CN101007633A - Silicon preparation method of PV industry - Google Patents
Silicon preparation method of PV industry Download PDFInfo
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- CN101007633A CN101007633A CN 200610146233 CN200610146233A CN101007633A CN 101007633 A CN101007633 A CN 101007633A CN 200610146233 CN200610146233 CN 200610146233 CN 200610146233 A CN200610146233 A CN 200610146233A CN 101007633 A CN101007633 A CN 101007633A
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Abstract
The invention discloses a manufacturing method of photovoltaic silicon, which comprises the following steps: A. breaking metal silicon; washing through industrial alcaine; removing ferric and calcium impurity in the metal silicon powder; B. placing metal silicon powder into plasma stove to refine; blowing composite gas with argon and hydrogen chloride into reacting chamber; C. cooling the silicon flux; placing the flux into middle-frequency inductive stove to heat slowly; blowing chlorine gas and oxygen separately; D. cooling flux in the crystallizer under negative vacuum pressure; solidifying from downwards to upwards; E. cutting impurity gathering area on the upper end; F. washing the silicon flux through distilled water to obtain the product.
Description
Technical field
The present invention relates to the production method of HIGH-PURITY SILICON, be specially the production method of photovoltaic industry, especially relate to chemical industry, metallurgical industry and plasma body refining and the multiple combination process flow preparation of directional solidification method photovoltaic industry production method with silicon with silicon (5N-8N).
Background technology
The energy is the important substance basis that the national economic development and living standards of the people improve.At present, China's power supply mainly relies on fossil energies such as coal, oil, Sweet natural gas, but the environmental problem that the resource-constrained of fossil energy and development and use bring is seriously restricting Sustainable development economic and society.Sun power is the abundantest renewable energy source of resource, has special advantages and huge development and use potentiality, is fully realized by people at present.Make full use of the coordinated development that sun power helps keeping getting along amiably and peacefully of man and nature and energy and environment.Chinese solar energy photovoltaic system accumulative total installation had reached 55MWp approximately in 2003, had not only satisfied the needs of domestic application, had also realized a large amount of outlets.At present, China has become the sun power consumer's goods producing country of output maximum in the world.Yet, China's photovoltaic industry size is little, most for producing the middle and lower reaches enterprise of solar module, solar level silicon material in upstream is from the useless time silicon single crystal of the solar level silicon materials-electronic-grade of semi-conductor industry for the source and expects end to end in the world, because useless silicon single crystal of electronic-grade and expect limited amount end to end can't satisfy the demand of downstream photovoltaic industry.Photovoltaic industry uses the purity requirement of silicon at 5N-8N, and the method for producing semiconductor industry silicon mostly is the improvement Siemens Method greatly, and the purity of its silicon can reach 11N-13N, but complex process, cost is too high, and investment is expensive, and product can not directly be used in the photovoltaic industry field because of purity is too high.
Number of patent application is that 02135840 denomination of invention discloses a kind of technological process of production of producing high purity silicon for " production method of high purity silicon ", this production technique melts intensification with Pure Silicon Metal in induction furnace, in temperature-rise period, add several addition materials or be blown into several gases, carry out directional freeze at last according to the sampling analysis result.This invention has the following disadvantages: do not require the metallic silicon raw material granular size 1., the size of metallic silicon particle directly has influence on refining time and product purity, if the metallic silicon particle diameter is excessive, impurity is difficult for removing, the refining time lengthening causes unnecessary energy loss.2. need Pure Silicon Metal is carried out sampling analysis in temperature-rise period, technical difficulty is big, is difficult for realizing.
Summary of the invention
The objective of the invention is to overcome existing photovoltaic industry with silicon complex manufacturing, shortcoming that production cost is high, the production technology scheme of a kind of efficient, cheap, stay-in-grade photovoltaic industry with silicon is provided.
