CN101293653A - Method for preparing high purity silicon with silicon waste material purification - Google Patents
Method for preparing high purity silicon with silicon waste material purification Download PDFInfo
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- CN101293653A CN101293653A CNA2008100585700A CN200810058570A CN101293653A CN 101293653 A CN101293653 A CN 101293653A CN A2008100585700 A CNA2008100585700 A CN A2008100585700A CN 200810058570 A CN200810058570 A CN 200810058570A CN 101293653 A CN101293653 A CN 101293653A
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- silicon
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- raw material
- high purity
- preparing high
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 54
- 239000010703 silicon Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000000746 purification Methods 0.000 title claims abstract description 15
- 239000002699 waste material Substances 0.000 title claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000009833 condensation Methods 0.000 claims abstract description 21
- 230000005494 condensation Effects 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000007738 vacuum evaporation Methods 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims description 20
- 238000007670 refining Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 3
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 6
- 239000002210 silicon-based material Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a method for purifying the silicon waste to prepare high purity silicon. The tailing material of massive monocrystal line silicon with the silicon content of more than 90 percent or pot material as raw material is treated by vacuum evaporation and directional condensation, refinement and purification. First, the raw material is heated to the temperature above the melting point of the raw material and carries out vacuum evaporation in the vacuum state with heat preservation to remove the volatile impurity, then, the raw material is stretched and cooled to carry out vacuum directional condensation, refinement and purification. Therefore, the metal impurities are collected at one end, which not only removes the non-metallic impurities but also removes the metallic impurities. The high purity silicon with purity of more than 99.999 percent can be prepared.
Description
One, technical field
The present invention relates to belong to a kind of method of preparing high purity silicon with silicon waste material purification, belong to the vacuum metallurgy method scrap silicon is recycled technical field, particularly the method for preparing high purity silicon with silicon waste material purification.
Two, background technology
At present, China's renewable energy source scale has only 8%, and the development in future space is very wide.And as the most potential energy of 21 century, solar energy industry is all obtaining considerable progress aspect research and development, industrialization, the market development, solar cell industry also become the world fast, one of the sunrise industry of stable development.Polysilicon is the base mateiral of electronic industry and photovoltaic industry.In recent years, be subjected to the driving of solar cell industry development, polysilicon market is increased rapidly.Problem becomes increasingly conspicuous and supply falls short of demand in polysilicon market, has caused global extensive concern, and the recycling of therefore useless silicon material becomes an important source of solar energy level silicon raw material.
Pot bottom material refers to after pulling into silicon single crystal rod, silicon material on remaining at the bottom of the quartz crucible, the silicon single crystal tailing is the afterbody part that produces at the monocrystal pulling silicon rod, if prepare adulterated n type single crystal silicon tailing and pot bottom material, then phosphorus (P) and antimony dopants such as (Sb) are many in the pot bottom material.
Present Xi'an Longji Silicon Technology Co., Ltd carries out acid corrosion to material end to end, the pot bottom material that produces in the monocrystalline production process and cleans the removal of impurities processing, and useless sheet of IC level and useless solar battery sheet are removed deielectric-coating, metal level, diffusion layer removal processing.Silicon materials after the processing can be used for the production of solar energy single crystal, device level monocrystalline; ShangHai JiuJing Electronic Materials Co., Ltd (a kind of solar energy grade silicon single crystal material prescription and preparation, the patent No. 200510027829.1) at first to the cleaning of classifying of policrystalline silicon pot bottom material and monocrystalline sheet stock, carry out acid treatment, with the deionization flushing, put into oven for drying then, then pack, with pot bottom material and the single-chip material formula after handling, pack into guide shell system or non-guide shell system of batching adopted the argon filling of finding time, and decompression technology is produced, and produces solar energy level silicon single crystal; Yuhui Yangguang Energy Resources Co., Ltd., Zhejiang Prov.'s (impurity-removing method of the flavoring food that the Grown by CZ Method silicon single-crystal produces, the patent No. 200610155648.1) at first the bottom of a pan silicon material is broken for granulated, acidleach is handled then, water washes the silicon grain again, oven dry silicon grain, impurity Fu Ji district corrosion in the flavoring food is removed, obtain meeting the silicon material of solar level technical requirements.
Present process draws rich long-pending impurity to be wrapped for several times again or the unmanageable pot bottom material of content height is discarded in a large number, simultaneously again drawing again after the remelting of a large amount of silicon single crystal tailing, be wrapped or the high unmanageable tailing of content is also discarded in a large number through impurity after drawing again for several times, caused the significant wastage of silicon raw material.So needs too impatient to wait are sought the method for the wide preparing high purity silicon with silicon waste material purification of a kind of practicality at present, and silicon single crystal tailing and pot bottom material are purified, and make it meet the technical requirements of solar level silicon materials.
