CN1221470C - High purity silicon and productive method thereof - Google Patents
High purity silicon and productive method thereof Download PDFInfo
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- CN1221470C CN1221470C CN 02135840 CN02135840A CN1221470C CN 1221470 C CN1221470 C CN 1221470C CN 02135840 CN02135840 CN 02135840 CN 02135840 A CN02135840 A CN 02135840A CN 1221470 C CN1221470 C CN 1221470C
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Abstract
The present invention provides high-purity silicon with 99.99999 to 99.99999999% of the purify and a production method thereof. The method has the steps that metallic silicon used as raw materials are fused into fused silicon mass; lime, iron oxide and fluorite or the lime and the fluorite are added into the fused silicon mass; oxygen, chlorine, aqueous hydrogen and argon are blown into the fused silicon mass; finally the fused silicon mass is orderly and directionally solidified in a crystallizer.
Description
Affiliated technical field
The present invention relates to the high purity silicon that the production method of high purity silicon, particularly silicone content are 99.99999-99.99999999% (weight), and relate to the production method of this high purity silicon.
Background technology
High purity silicon is the base mateiral of unicircuit or solar cell, representative highly purified silicon materials mainly are to be raw material with silicone content greater than 99% Pure Silicon Metal, with gas phase distillation method of purification it is purified, obtaining purity through solidifying processing again is the silicon materials of 99.999999999% (weight).This material is mainly used in the IC industry, section back the surplus tankage material that then can be used as solar cell use.Described tankage limited amount does not satisfy the requirement of producing solar cell, in addition.The silicon materials that are applicable to solar cell do not need so high purity yet.Though described gas phase distillation method of purification can be produced highly purified silicon, its complex process, apparatus expensive, result cause production cost of products very high.
Application publication number is CN 1176319A, and denomination of invention discloses a kind of method of producing the material of high purity silicon for the Chinese invention patent application of " smelting also directly from ultra-pure quartz material, the equipment of ingot casting reaches the technology of producing solar energy-level silicon wafer to section ".This method is a raw material with highly purified quartz material (quartz sand or/quartz ware waste material), with its melting and obtain silicon melt in electric furnace, makes this silicon melt obtain the silicon materials of solar level then after ingot casting, directional freeze.Though this technology is simple relatively, step back very harsh to the requirement of raw material.Because highly purified quartz sand supply of raw material instability, thereby limited this implementation of processes; This technology of this external application obtains the purity of product, is not reported so far.
Because the method for the production high-purity silicon material of prior art has above-mentioned shortcoming, so the present technique field method that always waits in expectation the production high purity silicon new.
Summary of the invention
Silicon and production method thereof that to the object of the present invention is to provide a kind of production high purity silicon, particularly purity be the 99.99999-99.99999999% solar battery grade.
The purity of high purity silicon of the present invention is 99.99999-99.99999999% (weight).
The method of production high purity silicon of the present invention comprises following processing step:
1, with liquid and/solid-state Pure Silicon Metal melts in induction furnace.Described induction furnace preferably has the medium-frequency induction furnace of plumbago crucible.
2, behind above-mentioned Pure Silicon Metal fine melt, the temperature of this silicon melt is progressively risen to 1900-1950 ℃, between temperature raising period, to take a sample, analytical results adds one or more following addition materials and is blown into the composition that one or more following gases are controlled this melt:
1) weight ratio is the addition material of lime, ferric oxide and the fluorite of 3-4: 0.5-1: 0.5-1; Its consumption is the 8-15% of described silicon melt weight;
2) amount is than being the lime of 3.5-4.5: 0.5-1.5 and the addition material of fluorite; Its consumption is the 8-15% of described silicon melt weight;
3) oxygen, chlorine and contain the water of 0.01-1.0% (weight) or the hydrogen of water vapour;
3, after having blown above-mentioned gas, be blown into argon gas at last;
4, when the temperature of this silicon melt progressively rises to 1900-1950 ℃, in the crystallizer with its impouring Controllable Temperature, make its with the 20-10 millimeter/hour setting rate order directional freeze from bottom to up, cut the impurity enriched district of gained silicon crystal upper end at last.Pressure when solidifying is preferably negative pressure.
5, the silicon crystal with gained in the step 4 melts in the medium-frequency induction furnace of step 1, heats up repeating step 4 when the temperature of this silicon melt progressively rises to 1900-1950 ℃.