The technical solution used in the present invention is: silicon preparation method of PV industry comprises the steps:
A is broken for the metallic silicon power particle with Pure Silicon Metal, carries out cleanup acid treatment with technical hydrochloric acid, reacts 0.5-1 hour, removes other impurity such as iron in the metallic silicon power, calcium or is muriate with its metallic impurity chlorination, then with its oven dry;
B puts into the plasma heating furnace reaction chamber with above-mentioned steps gained metallic silicon power, power-on, and the mixed gas that will contain argon gas and hydrogenchloride simultaneously is blown into reaction chamber, refining time 70-90 minute;
C puts into the medium-frequency induction furnace reaction chamber after previous step gained silicon melt is cooled off, slowly temperature risen between 1880-1980 ℃, and constant temperature 1-1.5 hour, in its temperature-rise period, be blown into chlorine and oxygen or the mixed gas of the two respectively;
D slowly lowers the temperature previous step gained silicon melt in crystallizer under the negative pressure of vacuum environment, from bottom to top directional freeze;
After E treats that the silicon melt of previous step solidifies fully, cut the accumulation of impurities district of upper end 1/4th;
F promptly obtains photovoltaic industry silicon with distilled water flushing previous step gained silicon melt.
If the too low meeting of the purity of feed metal silicon makes the refining time lengthening, the purity of general requirement metallic silicon raw material is greater than being advisable more than 95%.
Say on the principle that the metallic silicon power diameter is more little is convenient to refining more, but considers the difficulty of grinding and processing, the diameter of generally selecting Pure Silicon Metal for use is that 400-500 μ m gets final product.
Add the technical hydrochloric acid volume and get final product for covering metallic silicon power, the volume of generally controlling the technical hydrochloric acid volume is that 2 times of metallic silicon power volume are the best.
The temperature of technical hydrochloric acid is preferably constant between 80-90 ℃ in the A operation, and this is because the transition volatilization of hydrochloric acid appears in the too high meeting of temperature, and temperature cross low reaction speed can be slack-off.
The ratio of argon gas and hydrogen chloride gas volume is 1 in the B operation: 6-10, the effect of argon gas here is protection and cleans silicon melt.
B operation ionic medium stove power supply is 110-150V, 550-750A.
The reaction chamber of medium-frequency induction furnace is that high-purity stone mill crucible is made in the C operation.
The power of medium-frequency induction furnace can be between the 100KW-150KW in the C operation.
The ratio of chlorine that is blown in the C operation and oxygen volume is 1: 1, and aeration time continues one hour.
Crystallizer in the D operation has temperature control device, by attemperation, per hour controls from bottom to top the speed of directional freeze and be 25 millimeters, treat the complete crystallization of silicon melt after, cut the impurity range on top.General impurity accounts for 1/4 of total crystallization height.
The D operation can repeat repeatedly according to the purity difference that silicon requires.
C, D, E operation are implemented best under dustfree environment.
Use plasma smelting equipment advantage to be, in the plasma body that glow discharge produces, the energy of electronics is enough to make the gas molecule bond rupture, cause the generation of chemically-active particle, make chemical reaction that original needs at high temperature just can carry out greatly reduce temperature of reaction owing to the electricity of gas activates.And the ion in the plasma body obtains energy in electric field, constantly silica flour bombarded, and the surface temperature that makes silica flour more can be quickened the evaporation rate of chemical reaction and resultant of reaction than high many in inside.Therefore the using plasma smelting equipment can shorten the chemical reaction process of impurity in reactant gases and the silica flour, can reduce the purified reaction temperature greatly, improve speed of reaction, resultant of reaction can more promptly volatilize, both save the energy, obtained good refining effect again.The tail gas that discharge the analytical reaction chamber shows that metallic impurity and the reactions of reactive chlorine ion (the hydrogenchloride molecule of excited state, chlorine atom, chlorion) generation gas-solid out-phase such as the iron of silicon powder surface, aluminium, calcium, copper, manganese, lead generate volatile muriate.And non-metallic elements such as phosphorus, boron, a carbon part generates gaseous hydride, and a part is given birth to and volatile muriate, and major part has been discharged reaction chamber.It is as shown in the table to record the content that reacts various impurity in the silicon of front and back by spectrum analyzer:
The content of various impurity in the silicon before and after handling
| Impurity | Si | Al | Ca | Fe | P | Mn | B | Cu |
| % before the reaction | 98％ | 0.04 | 0.12 | 1.4 | 0.002 | 0.005 | 0.003 | 0.7 |
| Reaction back % | ≥4N | 0.005 | 0.0005 | 0.02 | 0.0004 | 0.001 | 0.001 | 0.09 |
| Impurity | Mo | Nb | W | Ti | V | Ni | Cr | Ni |
| % before the reaction | 0.0002 | 0.0008 | 0.00042 | 0.001 | 0.002 | 0.002 3 | 0.0036 | 0.1 |
| Reaction back % | 0.0001 | 0.00073 | 0.00034 | 0.0008 | 0.001 | 0.0008 | 0.0028 | 0.01 |
Use the plasma heating furnace refining after 90 minutes, unsatisfactory to the refining effect of silica flour as continuing time expand, this is because the impurity primitive reaction of silicon powder surface finishes, and the impurity in the silicon is very slow to the diffusion on surface.The purpose of using medium-frequency induction furnace is a purpose of removing impurity in the silicon in order to reach, under the high temperature about 1950 ℃, most of impurity elements have been oxidized to oxide compound or chlorination is a muriate, and these oxide compounds or muriate all are lower than the fusing point of Pure Silicon Metal mostly, under the negative pressure of vacuum environment, carry out directional freeze, thereby reach the effect of further purification silicon crystal.It is as shown in the table to record in the silicon content of various impurity by spectrum analyzer once more:
The content of various impurity in the silicon after the secondary treatment
| Impurity | Si | Al | Ca | Fe | P | Mn | B | Cu |
| % before the secondary treatment | ≥4N | 0.005 | 0.0005 | 0.02 | 0.0004 | 0.001 | 0.09 | 0.09 |
| % after the secondary treatment | 6-8N | 0.002 | 0.0003 | 0.005 | 0.0002 | 0.0005 | 0.02 | 0.006 |
| Impurity | Mo | Nb | W | Ti | V | Ni | Cr | Ni |
| % before the secondary reaction | 0.0001 | 0.00073 | 0.00034 | 0.0008 | 0.001 | 0.0008 | 0.0028 | 0.1 |
| % behind the secondary reaction | -- | 0.00041 | 0.0002 | 0.0006 | 0.00047 | 0.0002 | 0.0001 | 0.01 |
Studies have shown that in a large number: elements such as molybdenum, niobium, tungsten, titanium, vanadium, in concentration 10
13-10
14/ cm
3Promptly the cell photoelectric transformation efficiency is produced a very large impact.Elements such as nickel, aluminium, iron, manganese, chromium then will be in concentration 10
15/ cm
3Just influential to battery efficiency.And phosphorus and copper in concentration up to 10
18/ cm
3Be just the efficient of battery to be had a small amount of influence.Above data presentation, the present invention is satisfactory for result to removing above-mentioned metallic impurity, can improve the photoelectric transformation efficiency of solar cell, thereby has reduced cost, makes the universal possibility of having created of solar cell.
Specific embodiments
Take by weighing purity at the Pure Silicon Metal 200Kg more than 95%, after putting into pulverizer and being crushed to Pure Silicon Metal diameter 400-500 μ m, be poured into reaction taking-up after 1 hour in the technical hydrochloric acid of homo(io)thermism between 80-90 ℃, with distilled water flushing one time, put into the drying plant oven dry took out in 20 minutes, pouring power supply into is 150V, in the plasma electric stove of 750A, opening power, feeding volume ratio simultaneously is 1: 8 the argon gas and the mixed gas of hydrogenchloride, refining time 90 minutes, treat silicon cooling after, claim that its weight is 182.7Kg.
With medium-frequency induction furnace above-mentioned silica flour is warmed up to about 1920 ℃, the ratio that feeds volume simultaneously is 1: 1 chlorine and an oxygen, and keep constant temperature after 1 hour this silicon melt to be poured under vacuum environment, homo(io)thermism is slowly cooling in 1920 ℃ crystallizer, with 25 millimeters speed directional freeze from bottom to top per hour, after treating complete crystallization, cut the impurity range on top 25%, remaining silicon crystal is put into medium-frequency induction furnace once more to be warming up to about 1920 ℃, pour into again in the crystallizer with 25 millimeters speed directional freeze from bottom to top per hour, after treating complete crystallization, cut the impurity range on top 15%, come again once more, after the complete crystallization of silicon melt, cut the impurity range on top 10%.Claim that its weight is 106.1Kg, behind distilled water flushing, can obtain the photovoltaic industry silicon material.
