CN102219221B - Method for purifying polycrystalline silicon by directional solidification and slag refining - Google Patents
Method for purifying polycrystalline silicon by directional solidification and slag refining Download PDFInfo
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- CN102219221B CN102219221B CN 201110152163 CN201110152163A CN102219221B CN 102219221 B CN102219221 B CN 102219221B CN 201110152163 CN201110152163 CN 201110152163 CN 201110152163 A CN201110152163 A CN 201110152163A CN 102219221 B CN102219221 B CN 102219221B
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- slag
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- 239000002893 slag Substances 0.000 title claims abstract description 51
- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000007711 solidification Methods 0.000 title claims abstract description 23
- 230000008023 solidification Effects 0.000 title claims abstract description 23
- 238000007670 refining Methods 0.000 title claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052796 boron Inorganic materials 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000002210 silicon-based material Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 10
- 239000002699 waste material Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003723 Smelting Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 240000003936 Plumbago auriculata Species 0.000 claims 1
- 230000008018 melting Effects 0.000 abstract description 17
- 238000002844 melting Methods 0.000 abstract description 17
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000005272 metallurgy Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000005204 segregation Methods 0.000 abstract description 3
- 239000012141 concentrate Substances 0.000 abstract 1
- 229920005591 polysilicon Polymers 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 5
- 241000209456 Plumbago Species 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XUKUURHRXDUEBC-SXOMAYOGSA-N (3s,5r)-7-[2-(4-fluorophenyl)-3-phenyl-4-(phenylcarbamoyl)-5-propan-2-ylpyrrol-1-yl]-3,5-dihydroxyheptanoic acid Chemical compound C=1C=CC=CC=1C1=C(C=2C=CC(F)=CC=2)N(CC[C@@H](O)C[C@H](O)CC(O)=O)C(C(C)C)=C1C(=O)NC1=CC=CC=C1 XUKUURHRXDUEBC-SXOMAYOGSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- -1 boron oxide compound Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
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Abstract
The invention belongs to the technical field of purifying polycrystalline silicon by physical metallurgy technology. A method for purifying polycrystalline silicon by directional solidification and slag refining comprises the following steps: firstly, mixing polycrystalline silicon material and acid slag former uniformly so as to form mixture, then arranging the mixture into a melting crucible of a directional solidification furnace, slagging and melting the mixture in the melting crucible, simultaneously, conducting directional solidification so as to concentrate metal impurity and waste slag on the top of a silicon ingot, removing boron and metal impurity, and finally cutting the top of the silicon ingot, thus obtaining polycrystalline silicon ingot with low boron and metal content. The method has the following obvious effects: the acid slag former for slagging and melting and the directional solidification are adopted simultaneously, the impurity boron in the polycrystalline silicon is removed by the slagging of the acid slag former and the refining, simultaneously, the metal impurity with a smaller segregation coefficient in the polycrystalline silicon is removed by the directional solidification technology, the purity of the polycrystalline silicon material is improved, so that polycrystalline silicon material achieves the using requirement of solar-level polycrystalline silicon material.
Description
Technical field
The invention belongs to the technical field with physical metallurgy technology purifying polycrystalline silicon, particularly a kind of directional solidification technique that utilizes carries out the slag making melting, thereby removes the method for boron and metallic impurity in the polysilicon.
Background technology
In energy scarcity, the society that advocates low-carbon environment-friendly, sun power has great application value as a kind of environmental protection new forms of energy.In recent years, the global solar photovoltaic industry increases rapidly, and solar cell yield increases fast, direct pull the rapid expansion of solar energy polycrystalline silicon demand.
The method of purifying solar energy polysilicon mainly contains chemical purification and physical purification at present, and chemical purification mainly is Siemens Method, and its advantage is the product purity height, quality better, but its technology grasps in minority developed country, and corresponding investment is big, the cost height also can produce obnoxious flavour.Metallurgy method is to make the popular method of polysilicon at present, its output height, less investment, cost is low, pollution-free, along with the fast development of this research field in recent years, it is ripe that the technological line of metallurgy method purifying solar energy level polysilicon is tending towards, the employing directional solidification processes can effectively be removed metallic impurity wherein, and electron beam melting can be removed impurity P, and the difficult point of concentrating is the removal to impurity B at present, because the segregation coefficient of B big (being 0.8), saturation steam forces down, and can't remove with aforesaid way, is badly in need of a kind of less energy-consumption at present and can effectively removes the method for B.