Three, summary of the invention
The object of the present invention is to provide a kind of method of preparing high purity silicon with silicon waste material purification, with siliceous more than 90% blocky silicon single crystal tailing or pot bottom material as raw material, carry out vacuum-evaporation and directed condensation refining purification processes, at first be heated to more than the fusing point of raw material, vacuum-evaporation is carried out in insulation under vacuum state, remove volatile impurity, and then vacuum oriented condensation refining purification processes is carried out in the cooling that stretches, make metallic impurity be enriched in an end, promptly removed nonmetallic impurity, removed metallic impurity again, be prepared into purity in the HIGH-PURITY SILICON more than 99.999%.
The present invention utilizes vacuum oriented condensation method of refining that pot bottom material and silicon single crystal tailing are purified, and the preparation HIGH-PURITY SILICON can satisfy the silicon for solar cell purity requirement, becomes an important source of silicon for solar cell raw material, has the remarkable economical meaning.
The present invention finishes according to the following steps
(1) with siliceous more than 90% blocky silicon single crystal tailing or pot bottom material put into vacuum oriented condensation refining furnace as raw material, at first be heated to more than the fusing point of raw material, vacuum-evaporation is carried out in insulation under vacuum state, remove volatile impurity, controlled temperature is 1420 ℃～1650 ℃, and vacuum tightness is 1.0Pa～1.0 * 10
-4Pa, the vacuum-evaporation soaking time is 0.1h～24h;
(2) carry out directed condensation refining treatment then, directed condensation refining draw speed is 1 μ m/s～1000 μ m/s, the type of cooling be water-cooled, air cooling or metal alloy liquid cooling but.Be prepared into the HIGH-PURITY SILICON of purity more than 99.999%.
The invention has the beneficial effects as follows:
1. realized utilization of waste material.General producer is through after the pulling of crystals repeatedly, and remaining pot bottom material is used as waste treatment and has been fallen, and has produced the wasting of resources, utilizes present method its Impurity removal can be made its requirement of satisfying HIGH-PURITY SILICON, has improved its added value.
2. production efficiency height.In a body of heater,, better solved the problem of the removal of impurities difficulty of silicon single crystal tailing and pot bottom material, made refining effect and production efficiency that the variation of matter arranged in conjunction with the method for vacuum-evaporation and directed condensation refining removal of impurities;
3. Zhi Bei silicon purity can satisfy the requirement of solar level battery industry with silicon.
Four, embodiment
Embodiment one: use heavy doping pot bottom material or silicon single crystal tailing to be raw material, silicone content is 91wt%, major impurity composition Sb content 74120ppmw wherein, Fe content 5000ppmw, Ca content 2600ppmw, Al content 5000ppmw.
Raw material is placed vacuum oriented condensation refining furnace, and at first raw material being heated to temperature is 1450 ℃, and vacuum tightness is 1.0 * 10
-4Pa, insulation 0.5h carries out vacuum-evaporation, stretches with 800 μ m/s speed then, and the type of cooling is an air cooling, carries out vacuum oriented condensation refining purification processes.
Result of implementation: heavy doping pot bottom material or silicon single crystal tailing are after treatment, get vacuum oriented condensation refining ingot middle sample afterwards, detect, its purity is 99.999%, wherein the content of Fe is 2ppmw, and the content of Al is 2ppmw, and the content of Ca is 1ppmw, the content of Sb is 2ppmw, and other total impurities is less than 3ppmw.
Embodiment two: use pot bottom material or silicon single crystal tailing to be raw material, silicone content is 99wt%, major impurity composition Fe content 3500ppmw wherein, Ca content 1000ppmw, Al content 4500ppmw.
After raw material carried out preliminary broken pre-treatment, place the vacuum condensation refining furnace, at first sample being heated to temperature is 1550 ℃, and vacuum tightness is 1.0 * 10
-2Pa, insulation 13h carries out vacuum-evaporation, stretches with 20 μ m/s speed then, and the type of cooling is a water-cooled, carries out vacuum oriented condensation refining purification processes.
Result of implementation: pot bottom material or silicon single crystal tailing are after treatment, get vacuum oriented condensation refining ingot middle sample afterwards, detecting its purity is 99.9995%, wherein the content of iron contamination is 0.8ppmw, the content of aluminium impurity is 0.8ppmw, the content of calcium impurities is 1ppmw, and other total impurities is less than 2.4ppmw.
Embodiment three: use pot bottom material or silicon single crystal tailing to be raw material, silicone content is 99.9wt%, major impurity composition Fe content 650ppmw wherein, Ca content 100ppmw, Al content 150ppmw.
After raw material carried out preliminary broken pre-treatment, place vacuum oriented condensation refining furnace, at first sample being heated to temperature is 1650 ℃, and vacuum tightness is 1.0 * 10
-3Pa, insulation 20h carries out vacuum-evaporation, stretch with 3 μ m/s speed then, the type of cooling be the metal alloy liquid cooling but, carry out vacuum oriented condensation melting purification processes.