Step 5 can repeat repeatedly according to the requirement of silicon purity.The Pure Silicon Metal composition does not have particular requirement, and preferably its silicone content is greater than 90%.Pure Silicon Metal is at middle frequency furnace, preferably has in the process that fusing in the middle frequency furnace of protection of inert gas is warming up to 1550 ℃, and wherein contained high-melting-point impurity and lower boiling impurity are got rid of by major part.The purpose that adds lime, ferric oxide and fluorite and add lime, fluorite is to remove p and s contained in the Pure Silicon Metal etc.Oxygen blast can make the impurity oxygen such as iron, manganese, aluminium, titanium of element state contained in the Pure Silicon Metal change into corresponding oxide compound in the silicon melt, and this oxide compound can be excluded from silicon melt under the effect of electromagnetic force.In silicon melt, blow chlorine in order that remove impurity such as remaining aluminium, be blown into the hydrogen that contains moisture or water vapour and be removed, and the oxygen that moisture can generate helps to make metal remained impurity to be removed through oxidation in order that make residual sulphur and phosphorus become corresponding hydride.Be blown into argon gas at last and can further clean silicon melt.Add which kind of additive and be blown into which kind of gas and depend on foreign matter content in the silicon melt at that time.In induction furnace during melting, the heat-up rate of silicon melt and soaking time need not strict regulations, and these two parameters depend primarily on the capacity and the power of stove.Kind, time and the flow that is blown into gas depends on the foreign matter content in the silicon melt.The pressure of this gas slightly seethes with excitement with melt but does not make it degree of being splashed as.The kind of air blowing kind and time and addition material and consumption then can be controlled by the inter-level analysis.
Through the silicon melt of above-mentioned refinement step directional freeze from bottom to up in the crystallizer that temperature thermocouple and heating unit are housed.Under condition of negative pressure, solidify and to improve setting rate.Because the choosing of directional freeze divides crystallization effect, the silicon crystal purity of generation is very high, and remaining impurities is then upwards pushed away, and finally stays the upper surface place of silicon crystal, and in this directional freeze process, setting rate is controlled at 20-10 millimeter/hour be advisable.Setting rate is greater than 20 millimeters/hour, and then choosing divides the deleterious of crystallization despumation, and then the productivity of this technology is low excessively less than 10 millimeters/hour for this speed.According to the product purity requirement, can make the silicon crystal in the impurity enriched district that is cut the upper end bear repeatedly remelting and directional freeze.
By method of the present invention can production purity be the silicon of 99.99999-99.99999999% (weight).This silicon materials are applicable to the solar cell that class is lower.With the gas phase of routine distillation method of purification with to adopt ultra-pure quartz be that the method for raw material production high purity silicon is compared, method of the present invention has that technology is simple, equipment is simple, working cost is low, raw material can be stablized and the advantage of reliable acquisition.
Below in conjunction with embodiment the present invention is made specific description.
Embodiment
Embodiment 1
With silicone content be the commercial metals silicon of 92.8% (weight) to place power be 500KVA, melting under air and protection of inert gas in the medium-frequency induction furnace of plumbago crucible is housed.After treating the Pure Silicon Metal fine melt, be warming up to 1550 ℃ and be incubated after 20 minutes that to add the 50KG weight ratio be 3: 1: 1 lime, brown iron oxide and fluorite.After treating described addition material fine melt, be incubated 10 minutes.The temperature of this silicon melt is risen to 1650 ℃, add 50KG by 4 parts of weight lime and 1 part of addition material that the weight fluorite is formed.After treating this addition material fine melt, be incubated 10 minutes.Temperature with described silicon melt rises to 1950 ℃ then, and oxygen blast gas is 5 minutes in this process; Blew chlorine 5 minutes; Blow the hydrogen 8 minutes that contains 1.0% (weight) water vapour; Last blowing argon gas 10 minutes is incubated 30 minutes with silicon melt then under 1950 ℃ temperature.
Sampling analysis, this moment, the purity of silicon melt was 99.99%.This silicon melt impouring is had argon shield, be equipped with in the crystallizer of thermopair and heating unit.The monitoring by thermopair and the control of heating unit make described silicon melt with 15 millimeters/hour speed directional freeze from bottom to up.Treat that silicon melt coagulates the impurity enriched district that the upper end is removed in the back entirely, obtain purity and be 99.999% silicon crystal.The silicon crystal of gained is melted in above-mentioned medium-frequency induction furnace once more.When the temperature of this silicon melt rises to 1950 ℃, be poured in the above-mentioned crystallizer, and solidify with same condition.After cutting the impurity enriched district of upper end, it is 99.99999999% silicon crystal that the result obtains purity.