The slag making melting is a kind of method of effective removal B impurity, mode by high temperature slag making melting can effectively generate boron oxide compound with B impurity and the reaction of the oxidisability composition in the slag agent of melting in the silicon, sepn process with slag agent and silicon liquid is removed, and therefore utilizing slag making to remove B is a kind of efficient ways.Slag making melting slag former commonly used has CaO-SiO
2, Na
2O-CaO-SiO
2, CaF
2-CaO-SiO
2Deng, the Suzuki of Japan and Sano studied calcium be slag except B effect, BaO-CaO-SiO
2The maximum allocated coefficient that system obtains is about 2, and therefore will reach the solar energy level silicon material requirements just need carry out repeatedly slag making, perhaps very big slag silicon ratio, and this feasibility in requiring the low-cost industrial popularization is little.The Morita of Japan etc. has done systematic research to the slag making melting, draws the basicity that the principal element that influences partition ratio has the slag agent, oxygen partial pressure and the B distribution in melt, but finally neither be very desirable, be difficult to reach industrialization demands.
Disclose the patent No. in the prior art and be the preparation method of a kind of solar energy level silicon of 200810068908.0 and the patent No. and be 201010215098.4 metallurgy method and prepared the method for solar-grade polysilicon and the polysilicon of this method preparation, but the type of heating of the directional solidification furnace that the slag making melting is adopted in these two patents is the induction melting heating, this type of heating produces bigger disturbance to the white residue melt, be unfavorable for the stable separation of reacted waste residue from melt, the removal effect of boron is not good.
Summary of the invention
The objective of the invention is to overcome above-mentioned not enough problem, a kind of method of directional freeze slag making refining purifying polycrystalline silicon is provided, in conjunction with utilizing slag making melting and directional solidification technique, remove boron and metallic impurity simultaneously, reach the service requirements of solar grade polycrystalline silicon material.
The technical scheme that the present invention adopts for achieving the above object is: a kind of method of directional freeze slag making refining purifying polycrystalline silicon, at first polycrystalline silicon material and acid slag former are uniformly mixed to form compound, then compound is put in directional solidification furnace (referring to patent of invention: a kind of polysilicon directional freezing equipment, ZL200810012354.2) in the smelting pot, in smelting pot, carry out the slag making melting, carrying out directional freeze simultaneously makes metallic impurity and waste residue accumulate in the top of silicon ingot, remove boron and metallic impurity simultaneously, cut the top of silicon ingot at last, obtain low boron, the polycrystal silicon ingot of low metal.
Described concrete steps are as follows:
At first with polycrystalline silicon material washed with de-ionized water 4-5 time, put into 60 ℃ of oven dry of drying baker, polycrystalline silicon material and the acid slag former of drying is uniformly mixed to form compound in proportion;
Then compound is slowly poured in the smelting pot in the directional solidification furnace, close bell, opening mechanical pump is evacuated to below the 900Pa, after open lobe pump and be evacuated to below the 4Pa, open the top of directional solidification furnace, three graphite heaters in sidepiece and bottom, and keep the power of three heating elements identical, the beginning heat temperature raising, when temperature is increased to 1100-1200 ℃, the argon shield of feed flowing is incubated 0.5-3h after being warming up to 1500-1700 ℃, reduces bottom graphite heater power earlier, the back reduces sidepiece graphite heater power, make the white residue melt from the bottom to top formation temperature gradient, reduce simultaneously the temperature of white residue melt according to the rate of cooling of 0.1-5 ℃/min, produce directional freeze, the white residue melt all solidifies the after-acceleration cooling, up to being cooled to room temperature;
Take out silicon ingot at last, cut silicon ingot top metal impurity and waste residue, can obtain the polycrystal silicon ingot of low boron, low metal.
The polycrystalline silicon material of described adding is piece material or powder.
The acid slag former of described adding is SiO
2-CaO-Na
2CO
3Or SiO
2-CaO-Na
2O, wherein SiO
2Mass percent is 60-80%, and the CaO mass percent is 15-25%, Na
2CO
3Or Na
2The O mass percent is 5-15%.
The ratio of acid slag former and silicon material is 0.1-1.5 in the described compound.
Described smelting pot can be quartz crucible, plumbago crucible, SiC crucible, MgO crucible and Si
3N
4Crucible.
Unusual effect of the present invention is the method for using acid slag former slag making melting and directional freeze simultaneously, by the boron impurities in the acid slag former slag making refining removal polysilicon, remove the less metallic impurity of segregation coefficient in the polysilicon by directional solidification technique simultaneously, improve the purity of polycrystalline silicon material, make it reach the service requirements of solar grade polycrystalline silicon material, this technology is except boron, it is effective to remove metallic impurity, method is simple, use the stronger acid slag former oxidisable impurity boron of oxidisability to form the oxide compound of boron earlier, this oxide compound will be attached among the slag agent, after carry out directional freeze the slag agent constantly assembled to melt top, directional freeze also makes metallic impurity to the enrichment of melt top simultaneously, cut the silicon ingot top of being rich in impurity and can remove boron and metallic impurity, realize that simultaneously acid slag former slag making melting except boron and the directional freeze double effects except metallic impurity, reaches quick, effectively remove the purpose of impurity in the polysilicon.