Claims (13)
1. silicon preparation method of PV industry comprises the steps:
A is broken for the metallic silicon power particle with Pure Silicon Metal, carries out cleanup acid treatment with technical hydrochloric acid, reacts 0.5-1 hour, removes other impurity such as iron in the metallic silicon power, calcium or is muriate with its metallic impurity chlorination, then with its oven dry;
B puts into the plasma heating furnace reaction chamber with above-mentioned steps gained metallic silicon power, power-on, and the mixed gas that will contain argon gas and hydrogenchloride simultaneously is blown into reaction chamber, refining time 70-90 minute;
C puts into the medium-frequency induction furnace reaction chamber after previous step gained silicon melt is cooled off, slowly temperature risen between 1880-1980 ℃, and constant temperature 1-1.5 hour, in its temperature-rise period, be blown into chlorine and oxygen or the mixed gas of the two respectively;
D slowly lowers the temperature previous step gained silicon melt in crystallizer under the negative pressure of vacuum environment, from bottom to top directional freeze;
After E treats that the silicon melt of previous step solidifies fully, cut the accumulation of impurities district of upper end 1/4th;
F promptly obtains photovoltaic industry silicon with distilled water flushing previous step gained silicon melt.
2. according to the preparation method of the photovoltaic industry described in the claim 1 with silicon, the purity that requires metallic silicon raw material is greater than more than 95%.
3. according to the preparation method of the photovoltaic industry described in the claim 1, it is characterized in that the metallic silicon power diameter is 400-500 μ m in the A operation with silicon.
According to the photovoltaic industry described in claim 1 or 2 or 3 with the preparation method of silicon, it is characterized in that adding in the A operation technical hydrochloric acid volume and be 2 times of metallic silicon power volume.
5. use the preparation method of silicon according to the photovoltaic industry described in claim 1 or 2 or 3,
The best constant temperature of temperature that it is characterized in that technical hydrochloric acid in the A operation is between 80-90 ℃
According to the photovoltaic industry described in claim 1 or 2 or 3 with the preparation method of silicon, it is characterized in that the ratio of argon gas and hydrogen chloride gas volume is 1 in the B operation: 6-10.
7. according to the preparation method of the photovoltaic industry described in claim 1 or 2 or 3, it is characterized in that B operation ionic medium stove power supply is 110-150V, 550-750A with silicon.
8. according to the preparation method of the photovoltaic industry described in claim 1 or 2 or 3 with silicon, the reaction chamber that it is characterized in that medium-frequency induction furnace in the C operation is that high-purity stone mill crucible is made.
9. according to the preparation method of the photovoltaic industry described in claim 1 or 2 or 3, it is characterized in that the power of medium-frequency induction furnace in the C operation can be between the 100KW-150KW with silicon.
According to the photovoltaic industry described in claim 1 or 2 or 3 with the preparation method of silicon, it is characterized in that the chlorine that is blown in the C operation and the ratio of oxygen volume are 1: 1, aeration time continues one hour.
11. according to the preparation method of the photovoltaic industry described in claim 1 or 2 or 3 with silicon, it is characterized in that the crystallizer in the D operation has temperature control device, pass through attemperation, per hour control from bottom to top the speed of directional freeze and be 25 millimeters, after treating the complete crystallization of silicon melt, cut the impurity range on top.
12. the photovoltaic industry described in claim 1 or 2 or 3 is characterized in that with the preparation method of silicon the D operation can repeat repeatedly according to the purity difference of silicon requirement.
13. the photovoltaic industry described in claim 1 or 2 or 3 is implemented best under dustfree environment with the preparation method of silicon, operation C, D, E.
