the present invention adopted is the highest can to arrive 4; Repeatedly the 2 kinds of different slag systems that add of repeatability are compared with traditional slag practice; Can better arrive the effect of removing P except that B, the silicide in slag charge 2 components is as additive, and it can be good at dissolving P; With P impurity with phosphatic form from silicon, be transferred to slag mutually in, need not adopt high vacuum to remove P and just can phosphorus be dropped to below the content that meets the solar level standard.Adopt this novel slag agent, can the content of B be reduced to 0.4～1ppmw from 10ppmw, P content is reduced to 1～1.8ppmw from 30ppmw.Whole technological operation is simple, and cost is moderate, and is low for equipment requirements, is applicable to suitability for industrialized production.
Embodiment
Embodiment 1
1) slag silicon ratio selects 1: 1, gets slag charge 1:Na
2CO
3(30%wt)-SiO
2(60%wt)-CaF
2(10%wt) 25kg and slag charge 2:CaO (55%)-CaSi
2(45%) 25kg places separately, and slag charge 2 is carried out presmelting, and temperature is controlled at 1700～1850 ℃, and it is the bead of 5cm that slag charge 1 becomes diameter through art breading; The industrial silicon (B in the industrial silicon, the content of P is respectively 10ppmw and 30ppmw) of getting 1/2 slag charge 1 and 50kg mixes and adds in the crucible.
2) be evacuated to vacuum tightness below 500Pa, start the medium frequency induction power supply heating, power increases gradually, and plumbago crucible begins induction heating, and silicon begins fusing;
3) as power to 80～100kW, when temperature is 1300～1500 ℃, a part of slag charge 2 is joined in the crucible through storage hopper, venting pin drops to 3cm place in the liquid, and logical Ar gas mixing is mixed, and stops behind the ventilation 5min;
4) continue rising power to 100～120kW, when temperature is 1600～1800 ℃, a part of slag charge 1 is added in the crucible, begin to the logical Cl of system
2Gas, aeration-agitation, Ventilation Rate is 1L/min, the aeration-agitation time is 5min, reduces power then to 80kW, keeps for some time, treats that temperature lowers.
5) repeating step (3)～(4), multiplicity is 4 times;
6) after the slag making, venting pin is lifted away from crucible, silicon liquid is transferred to accepts plumbago crucible, leaves standstill and treats after its naturally cooling, broken silicon ingot, and B in the silicon, the content of P are measured after the melting through plasma inductance coupling mass spectrograph (ICP-MS) in the sampling back.The about 45min consuming time of whole slagging process records through ICP-MS that B content is 0.5ppmw in the silicon, and P content is 1ppmw.
Embodiment 2: technological process is with embodiment 1, used slag agent components unchanged, and slag charge 1 still is Na
2CO
3(30%wt)-SiO
2(60%wt)-CaF
2(10%wt), slag system 2 is CaO (55%)-CaSi
2(45%); Slag charge 50kg, slag charge 1 and slag charge 2 respectively account for half the, industrial silicon 50kg, and slag charge 1 becomes the bead appearance of 10cm through art breading, and slag charge 2 carries out fritting, and prefusing temperature is controlled at 1800 ℃; Slag charge 1 with 1/2 mixes with industrial silicon to be put in the plumbago crucible, vacuumizes, and starts Frequency Induction Heating; Slowly increase power, during power to 80～100kW, add a part of slag charge 2 and logical Ar gas 3min; Continue rising power to 100～120kW, add a part of slag charge 1, logical Cl
2Gas mixing is mixed and is stopped behind the 5min and reduce power to 80kw, keeps for some time, treats to add power again after temperature lowers; Repeat to add slag charge 2 and slag charge 1 then successively, repeat 5 times, behind the slag making 50min; Smelting furnace liquid is transferred to accepts in the plumbago crucible; Get silicon ingot after leaving standstill cooling, sampling detects to such an extent that B content is 0.65ppmw through ICP-MS, and P content is 1ppmw.