Description of drawings
Accompanying drawing 1 is the method flow diagram of directional freeze slag making refining purifying polycrystalline silicon of the present invention.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiments and the drawings, but the present invention is not limited to specific embodiment.
Embodiment 1
At first getting boron content is 0.001%, and total metal content is 0.05% polysilicon block material, uses washed with de-ionized water 5 times, puts into 60 ℃ of oven dry down of drying baker, gets polysilicon block material and the acid slag former SiO of 500g of 500g oven dry
2-CaO-Na
2CO
3Be 1 evenly to mix by slag silicon ratio, form compound, wherein acid slag former SiO
2-CaO-Na
2CO
3The shared mass percent of each component is SiO
280%, CaO15% and Na
2CO
35%;
Then compound is slowly poured in the plumbago crucible in the directional solidification furnace, close bell, open mechanical pump and be evacuated to 800Pa, after open lobe pump and be evacuated to 3Pa, open the top of directional solidification furnace, three graphite heaters in sidepiece and bottom, and keep the power of three heating elements identical, the beginning heat temperature raising, when temperature is increased to 1200 ℃, the argon shield of feed flowing is incubated 1h after being warming up to 1500 ℃, reduces bottom graphite heater power earlier, the back reduces sidepiece graphite heater power, make the white residue melt from the bottom to top portion formation temperature gradient, reduce simultaneously the temperature of white residue melt according to the rate of cooling of 0.1 ℃/min, produce directional solidification effect, the white residue melt all solidifies the after-acceleration cooling, up to being cooled to room temperature;
Take out silicon ingot at last, cut silicon ingot top metal impurity and waste residue, the polycrystal silicon ingot that obtains boron content by analysis is lower than 0.0001%, and the metallic impurity total content is lower than 0.0005%.
Embodiment 2
At first getting boron content is 0.0015%, and total metal content is 0.06% polysilicon block material, uses washed with de-ionized water 5 times, puts into 60 ℃ of oven dry down of drying baker, gets polysilicon block material and the acid slag former SiO of 600g of 500g oven dry
2-CaO-Na
2O is 1.2 to be uniformly mixed to form compound by slag silicon ratio, wherein acid slag former SiO
2-CaO-Na
2The shared mass percent of each component of O is SiO
260%, CaO25% and Na
2O15%;
Then compound is slowly poured in the plumbago crucible in the directional solidification furnace, close bell, open mechanical pump and be evacuated to 800Pa, after open lobe pump and be evacuated to 3Pa, open the top of directional solidification furnace, three graphite heaters in sidepiece and bottom, and keep the power of three heating elements identical, the beginning heat temperature raising, when temperature is increased to 1200 ℃, the argon shield of feed flowing is incubated 2h after being warming up to 1600 ℃, reduces bottom graphite heater power earlier, the back reduces sidepiece graphite heater power, make the white residue melt from the bottom to top portion formation temperature gradient, reduce simultaneously the temperature of white residue melt according to the rate of cooling of 0.2 ℃/min, produce directional solidification effect, the white residue melt all solidifies the after-acceleration cooling, up to being cooled to room temperature;
Take out silicon ingot at last, cut silicon ingot top metal impurity and waste residue, the polycrystal silicon ingot that obtains boron content by analysis is lower than 0.00008%, and the metallic impurity total content is lower than 0.0008%.
The present invention is except boron, consistent through case test except metal effect, and refining effect is good, and energy consumption is little, and cost is low, and technology is simple, and the cycle is short, and production efficiency is higher.