Result of implementation: pot bottom material or silicon single crystal tailing are after treatment, get vacuum oriented condensation refining ingot middle sample afterwards, detect, its purity is 99.9999%, wherein the content of iron contamination is 0.3ppmw, the content of aluminium impurity is 0.2ppmw, and the content of calcium impurities is 0.2ppmw, and other total impurities is less than 0.3ppmw.
Claims (2)
1, a kind of method of preparing high purity silicon with silicon waste material purification, it is characterized in that: it is finished according to the following steps,
(1) with siliceous more than 90% blocky silicon single crystal tailing or pot bottom material put into vacuum oriented condensation refining furnace as raw material, at first be heated to more than the fusing point of raw material, vacuum-evaporation is carried out in insulation under vacuum state, remove volatile impurity, controlled temperature is 1420～1650 ℃, and vacuum tightness is 1.0～1.0 * 10
-4Pa, the vacuum-evaporation soaking time is 0.1～24h;
(2) carry out directed condensation refining treatment then, directed condensation refining draw speed is 1 μ m/s～1000 μ m/s.
2, ask the method for 1 described preparing high purity silicon with silicon waste material purification according to right, it is characterized in that: the described directed condensation type of cooling be water-cooled, air cooling or metal alloy liquid cooling but.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100585700A CN101293653A (en) | 2008-06-23 | 2008-06-23 | Method for preparing high purity silicon with silicon waste material purification |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100585700A CN101293653A (en) | 2008-06-23 | 2008-06-23 | Method for preparing high purity silicon with silicon waste material purification |
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| Publication Number | Publication Date |
|---|---|
| CN101293653A true CN101293653A (en) | 2008-10-29 |
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| CNA2008100585700A Pending CN101293653A (en) | 2008-06-23 | 2008-06-23 | Method for preparing high purity silicon with silicon waste material purification |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905885A (en) * | 2009-06-05 | 2010-12-08 | 贵阳宝源阳光硅业有限公司 | Low-boron molten slag for purifying silicon and preparation method thereof |
| CN101774586B (en) * | 2010-02-05 | 2011-12-28 | 大连隆田科技有限公司 | Method and device for removing impurity boron out of polysilicon by induction evaporation mode |
| CN107557860A (en) * | 2017-07-25 | 2018-01-09 | 昆明理工大学 | A kind of method that titanium silicon materials prepare solar-grade polysilicon |
| CN109052407A (en) * | 2018-08-22 | 2018-12-21 | 昆明理工大学 | A kind of recycling and method of purification of silicon cutting waste material |
| CN111646478A (en) * | 2020-07-14 | 2020-09-11 | 昆明理工大学 | Micro-negative pressure external refining method for industrial silicon melt |
| CN111792647A (en) * | 2020-07-21 | 2020-10-20 | 昆明理工大学 | Method for smelting silicon wafer cutting waste under micro-negative pressure |
| CN113023732A (en) * | 2021-03-05 | 2021-06-25 | 昆明理工大学 | Method for preparing high-purity silicon by recovering silicon wafer cutting waste |
| CN115491493A (en) * | 2022-08-31 | 2022-12-20 | 隆基绿能科技股份有限公司 | Waste recovery device and method |
-
2008
- 2008-06-23 CN CNA2008100585700A patent/CN101293653A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905885A (en) * | 2009-06-05 | 2010-12-08 | 贵阳宝源阳光硅业有限公司 | Low-boron molten slag for purifying silicon and preparation method thereof |
| CN101774586B (en) * | 2010-02-05 | 2011-12-28 | 大连隆田科技有限公司 | Method and device for removing impurity boron out of polysilicon by induction evaporation mode |
| CN107557860A (en) * | 2017-07-25 | 2018-01-09 | 昆明理工大学 | A kind of method that titanium silicon materials prepare solar-grade polysilicon |
| CN109052407A (en) * | 2018-08-22 | 2018-12-21 | 昆明理工大学 | A kind of recycling and method of purification of silicon cutting waste material |
| CN111646478A (en) * | 2020-07-14 | 2020-09-11 | 昆明理工大学 | Micro-negative pressure external refining method for industrial silicon melt |
| CN111646478B (en) * | 2020-07-14 | 2022-07-29 | 昆明理工大学 | Micro-negative pressure external refining method for industrial silicon melt |
| CN111792647A (en) * | 2020-07-21 | 2020-10-20 | 昆明理工大学 | Method for smelting silicon wafer cutting waste under micro-negative pressure |
| CN111792647B (en) * | 2020-07-21 | 2021-09-10 | 昆明理工大学 | Method for smelting silicon wafer cutting waste under micro-negative pressure |
| CN113023732A (en) * | 2021-03-05 | 2021-06-25 | 昆明理工大学 | Method for preparing high-purity silicon by recovering silicon wafer cutting waste |
| CN115491493A (en) * | 2022-08-31 | 2022-12-20 | 隆基绿能科技股份有限公司 | Waste recovery device and method |
| CN115491493B (en) * | 2022-08-31 | 2024-03-01 | 隆基绿能科技股份有限公司 | Waste recycling device and method |
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Open date: 20081029 |