Embodiment 3: technological process is with embodiment 1, and used slag charge 1 is adjusted into Na
2CO
3(40%wt)-SiO
2(50%wt)-CaF
2(10%wt), slag charge 2 is constant still is CaO (55%)-CaSi
2(45%); Slag charge 50kg, slag charge 1 and slag charge 2 respectively account for half the, industrial silicon 50kg, and slag charge 1 becomes the bead appearance of 5cm through art breading, and slag charge 2 carries out fritting, and prefusing temperature is controlled at 1800 ℃; Slag charge 1 with 1/2 mixes with industrial silicon to be put in the plumbago crucible, vacuumizes, and starts Frequency Induction Heating; Slowly increase power, during power to 80～100kW, add a part of slag charge 2 and logical Ar gas 5min; Continue rising power to 100～120kW, add a part of slag charge 1, logical Cl
2Gas mixing is mixed and is stopped behind the 5min and reduce power to 80kW, keeps for some time, treats to add power again after temperature lowers; Repeat to add slag charge 2 and slag charge 1 then successively, repeat 4 times, behind the slag making 50min; Smelting furnace liquid is transferred to accepts in the plumbago crucible; Get silicon ingot after leaving standstill cooling, sampling detects to such an extent that B content is 0.4ppmw through ICP-MS, and P content is 1.5ppmw.
Embodiment 4: technological process is with embodiment 1, and used slag charge 1 is Na
2CO
3(30%wt)-SiO
2(60%wt)-CaF
2(10%wt), slag charge 2 is adjusted into CaO (60%)-CaSi
2(40%); Slag charge 50kg, slag charge 1 and slag charge 2 respectively account for half the, industrial silicon 50kg, and slag charge 1 becomes the bead appearance of 5cm through art breading, and slag charge 2 carries out fritting, and prefusing temperature is controlled at 1750 ℃; Slag charge 1 with 1/2 mixes with industrial silicon to be put in the plumbago crucible, vacuumizes, and starts Frequency Induction Heating; Slowly increase power, during power to 80～100kW, add a part of slag charge 2 and logical Ar gas 5min; Continue rising power to 100～120kW, add a part of slag ball 1, logical Cl
2Gas mixing is mixed and is stopped behind the 5min and reduce power to 80kW, keeps for some time, treats to add power again after temperature lowers; Repeat to add slag charge 2 and slag charge 1 then successively, repeat 4 times, behind the slag making 55min; Smelting furnace liquid is transferred to accepts in the plumbago crucible; Get silicon ingot after leaving standstill cooling, sampling detects to such an extent that B content is 0.5ppmw through ICP-MS, and P content is 1.8ppmw.
Embodiment 5: technological process is with embodiment 1, and used slag charge 1 is adjusted into Na
2CO
3(30%wt)-SiO
2(60%wt)-CaF
2(10%wt), slag charge 2 is CaO (55%)-CaSi
2(45%).Slag charge 50kg, slag charge 1 and slag charge 2 respectively account for half the, industrial silicon 50kg, and slag charge 1 becomes the bead appearance of 5cm through art breading, and slag charge 2 carries out fritting, and prefusing temperature is controlled at 1800 ℃; Slag charge 1 with 1/2 mixes with industrial silicon to be put in the plumbago crucible, vacuumizes, and starts Frequency Induction Heating; Slowly increase power, during power to 80～100kW, add a part of slag charge 2 and logical Ar gas 5min; Continue rising power to 100～120kW, add a part of slag charge 1, logical Cl
2Gas mixing is mixed and is stopped behind the 5min and reduce power to 80kW, keeps for some time, treats to add power again after temperature lowers; Repeat to add slag charge 2 and slag charge 1 then successively, repeat 6 times, behind the slag making 60min; Smelting furnace liquid is transferred to accepts in the plumbago crucible; Get silicon ingot after leaving standstill cooling, sampling detects to such an extent that B content is 0.65ppmw through ICP-MS, and P content is 1ppmw.