Claims (3)
1. the method for a directional freeze slag making refining purifying polycrystalline silicon is characterized in that concrete steps are as follows:
At first with polycrystalline silicon material washed with de-ionized water 4-5 time, put into 60 ℃ of oven dry of drying baker, polycrystalline silicon material and the acid slag former of drying is uniformly mixed to form compound by a certain percentage; Described acid slag former is SiO
2-CaO-Na
2CO
3Or SiO
2-CaO-Na
2O, wherein SiO
2Mass percent is 60-80%, and the CaO mass percent is 15-25%, Na
2CO
3Or Na
2The O mass percent is 5-15%; The acid slag former of described compound and the ratio of silicon material are 0.1-1.5;
Then compound is slowly poured in the smelting pot in the directional solidification furnace, close bell, opening mechanical pump is evacuated to below the 900Pa, after open lobe pump and be evacuated to below the 4Pa, open the top of directional solidification furnace, three graphite heaters in sidepiece and bottom, and keep the power of three heating elements identical, the beginning heat temperature raising, when temperature is increased to 1100-1200 ℃, the argon shield of feed flowing is incubated 0.5-3h after being warming up to 1500-1700 ℃, reduces bottom graphite heater power earlier, the back reduces sidepiece graphite heater power, make the white residue melt from the bottom to top formation temperature gradient, reduce simultaneously the temperature of white residue melt according to the rate of cooling of 0.1-5 ℃/min, produce directional solidification effect, the white residue melt all solidifies the after-acceleration cooling, up to being cooled to room temperature;
Take out silicon ingot at last, cut silicon ingot top metal impurity and waste residue, can obtain the polycrystal silicon ingot of low boron, low metal.
2. require the method for described directional freeze slag making refining purifying polycrystalline silicon according to right 1, it is characterized in that the polycrystalline silicon material of described adding is piece material or powder.
3. require the method for described directional freeze slag making refining purifying polycrystalline silicon according to right 1, it is characterized in that described smelting pot can be quartz crucible, plumbago crucible, SiC crucible, MgO crucible and Si
3N
4Crucible.
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|---|---|---|---|
| CN 201110152163 CN102219221B (en) | 2011-06-08 | 2011-06-08 | Method for purifying polycrystalline silicon by directional solidification and slag refining |
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|---|---|---|---|
| CN 201110152163 CN102219221B (en) | 2011-06-08 | 2011-06-08 | Method for purifying polycrystalline silicon by directional solidification and slag refining |
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| CN102219221A CN102219221A (en) | 2011-10-19 |
| CN102219221B true CN102219221B (en) | 2013-07-17 |
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Families Citing this family (12)
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|---|---|---|---|---|
| CN102530954B (en) * | 2012-03-07 | 2015-05-20 | 昆明理工大学 | Composite refining agent for secondary refining to purify industrial silicon and remove boron |
| TWI498282B (en) * | 2012-06-25 | 2015-09-01 | Silicor Materials Inc | Flux composition useful in directional solidification for purifying silicon and method thereof |
| CN102730697B (en) * | 2012-06-26 | 2014-04-30 | 上海太阳能电池研究与发展中心 | System and method for purifying polysilicon through continuous slagging under electric field |
| CN103043664B (en) * | 2012-12-13 | 2014-08-27 | 青岛隆盛晶硅科技有限公司 | Method and device for directionally solidifying and purifying polysilicon by vacuum extraction of tailing |
| CN104195638A (en) * | 2014-09-01 | 2014-12-10 | 大连理工大学 | Method for preparing boron master alloy by using metallurgy method |
| CN104817087A (en) * | 2015-05-04 | 2015-08-05 | 佳科太阳能硅(龙岩)有限公司 | Method of refining silicon with non-graphite crucible on medium-frequency furnace |
| CN105063749B (en) * | 2015-06-08 | 2017-07-18 | 朱超 | A kind of method for preparing high-purity polycrystalline silicon |
| CN107099841B (en) * | 2017-04-24 | 2019-02-26 | 武汉理工大学 | A kind of method that short route, high efficiency and inexpensive purification prepare polycrystalline silicon used for solar battery |
| CN107523861A (en) * | 2017-08-10 | 2017-12-29 | 镇江仁德新能源科技有限公司 | A kind of method that impurity is captured in directional solidification process |
| CN110156024B (en) * | 2019-06-14 | 2022-10-21 | 宝兴易达光伏刃料有限公司 | Method for refining high-purity silicon from metallic silicon |
| CN112064113B (en) * | 2020-10-22 | 2021-05-25 | 新余学院 | Polycrystalline silicon ingot furnace convenient to get rid of impurity layer |
| CN115124041B (en) * | 2022-05-27 | 2023-11-17 | 大连理工大学 | Method for purifying polycrystalline silicon waste by utilizing waste glass of solar cell |
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| CN101323972B (en) * | 2008-07-14 | 2010-06-02 | 大连理工大学 | Polysilicon directional freezing equipment |
| CN102040220A (en) * | 2009-10-13 | 2011-05-04 | 上海太阳能科技有限公司 | Manufacturing method of solar-grade polycrystalline silicon |
| CN101920960B (en) * | 2010-06-29 | 2012-07-25 | 华南师范大学 | Method for preparing solar grade polysilicon by metallurgy method and polysilicon prepared thereby |
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