Claims (4)
1, a kind of method of producing high purity silicon the steps include:
The first step, liquid and solid-state Pure Silicon Metal are melted in induction furnace;
Second step, the temperature of this silicon melt is progressively risen to 1900-1950 ℃, in temperature-rise period according to the sampling analysis result add following one or more addition material and be blown into following one or more gases:
A, weight ratio are lime, ferric oxide and the fluorite addition material of 3-4: 0.5-1: 0.5-1, and its amount is the heavy 8-15% of this silicon melt;
B, weight ratio are lime and the fluorite addition material of 3.5-4.5: 0.5-1.5, and its amount is the 8-15% of this silicon melt weight;
C, oxygen, chlorine and contain the water of 0.01-1.0% (weight) or the hydrogen of water vapour; In the 3rd step, be blown into argon gas at last after having blown above-mentioned gas;
The 4th the step, when the temperature of this silicon melt progressively rises to 1900-1950 ℃, in the crystallizer with its impouring Controllable Temperature, make its with the 20-10 millimeter/hour setting rate order directional freeze from bottom to up, cut the impurity enriched district of gained crystal upper end at last;
The 5th step, the silicon crystal of step 4 gained is melted in the medium-frequency induction furnace of step 1, heat up repeating step four when the temperature of this silicon melt progressively rises to 1900-1950 ℃.
2, a kind of method of producing high purity silicon according to claim 1, wherein said induction furnace is the medium-frequency induction furnace that is provided with plumbago crucible.
3, a kind of method of producing high purity silicon according to claim 1, wherein said coagulation step is to carry out under negative pressure.
4, a kind of method of producing high purity silicon according to claim 1, wherein said step 5 repeats repeatedly.
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| CN 02135840 CN1221470C (en) | 2002-11-26 | 2002-11-26 | High purity silicon and productive method thereof |
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| CN 02135840 CN1221470C (en) | 2002-11-26 | 2002-11-26 | High purity silicon and productive method thereof |
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| CN1502556A CN1502556A (en) | 2004-06-09 |
| CN1221470C true CN1221470C (en) | 2005-10-05 |
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| CN 02135840 Expired - Fee Related CN1221470C (en) | 2002-11-26 | 2002-11-26 | High purity silicon and productive method thereof |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100595352C (en) * | 2007-07-17 | 2010-03-24 | 佳科太阳能硅(龙岩)有限公司 | Method for preparing big ingot of polysilicon in level of solar energy |
| MX2010002728A (en) | 2007-09-13 | 2010-08-02 | Silicium Becancour Inc | Process for the production of medium and high purity silicon from metallurgical grade silicon. |
| CN101386413B (en) * | 2008-04-15 | 2011-05-18 | 南安市三晶阳光电力有限公司 | Method for reducing oxygen and carbon content in metal silicon |
| CN101559949B (en) * | 2008-04-15 | 2011-07-27 | 南安市三晶阳光电力有限公司 | Method for leading mixed gas into metal silicon solution |
| CN101602506B (en) * | 2009-07-03 | 2012-10-24 | 锦州市三特真空冶金技术工业有限公司 | Production method and production equipment for high-purity polysilicon |
| CN102351197A (en) * | 2010-03-19 | 2012-02-15 | 姜学昭 | Method for purifying silicon |
| TWI539039B (en) * | 2012-01-26 | 2016-06-21 | 希利柯爾材料股份有限公司 | Method for purification of silicon |
| CN102627394B (en) * | 2012-04-02 | 2014-03-05 | 锦州新世纪多晶硅材料有限公司 | Method for decreasing content of boron impurity in silicon metal through metallurgical process |
| CN105063749B (en) * | 2015-06-08 | 2017-07-18 | 朱超 | A kind of method for preparing high-purity polycrystalline silicon |
| 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 |
| CN107043955A (en) * | 2017-01-09 | 2017-08-15 | 常州天合光能有限公司 | A kind of method of active gases assisting growth crystalline silicon |
| CN108914203B (en) * | 2018-07-18 | 2020-02-07 | 成都斯力康科技股份有限公司 | Deep impurity removal method for refining metallic silicon |
| WO2020192913A1 (en) * | 2019-03-27 | 2020-10-01 | Wacker Chemie Ag | Method for producing technical silicon |
| US20220212937A1 (en) * | 2019-04-30 | 2022-07-07 | Wacker Chemie Ag | Method for refining crude silicon melts using a particulate mediator |
| CN111747415B (en) * | 2020-07-13 | 2022-08-23 | 昆明理工大学 | Method for removing impurity iron in industrial silicon |
| CN115196656B (en) * | 2022-08-26 | 2023-09-19 | 华中科技大学鄂州工业技术研究院 | CsBr purifying method |
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