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| CN 200610146233 CN101007633A (en) | 2006-12-15 | 2006-12-15 | Silicon preparation method of PV industry |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009036686A1 (en) * | 2007-09-14 | 2009-03-26 | Shaoguang Li | Method of manufacturing polycrystalline silicon for solar cell |
| WO2010048885A1 (en) * | 2008-10-28 | 2010-05-06 | Liu Tielin | Process and apparatus for purifying silicon |
| CN101671025B (en) * | 2009-09-30 | 2011-03-23 | 靳瑞敏 | Process for preparing polysilicon for P-type solar cell |
| CN101565186B (en) * | 2009-05-26 | 2011-03-23 | 昆明理工大学 | Method for removing boron impurities in silicon |
| CN102040221A (en) * | 2009-10-13 | 2011-05-04 | 上海太阳能科技有限公司 | Method for purifying metal silicon |
| CN102363528A (en) * | 2011-06-30 | 2012-02-29 | 常州天合光能有限公司 | Cold ion solar-grade polycrystalline silicon material purification method and apparatus thereof |
| WO2012068717A1 (en) * | 2010-11-22 | 2012-05-31 | 矽明科技股份有限公司 | Method for manufacturing solar-grade silicon |
| CN107055545A (en) * | 2016-12-09 | 2017-08-18 | 永平县泰达废渣开发利用有限公司 | It is a kind of to carry out the technique that melting produces silicon ingot using silica flour |
| CN112723358A (en) * | 2021-01-29 | 2021-04-30 | 昆明理工大学 | Method for reducing iron and removing phosphorus of industrial silicon |
| CN113412237A (en) * | 2019-04-30 | 2021-09-17 | 瓦克化学股份公司 | Method for refining a crude silicon melt using a particulate medium |
| CN113772675A (en) * | 2021-11-12 | 2021-12-10 | 山西烁科晶体有限公司 | Purification method of semiconductor grade silicon powder |
| CN114408928A (en) * | 2021-12-31 | 2022-04-29 | 隆基绿能科技股份有限公司 | Silicon material processing method and silicon material processing device |
| CN116161666A (en) * | 2023-03-07 | 2023-05-26 | 安阳工学院 | Method for removing metallic silicon impurities at low temperature |
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2006
- 2006-12-15 CN CN 200610146233 patent/CN101007633A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009036686A1 (en) * | 2007-09-14 | 2009-03-26 | Shaoguang Li | Method of manufacturing polycrystalline silicon for solar cell |
| WO2010048885A1 (en) * | 2008-10-28 | 2010-05-06 | Liu Tielin | Process and apparatus for purifying silicon |
| CN101565186B (en) * | 2009-05-26 | 2011-03-23 | 昆明理工大学 | Method for removing boron impurities in silicon |
| CN101671025B (en) * | 2009-09-30 | 2011-03-23 | 靳瑞敏 | Process for preparing polysilicon for P-type solar cell |
| CN102040221A (en) * | 2009-10-13 | 2011-05-04 | 上海太阳能科技有限公司 | Method for purifying metal silicon |
| WO2012068717A1 (en) * | 2010-11-22 | 2012-05-31 | 矽明科技股份有限公司 | Method for manufacturing solar-grade silicon |
| CN102363528A (en) * | 2011-06-30 | 2012-02-29 | 常州天合光能有限公司 | Cold ion solar-grade polycrystalline silicon material purification method and apparatus thereof |
| CN107055545A (en) * | 2016-12-09 | 2017-08-18 | 永平县泰达废渣开发利用有限公司 | It is a kind of to carry out the technique that melting produces silicon ingot using silica flour |
| CN107055545B (en) * | 2016-12-09 | 2019-01-25 | 成都斯力康科技股份有限公司 | A kind of technique carrying out melting production silicon ingot using silicon powder |
| CN113412237A (en) * | 2019-04-30 | 2021-09-17 | 瓦克化学股份公司 | Method for refining a crude silicon melt using a particulate medium |
| CN113412237B (en) * | 2019-04-30 | 2024-06-07 | 瓦克化学股份公司 | Method for refining crude silicon melt using particulate medium |
| CN112723358A (en) * | 2021-01-29 | 2021-04-30 | 昆明理工大学 | Method for reducing iron and removing phosphorus of industrial silicon |
| CN113772675A (en) * | 2021-11-12 | 2021-12-10 | 山西烁科晶体有限公司 | Purification method of semiconductor grade silicon powder |
| CN114408928A (en) * | 2021-12-31 | 2022-04-29 | 隆基绿能科技股份有限公司 | Silicon material processing method and silicon material processing device |
| CN116161666A (en) * | 2023-03-07 | 2023-05-26 | 安阳工学院 | Method for removing metallic silicon impurities at low temperature |
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Open date: 20070801 |