Embodiment 6: technological process is with embodiment 1, and used slag charge 1 is adjusted into Na
2CO
3(40%wt)-SiO
2(50%wt)-CaF
2(10%wt), slag charge 2 is constant still is CaO (55%)-CaSi
2(45%).Slag charge 50kg, slag charge 1 and slag charge 2 respectively account for half the, industrial silicon 50kg, and slag charge 1 becomes the bead appearance of 8cm through art breading, and slag charge 2 carries out fritting, and prefusing temperature is controlled at 1750 ℃; Slag charge 1 with 1/2 mixes with industrial silicon to be put in the plumbago crucible that coating is handled, and vacuumizes, and starts Frequency Induction Heating; Slowly increase power, during power to 80～100kW, add a part of slag charge 2 and logical Ar gas 5min; Continue rising power to 100～120kW, add a part of slag charge 1, logical Cl
2Gas mixing is mixed and is stopped behind the 5min and reduce power to 80kW, keeps for some time, treats to add power again after temperature lowers; Repeat to add slag charge 2 and slag charge 1 then successively, repeat 5 times, behind the slag making 50min; Smelting furnace liquid is transferred to accepts in the plumbago crucible; Get silicon ingot after leaving standstill cooling, sampling detects to such an extent that B content is 0.55ppmw through ICP-MS, and P content is 1.5ppmw.
Claims (10)
1. method of removing boron and phosphorus matter in the industrial silicon is characterized in that may further comprise the steps:
1) with slag charge 2 fritting, said slag charge 2 is CaO-CaSi
2, by mass percentage, CaO is 40%～70%, CaSi
2Be 30～50%;
2) slag charge 1 is pressed into the slag ball, puts part slag charge 1 and industrial silicon into crucible, vacuumize, open the medium frequency induction power supply heating, make material melting, said slag charge 1 is SiO
2-Na
2CO
3-CaF
2, by mass percentage, SiO
2Be 40%～80%, Na
2CO
3Be 20%～50%, CaF
2Be 5%～20%;
3) power to 80 of rising medium frequency induction power supply～100kW when temperature during at 1300～1500 ℃, joins part slag charge 2 in the crucible; Aeration-agitation continues power to the 100～120kW of rising medium frequency induction power supply, when temperature during at 1600～1800 ℃; Part slag charge 1 is joined in the crucible, and aeration-agitation again reduces power to 80kw; Keep for some time, treat that temperature lowers;
4) repeating step 3);
5) after the slag making silicon liquid poured into and accept crucible, leave standstill the cooling back and take out silicon ingot, the polycrystal silicon ingot that the physics fragmentation obtains purifying.
2. a kind of method of removing boron and phosphorus matter in the industrial silicon as claimed in claim 1 is characterized in that in step 1), and said temperature of dissolving in advance is 1650～1850 ℃; By mass percentage, CaO can be 50%～60%, CaSi
2Be 40～50%.
3. a kind of method of removing boron and phosphorus matter in the industrial silicon as claimed in claim 1 is characterized in that in step 2) in, the said slag ball that is pressed into adopts spherical grinding tool, and the diameter of said slag ball can be 5～20cm.
4. a kind of method of removing boron and phosphorus matter in the industrial silicon as claimed in claim 1 is characterized in that in step 2) in, by mass percentage, SiO
2Be 50%～70%; Na
2CO
3Be 30%～45%; CaF
2Be 8%～15%.
5. a kind of method of removing boron and phosphorus matter in the industrial silicon as claimed in claim 1 is characterized in that in step 2) in, said part slag charge 1 is 1 with the mass ratio of industrial silicon: (10～0.5), preferred 1: (5～0.5) are preferably 1: (2.5～0.5).
6. a kind of method of removing boron and phosphorus matter in the industrial silicon as claimed in claim 1 is characterized in that in step 2) in, said part slag charge 1 accounts for 1/3～1/2 of whole slag charges 1 by mass ratio; The said vacuum tightness that vacuumizes can be below the 450Pa.
7. a kind of method of removing boron and phosphorus matter in the industrial silicon as claimed in claim 1 is characterized in that in step 3) the gas of said aeration-agitation is Ar gas, and the time of said aeration-agitation is kept 1～10min, preferably keeps 2～5min.
8. a kind of method of removing boron and phosphorus matter in the industrial silicon as claimed in claim 1 is characterized in that in step 3) the gas of said aeration-agitation again is Cl
2Gas, the time of said aeration-agitation again is 2～15min, is preferably 3～10min.
9. a kind of method of removing boron and phosphorus matter in the industrial silicon as claimed in claim 1 is characterized in that in step 4) said multiple number of times is 3～10 times, is preferably 4～6 times.
10. a kind of method of removing boron and phosphorus matter in the industrial silicon as claimed in claim 1 is characterized in that in step 5) the time of said slag making is 20～80min, is preferably 30～60min; The said time of leaving standstill can be 40～60min.
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| CN103318895A (en) * | 2013-07-05 | 2013-09-25 | 昆明理工大学 | Method for removing impurity phosphorous in silicon |
| CN104276572A (en) * | 2013-07-02 | 2015-01-14 | 青岛隆盛晶硅科技有限公司 | Slagging agent for melting of polysilicon medium and application method thereof |
| CN104641009A (en) * | 2012-06-25 | 2015-05-20 | 希利柯尔材料股份有限公司 | Method to purify aluminum and use of purified aluminum to purify silicon |
| US9676632B2 (en) | 2012-06-25 | 2017-06-13 | Silicor Materials Inc. | Method for purifying silicon |
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| CN101555015A (en) * | 2009-05-19 | 2009-10-14 | 厦门大学 | Purifying method and device for removing boron from polysilicon |
| WO2010062735A2 (en) * | 2008-11-03 | 2010-06-03 | Crystal Systems, Inc. | Method and apparatus for refining metallurgical grade silicon to produce solar grade silicon |
| CN101837980A (en) * | 2010-05-20 | 2010-09-22 | 厦门大学 | Method for removing boron and phosphorus impurities in industrial silicon through sulphide |
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| WO2010062735A2 (en) * | 2008-11-03 | 2010-06-03 | Crystal Systems, Inc. | Method and apparatus for refining metallurgical grade silicon to produce solar grade silicon |
| CN101555015A (en) * | 2009-05-19 | 2009-10-14 | 厦门大学 | Purifying method and device for removing boron from polysilicon |
| CN101837980A (en) * | 2010-05-20 | 2010-09-22 | 厦门大学 | Method for removing boron and phosphorus impurities in industrial silicon through sulphide |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104641009A (en) * | 2012-06-25 | 2015-05-20 | 希利柯尔材料股份有限公司 | Method to purify aluminum and use of purified aluminum to purify silicon |
| US9676632B2 (en) | 2012-06-25 | 2017-06-13 | Silicor Materials Inc. | Method for purifying silicon |
| US10773963B2 (en) | 2012-06-25 | 2020-09-15 | Silicor Materials Inc. | Method of purifying aluminum and use of purified aluminum to purify silicon |
| CN104276572A (en) * | 2013-07-02 | 2015-01-14 | 青岛隆盛晶硅科技有限公司 | Slagging agent for melting of polysilicon medium and application method thereof |
| CN104276572B (en) * | 2013-07-02 | 2016-08-10 | 青岛隆盛晶硅科技有限公司 | The slag former of polycrystalline silicon medium melting and using method thereof |
| CN103318895A (en) * | 2013-07-05 | 2013-09-25 | 昆明理工大学 | Method for removing impurity phosphorous in silicon |
| CN103318895B (en) * | 2013-07-05 | 2016-02-24 | 昆明理工大学 | A kind of method removing foreign matter of phosphor in silicon |
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| CN102616787B (en) | 2014-05-07 |
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